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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

Sankt Lorenzen 36, 8715, Sankt Lorenzen, Austria

Mechanics, Materials Science & Engineering Journal

May 2017

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

Mechanics, Materials Sciences & Engineering Journal, Austria, Sankt Lorenzen, 2017

Mechanics, Materials Science & Engineering Journal (MMSE Journal) is journal that deals in peer-
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peer-review procedure. Published by industrial company Magnolithe GmbH

Editor-in-Chief Mr. Peter Zisser

Dr. Zheng Li, University of Bridgeport, USA

Prof. Kravets Victor, Ukraine

Ph.D., Shuming Chen, College of Automotive Engineering, China

Dr. Yang Yu, University of Technology Sydney, Australia

Prof. Amelia Carolina Sparavigna, Politecnico di Torino, Italy

ISSN 2412-5954 Design and layout: Mechanics, Materials Science &


Engineering Journal (Magnolithe GmbH)
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2017, Magnolithe GmbH

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

CONTENT
I. Materials Science MMSE Journal Vol. 10 ................................................................................... 5
The Comparison of Micro Mechanics Analyses to Some Empirical Properties of Ukam
(Cochlospermum Planconii) Fibre Reinforced Polyester Composite. Ogbodo N. Joy,
Ihom .P. Aondona, Dennis O. Onah ................................................................................................. 7
Multi-Response Optimization and Regression Analysis of Process Parameters for Wire-
EDMed HCHCr Steel Using Taguchis Technique. K. Srujay Varma, M Jagadeeswara Rao, Shaik
Riyaaz Uddien ................................................................................................................................... 17
Reflection Enhancement Using TiO2/SiO2 Bilayer Films Prepared by Cost-Effective Sol-gel
Method. R. Ajay Kumar, R. S. Dubey, V. Ganesan .......................................................................... 28
Green Biosynthesis of Silver Nanoparticles using Aqueous Urginea Indica Bulbs Extract and
Their Catalytic Activity Towards 4-NP. R. Manigandan, S. Praveen Kumar, S. Munusamy, T.
Dhanasekaran, A. Padmanaban, K. Giribabu, R. Suresh, V. Narayanan ......................................... 32
Synthesis, Morphological Characterization and Photocatalytic Property of Silver
Molybdate. S. Muthamizh, S. Munusamy, S. Praveen Kumar, V. Narayanan ................................. 38
Electrocatalytic and Photocatalytic Application of Carbon Nitride Ag Hybrid
Nanocomposite. S. Munusamy, R. Suresh, K. Giribabu, R. Manigandan, S. Preenkumar, S.
Muthamizh, T. Dhanasekaran, A. Padmanapan, G. Ganamoorthy, A. Stephen, V. Narayanan ...... 43
Variation in Structural and Optical Properties of Al Doped ZnO Nanoparticles Synthesized
by Sol-gel Process. Vanaja Aravapalli, Seshu Kalakatla, G. K. S. Prakash Raaju,
Srinivasa Karumuri ........................................................................................................................... 51
Synthesis of SnS Nanoparticles by a Green Hydrothermal Route. L. Ansel Mely, P. Annie
Vinosha, M. Mary Jaculine, Rudhra Nivedita Nathan, S. Jerome Das ............................................ 57
Kinetics of Corrosion Rate of Carbon Steels in Different Acidic Media. Ashok Kumar ....... 63
Exploring the Properties of NiO Nanoparticles Prepared by Reflux Method. A. Dhayal Raj,
A. Albert Irudayaraj, A. Reenaarul Vani .......................................................................................... 68
Effect of Precursor Concentration of MgO Nanostructure by using Sol-Gel Method.
V.T. Srisuvetha, S.L. Rayar, G. Shanthi, A. Dhayal Raj, S. Karthikeyan ........................................ 73
Synthesis, Structural, Optical and Photocatalytic Studies of Nanostructured Cadmium
Doped ZnO Nanorods by Hydrothermal Method. P. Logamani, G. Poongodi, R. Rajeswari .... 78
Fabrication of Ni/Pd/Ni Multilayer by Pulsed Electrodeposition. T.A. Revathy, T. Sivaranjani,
K. Dhanapal, V. Narayanan, A. Stephen .......................................................................................... 83
Polymer Composites for Thermal Sensing Application. Isha Pandey, D. Arthisree, A.
Sivakumar, Girish M. Joshi ............................................................................................................... 87
Resonance Frequency, Bandwidth and Quality factor of Varying Grades of Poly
(Tetrafluroethylene) Films. Shantanu Dixit, E. Dhanumalayan, J. Anandraj, Mayank Pandey,
Girish M. Joshi, N. Madhusudhana Rao, S. Kaleemulla, D.J. Shirale, M. Teresa Cuberes ............. 91
Optical Absorption Spectral Investigation of Dy2O3 Doped Zinc Strontium Bismuth Borate
Glasses. D. Kothandan, K. Chandra Babu Naidu, R. Jeevan Kumar ............................................... 95
An Assessment of Mechanical and Tribological Property of Hybrid Aluminium Metal
Matrix Composite. R. Santosh Kumar, R. Nishanth, V. Seenivasan, S. Sarath Sanmugam, S. Johny
James ............................................................................................................................................... 100
Dielectric Loss Behavior of SrxZn1-xMnTiO5 (x = 0.1 to 0.9) Ceramics. M. Maddaiah, T. Sofi
Sarmash, T. Vidya Sagar, T. Subbarao ........................................................................................... 106

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

Effects of Manganese (Ii) Sulphate on Structural, Spectral, Optical, Thermal and


Mechanical Properties of L-Alanine Sodium Sulphate Single Crystals. F. Praveena,
S.L. Rayar ........................................................................................................................................ 110
Structural, Spectroscopic and Thermal Studies of Potassium Di-Hydrogen Citrate Crystal.
N.D. Pandya, J.H. Joshi, H.O. Jethva, M.J. Joshi .......................................................................... 116
Synthesis of Nd3+ Doped TiO2 Nanoparticles and Its Optical Behaviour. Ezhil Arasi S., Victor
Antony Raj M., Madhavan J. ........................................................................................................... 122
Electrochemical Determination of 4-Nitrophenol by Manganese (II) Schiff Base Complex
Modified GCE. S. Praveen Kumar, S. Munusamy, S. Muthamizh, A. Padmanaban, T. Dhanasekaran,
G. Gnanamoorthy, V. Narayanan ................................................................................................... 125
Synthesis of Vanadium (III) Schiff Base Complex and its Electrocatalytic Sensing
Application. P. Supriya Prasad, Praveen Kumar, K. Bharathi, V. Narayanan ............................ 130
II. Mechanical Engineering & Physics MMSE Journal Vol. 10 ............................................... 135
Negative Impacts on Railway Embankments Exposed to Wind-Blown Sand and Optimizing
the Economic Height. Ahmed Abdelmoamen Khalil ...................................................................... 136
The Topology and Weight optimization of a truss using Imperialist Competitive Algorithm
(ICA). Arash Mohammadzadeh Gonabadi, Mohsen Mohebbi, Ali Sohan Ajini ............................ 149
Topology and Weight Optimization of a 3D Truss by Numerical Method. Arash
Mohammadzadeh Gonabadi, Mohsen Mohebbi, Ali Sohan Ajini ................................................... 162
Some Aspects of Model Equations Development for Viscous Materials. Irina Viktorova, Sofya
Alekseeva, Muhammed Kose ........................................................................................................... 179
A Study on the COP of CO2 Air Conditioning System with Minichannel Evaporator Using
Subcooling Process. Thanhtrung Dang, Chihiep Le, Tronghieu Nguyen, Minhhung Doan ......... 191
VII. Environmental Safety MMSE Journal Vol. 10 ................................................................... 203
Dark-Black Stains on Rooftops: Implications on the Quality of Water Harvested from
Rooftops in Uyo Metropolis-Nigeria. Ihom A.P., Uko D.K., Markson I.E., Eleghasim O.C. ...... 204
Study of the Efficiency of Dust Filters in Terms of Coal Mines. S.. Cheberiachko,
Yu.. Cheberiachko, .A. Yavorska, D.. Radchuk ........................................................................ 218
IX. Philosophy of Research and Education MMSE Journal Vol. 10 ....................................... 229
Model of Professionally Important Qualities of Bachelor Degree Students of Higher
Technical Educational Institution for the Admission to Masters Course. O. Artemenko,
D. Artemenko, N. Cherednychenko ................................................................................................. 230
The Zenith Passage of the Sun and the Architectures of the Tropical Zone. Amelia Carolina
Sparavigna ...................................................................................................................................... 239

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

I . M a t e r i a l s S c i e n c e
M M S E J o u r n a l V o l . 1 0

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

The Comparison of Micro Mechanics Analyses to Some Empirical Properties of


Ukam (Cochlospermum Planconii) Fibre Reinforced Polyester Composite 1

Ogbodo N. Joy1, Ihom .P. Aondona2, a, Dennis O. Onah2

1 Scientific Equipment Development Institute (SEDI) Enugu, Enugu State, Nigeria


2 Department of Mechanical and Aerospace Engineering, University of Uyo, Uyo, PMB 1017 Uyo, Akwa Ibom State,
Nigeria
a Ihomaondona@uniuyo.edu.ng, ihomaondona@gmail.com

DOI 10.2412/mmse.22.16.844 provided by Seo4U.link

Keywords: law of mixtures, proportions, polyester, Ukam fibre, micromechanics analyses, composites, properties,
reinforcement.

ABSTRACT. The comparison of micro mechanics analyses to some empirical properties of cochlospermum planchonii
(ukam) fibre reinforced polyester composite has been undertaken. The study developed the composites, which were
characterized, and empirical values were generated. The polyester and the ukam fibre, which were used in the manufacture
of the composites via weight fractions were also characterized. The properties of the polyester and ukam fibre were then
used in the micro mechanics analyses of the developed composites. The study revealed that reinforcement-matrix
proportion played a major role in composite property determination. This was observed from both the empirical properties
measured and the micro mechanics analyses. It was also observed that micro mechanics analyses did not agree with
empirical properties in all cases; this the study revealed that it was because of the complex nature of the interactions
between parameters responsible for properties in composites. The study has indicated that where micro mechanics
analyses agree with empirical property of the composite the law of mixtures can be used to predict the property of the
composite.

Introduction. According to [11] the fabrication and properties of composites are strongly influenced
by the proportions and properties of the matrix and the reinforcement. The proportions can be
expressed either via the weight fraction (), which is relevant to fabrication, or via the volume
fraction (), which is commonly used in property calculation. The definitions of and are related
simply to the ratios of weight (W) or volume (V) as shown below.
Volume fractions:

= / and = / (1, a)

Weight fractions:

wf = Wf / Wc and wm = Wm / Wc (1, b)

where the subscripts m, f and c refer to the matrix fibre (or in the more general case, reinforcement)
and composite respectively.

1
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http://creativecommons.org/licenses/by-nc-nd/4.0/

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

We note that,

vf + vm = 1 and + = 1

We can relate weight to volume fractions by introducing the density, , of the composite and its
constituents.

Wc = Wf + Wm , which as W = V, becomes

cVc = fVf + mVm c= fVf + mVm (2)

It may also be shown that,

1
= + (3)

And similarly,


= W = = (4)

We can see that it is possible to convert from weight fraction to volume fraction, and vice versa,
provided that the densities of the reinforcement (f) and the matrix (m) are known. Equation 2, shows
that, the density of the composite is given by the volume fraction adjusted sum of the densities of the
constituents. This equation is not only applicable to density, but in certain circumstances, may apply
to other properties of constituents. A generalized form of the equation is

Xc = XmVm + XfVf (5)

where Xc represents an appropriate property of the composite;


V is the volume fraction and the subscripts m and f refer to the matrix and reinforcement
respectively.
This equation is known as the Law of Mixtures [11].
The properties of composites are very important since they determine their areas of application. Most
properties of a composite are a complex fraction of a number of properties as the constituents usually
interact in a synergistic way so as to provide properties in the composite that are not fully accounted
for by the law of mixtures [[1], [2], [3], [7], [11]]. The chemical and strength characteristics of the
interface between the fibres and the matrix, is particularly important in determining the properties of
the composite. The interfacial bond strength has to be sufficient for load to be transferred from the
matrix to the fibre, if the composite is to be stronger than the unreinforced matrix. On the other hand,
if we are concerned with the toughness of the composite, the interface must not be so strong that it

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

does not fail and allow toughening mechanisms such as debonding and fibre pull-out to take place
[[6], [7], [8], [9], [10], [12].
Other parameters which may significantly affect the properties of a composite are the shape, size,
orientation and distribution of the reinforcement and various features of the matrix such as the grain
size for polycrystalline matrices. These, together with volume fraction, constitute what is called the
microstructure of the composite [[11], [13], [14], [15], [16], [17].
The use of the law of mixtures in studying the properties of composites has its basis in what is called
micromechanics analyses. Because. the starting point of a significant proportion of composites
manufacture is the combination of fibres and matrix, it would be very helpful if we could predict the
behavior of the composite from knowledge of the properties of the constituents alone. There are
however, many limitations to such micromechanics analyses [[11], [19], [20]]. However, studying
performance on a micro scale is essential if we are to understand fully what controls the strength,
toughness, etc. of composites. The impact strength of fibre reinforced composite increases as the bre
volume fraction increases [21]. The strength also improves with increase in bre volume fractions,
bre treatment, bre length, bre orientation and the addition of additives. Rasheed et al [18] found
that the tensile strength of the composite increases with the fibre volume fraction up to 40% and after
which it decreases slightly
The objective of this research is to apply the law of mixtures in the micromechanics analyses of some
properties of polyester composite reinforced with cochlospermum planchonii fibre.
Materials and Method
Materials
The materials used for this work were: polyester resin, ukam fibre (cochlospermum planchonii fibres),
sodium hydroxide, acetic acid, releasing agent, methyl ethyl ketone peroxide, calcium carbonate,
cobalt naphthenate and water.
Equipment
The equipment used for the study were as follows: rule, digital weighing balace, Moulds, Tensile
Strength Tester, Scanning Electron Microscope, Universal Testing Machine, Flexural Testing
Machine, Compression Testing Machine, Rockwell B scale, and Impact Testing Machine
Method
The work commenced with the production of the composite using polyester as the matrix and
cochlospermum planchonii as the fibres. Cut stems of the plants were soaked inside flowing water
for thirty days. This enhanced the decay and removal of the thin back of the plant leaving behind,
white fibrous stems (see Fig. 1). The fibres were removed from the fibrous stems with hands (see
Fig. 2). The density, tensile strength, SEM analysis, and water absorption characteristics of the
produced fibres were all determined. The produced fibres were then used in the development of
polyester composite using various weight fractions of the fibre, which were randomly oriented in the
matrix (see Table 1). The produced composites were allowed to cure for 24 hours before the
commencement of their processing into standard test specimens which were used for characterization
of the produced composites. Figs. 3-6 show some equipment, the developed composites, and some
specimens which were used for the characterization of the produced composites.

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

Fig. 1. Cut stems of cochlospermum planchonii fibres.

Fig. 2. Treated and dried cochlospermum planchonii fibres.

Fig. 3. Scanning electron microscope.

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

Fig. 4. Developed samples of cochlospermum planchonii reinforced polyester composites.

Fig. 5. Test Specimens of cochlospermum planconii reinforced composite for tensile test.

Fig. 6. Universal strength testing machine (Testometric).

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

Results and Discussion


Results. The results of the research are as presented in Tables 1-4. The micromechanics analyses
was accomplished using equation 5.
The initial conditions:
Density of fibres = 1.6 g/cm3
Tensile strength of fibre = 1803.11 MPa
Water absorption of fibre= 0.83%
Extension: 0.46mm
Polyester properties:
Density = 1.45 g/cm3
Tensile strength = 15.59 MPa
Water absorption = 0.38%
Elongation = 2%

Table 1. Weight and Weight Fractions of Cochlospermum Planchonii fibre and Polyester.
Wt. of wt. of matrix wt. fraction of wt. fraction of matrix ( )
Reinforcement ( ) ( ) reinforcement ( )

20 80 0.20 0.80
30 70 0.30 0.70
40 60 0.40 0.60
60 40 0.60 0.40

Table 2. Density values of the Developed Composites with the Micromechanics Analyses values.
S/no. % Reinforcement Density (Empirical Density (Micromechanics
values) g/cm3 analyses) g/cm3
1 0 1.45 1.45
2 20 1.55 1.48
3 30 1.60 1.50
4 40 1.90 1.51
5 60 1.83 1.54

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

Table 3. Water absorption Capacity of the developed composites with the Micromechanics Analyses
values.
S/no. % Reinforcement Water absorption capacity Water absorption capacity
(Empirical values) % (Micromechanics analyses values)
%
1 0 0.31 0.31
2 20 0.31 0.46
3 30 0.38 0.49
4 40 0.38 0.52
5 60 0.53 0.57

Table 4. Tensile strength values of the Developed Composites with the Micromechanics Analyses
values.
S/no. % Reinforcement Tensile strength (Empirical Tensile strength
values) MPa (Micromechanics analyses
values) MPa
1 0 15.59 15.59
2 20 27.14 373.094
3 30 41.67 551.846
4 40 49.40 730.598
5 50 - 909.35
6 60 46.13 1088.102
7 70 - 1266.854

Table 5. Extension values of the Developed Composites with the Micromechanics Analyses values
Extension.
S/No. % Reinforcement Extension (Empirical values), Extension (Micromechanics
mm analyses values), mm
1 0 3.07 3.07
2 20 4.70 2.548
3 30 5.63 2.287
4 40 6.90 2.026
5 50 - 1.765
6 60 6.50 1.504
7 70 - 1.243

Discussion. Table 2 shows the densities of the developed composites with the micromechanics values
of the densities of the composites. The micromechanics analyses show that as the fibre reinforcement
is increasing, the density property of the composite is also increasing. The same trend can be observed

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

in the empirical values; however, the empirical values are higher than the micromechanics values,
reasons have been advanced earlier in the introducing part of this paper. Another reason is that, the
law of mixtures accuracy also depends on the correct measurement of the property of the matrix and
the reinforcement [[1], [2], [3], [7], [11]].
Table 3 shows the water absorption capacity values of the developed composites with the
micromechanics values of the water absorption capacity of the composites. The micromechanics
analyses show that the water absorption capacity increases with increase in fibre reinforcement in the
composite. This trend can also be seen with the empirical values of water absorption capacity. The
water absorption capacity values of the micromechanics analyses are however, higher than those of
the empirical values. Again, it should be noted that the closeness or accuracy of the micromechanics
values to empirical values depend on the correct measurement of the values of the matrix and the
fibre in addition to other factors [[6], [7], [8], [9], [10], [12]].
Table 4 shows the tensile strength values of the developed composites with the micromechanics
Analyses values. The micromechanics analyses show that as the fibre reinforcement is increasing the
tensile property of the composites is also increasing. The same trend is observed with the empirical
values. The empirical values are however, higher than the micromechanics values. This is not
surprising because the matrix tensile strength of 15.59 MPa is quite lower than the 45 85 MPa range
obtained from most polyesters. The micromechanics analyses values are more realistic since they are
closer to strength values commonly found in polyester fibre reinforced composites (140 MPa and
above) [[11], [13], [14], [15], [17]].
Table 5 shows the extension values of the developed composites with the micromechanics analyses
values of the extension of the composites. The micromechanics analyses show that as fibre
reinforcement is increasing, the extension property of the developed composites is decreasing.
This does not agree with the empirical values trend, which show that as the reinforcement is
increasing, the extension property of the composites is also increasing. It has earlier been mentioned
in the introductory part of this paper, that most properties of a composite are a complex function of a
number of parameters as the constituents usually interact in a synergistic way so as to provide
properties in the composite that are not fully accounted for by the law of mixtures [[11], [19], [20]].
Tables 4 and 5 have shown that it is possible to use micro mechanics analysis to predict the properties
of composites. This can also be seen in previous work of Matthews and Rawlings [11]. Previous
researchers [[11], [13], [14], [15], [16], [17]] have shown that the fabrication and properties of
composites are strongly influenced by the proportions and properties of the matrix and the
reinforcement. Several authors are also of the opinion that studying performance on a micro scale is
essential if we are to understand fully what controls the strength, toughness, etc. of composites [[6],
[7], [8], [9], [10], [12]]. There are however many limitations to such micro mechanics analysis.
Because the starting point of a significant proportion of composites manufacture is a combination of
fibres and matrix, it would be very helpful if we could predict the behaviour of the composite from
knowledge of the properties of the constituents alone [[11], [18], [21]].
Summary. The research work titled The Comparison of Micro Mechanics analyses to some
empirical properties of polyester based composition reinforced with cochlosoermum planchonii
fibre was extensively undertaken and the following conclusions were drawn from the work:
1. Most properties of composites are a complex function of a number of parameters as the constituents
usually interact in a synergistic way so as to provide projections in the composite that are not fully
accounted for by the law of mixtures.
2. Provided the property of the matrix and the fibre has been measured correctly, micromechanics
analyses can be used to predict some properties of the composite.
3. The study has shown that micromechanics analyses of the properties of polyester based / composite
reinforced with cochlospermum planchonii (ukam) fibre does agree with the trend of empirical

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

properties for density water absorption capacity and tensile strength, but disagree with extension
property.
4. Both the empirical results and micromechanics analyses have shown that proportions of the matrix
and reinforcements expressed in weight fractions or volume fractions is a major determinant of
cochlospermum planchonii reinforced polyester composite properties.
Acknowledgement
The authors of this work are sincerely indebted to the technologists in the Materials Testing
Laboratory of NMDC and other technologists in DICON, Kaduna, who assisted with the
characterization of the composite specimen and time will not allow in mentioning you by names.
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[22] Ihom A.P., Dennis O. Onah. (2016). The Effects of Ukam (Cochlospermum Planchonii) Plant
Fiber Variation on the Properties of Polyester Matrix Fiber Reinforced Composite. Mechanics,
Materials Science & Engineering Vol.6, doi: 10.13140/RG.2.2.35903.923202

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Multi-Response Optimization and Regression Analysis of Process Parameters


for Wire-EDMed HCHCr Steel Using Taguchis Technique2

K. Srujay Varma1, M Jagadeeswara Rao1 , Shaik Riyaaz Uddien1,a

1 Department of Mechanical Engineering, Osmania University, Hyderabad, Telangana, India


a dfmriyaaz@gmail.com

DOI 10.2412/mmse.59.23.582 provided by Seo4U.link

Keywords: wire EDM, HCHCr, copper, Taguchi, ANOVA, pulse-on, pulse-off, hardness.

ABSTRACT. In this study, effect of machining process parameters viz. pulse-on time, pulse-off time, current and servo-
voltage for machining High Carbon High Chromium Steel (HCHCr) using copper electrode in wire EDM was
investigated. High Carbon High Chromium Steel is a difficult to machine alloy, which has many applications in low
temperature manufacturing, and copper is chosen as electrode as it has good electrical conductivity and most frequently
used electrode all over the world. Tool making culture of copper has made many shops in Europe and Japan to used
copper electrode. Experiments were conducted according to Taguchis technique by varying the machining process
parameters at three levels. Taguchis method based on L9 orthogonal array was followed and number of experiments was
limited to 9. Experimental cost and time consumption was reduced by following this statistical technique. Targeted output
parameters are Material Removal Rate (MRR), Vickers Hardness (HV) and Surface Roughness (SR). Analysis of
Variance (ANOVA) and Regression Analysis was performed using Minitab 17 software to optimize the parameters and
draw relationship between input and output process parameters. Regression models were developed relating input and
output parameters. It was observed that most influential factor for MRR, Hardness and SR are Ton, Toff and SV.

Introduction. High Carbon High Chromium (HCHCr) steel is a type of tool steel which comes under
one of the three series of cold work group. As the name of the group indicates, these steels are used
for cutting or forming materials at low temperatures. Comparatively more alloying elements are used
in this type of steels and surface hardness is also high. This has applications in thread rolling dies,
punches, dies, reamers, finishing rolls for tire mills etc., This material has low machinability
comparing to other steels and so this material was chosen in this study to machine using wire EDM
[1-3].
Wire Electrical Discharge Machining (wEDM) is one of the indispensable machining techniques for
making complicated shapes on difficult to machine metals with low residual stresses and good surface
finish [4]. This is particularly used for die materials which require high strength and hardness as well
as good wear resistance. It does not require any special tool or technique and the process time is also
less comparing to conventional manufacturing process. A conductive wire acts as an electrode and
material is eroded from the work piece by series of discrete sparks between the work piece and wire
electrode separated by a thin film of dielectric fluid. Dielectric fluid flashes away the eroded material
and it also acts as coolant [5]. Because of its less cutting forces, its application has been extended to
machine metal foams used in heat exchangers and slicing silicon wafers used in solar cells and
microelectronic components [6-9]. In this study, HCHCr was machined using wire EDM to study the
process parameters for this material.
An important aspect while machining using wire EDM is the selection of electrode material. There
are various conductive materials that can be used as electrodes but the more frequently used electrode
material copper is used in this study. Copper became the metallic electrode material of choice with

2
2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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development of the transistorized and pulse-type power supplies. Shops in Europe and Japan prefer
to use copper as electrode material due to its tool making culture [10].
The Taguchi method, a statistical and efficient technique for product design and optimization was
used to achieve the off-line quality control [11-12]. As the most reliable step in the Taguchi approach,
the parameter design emphasizes on obtaining the optimum combination of parameters to improve a
quality characteristic with low variability [13-14]. Taguchi method was developed on orthogonal
array (OA) concept and experiments were also designed using the same concept. Using Design of
Experiments (DOE) in Minitab software, an L9 standard Orthogonal Array was adopted in this study.
In comparison with full factorial design method, Orthogonal Array is efficient and cost saving due to
small number of experimental runs. Further regression analysis was conducted and regression
equations were developed for the parameters.
Experimental Method.
The workpiece material, electrode wire and machine used to carry out the experiments are described
below. Design factors and response variable as well as methodology implemented for the
experimentation is also outlined.
Material and Equipment used.
The wire EDM used to carry out the experiments was CNC Sprint Cut 734 (Electranica Sprint Cut
734) from Electrionica Ltd., Pune (Fig 1). Dielectric fluid used in this machine is de-ionized water
and copper wire of diameter 0.25 mm is taken as electrode material. HCHCr steel substrates of
dimension 100 x 50 x 10 mm were considered for machining. Vickers Hardness Tester with diamond
indenter and Surface-SJ 301 surface roughness tester made by Mitutoyo Company were used.

Fig. 1. Wire cut CNC.

Experimental Design.
Taguchi method based on orthogonal array was used to design experiments in this study. The process
parameters were selected depending upon machine, cutting tool and work piece capability. The input
process parameters taken in this experiment are pulse-on time (Ton), pulse-off time (Ton), current (Ip)
and servo voltage (SV) as shown in Table 1.

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Table 1. Input process parameters of Wired EDM.


S.NO. PROCESS PARAMETERS LEVEL 1 LEVEL 2 LEVEL 3
1 PULSE TIME ON (TON) 100 105 110
2 PULSE TIME OFF (TOFF) 55 59 63
3 PEAK CURRENT (IP) 10 11 12
4 SERVO VOLTAGE (SV) 10 55 90

Experimental Procedure:
The number of experiments was limited to 9 according to L9 orthogonal array using Taguchis
statistical technique. The experiments were carried out by varying process parameters at three levels.
After conducting experiments, the substrates were taken out, dried and measured for Material
Removal Rate (mm3/min), Hardness (HV) and Surface Roughness (m) were measured. Material
Removal Rate (MRR) was calculated using the formula in equation (1).

VR
MRR (1)
TM

where VR volume of material removed after machining;


TM machining time.
The surface roughness tester is used to measure the roughness on the work piece after machining.
This observation helped in finding how the experiment conditions are affecting the surface roughness.
Then hardness of the surface was tested using micro hardness tester having Vickers diamond indenter
and indenter is pressed into the materials surface with a penetrator and a weight of 1000 gms. The
result of applying the load with a penetrator is an indent or permanent deformation of material surface
caused by the shape of the indentor. The values obtained for MRR, Surface Roughness and Hardness
are shown in Table 2.

Table 2. Experimental readings.


Actual Coded Surface
MRR Hardness
values values roughness
Exp
Ton Toff Ip SV Ton Toff Ip SV (mm3/min) HV m
no
1 100 55 10 10 -1 -1 -1 -1 0.0658 33 2.695
2 100 59 11 55 -1 0 0 0 0.1976 34 3.497
3 100 63 12 90 -1 1 1 1 0.2045 32 3.855
4 105 55 11 90 0 -1 0 1 0.2272 34 3.8
5 105 59 12 10 0 0 1 -1 0.0946 33 2.8
6 105 63 10 55 0 1 -1 0 0.3073 34 3.32
7 110 55 12 55 1 -1 1 0 0.3246 34 3.45
8 110 59 10 90 1 0 -1 1 0.3719 34 3.82
9 110 63 11 10 1 1 0 -1 0.1515 29 3.82

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Process optimization.
Process optimization was done by optimizing parameters using MINITAB 17 software. This software
optimizes both static and dynamic responses provided but the quality characteristic of static response
is limited. This software optimizes by calculating signal to noise ratio which is one of the important
parameter in Taguchi Method. The three important concepts under Signal to Noise ratio are Larger-
The-Best, Smaller-The-Best and Nominal-The-Best. Among them, Larger the better is taken for MRR
and Hardness whereas Smaller the better is taken for Surface Roughness. S/N ratios of MRR,
Hardness and surface roughness are calculated using formulae in eqs. (2) and (3) using Minitab 17
software are tabulated in table 3.
(a) Larger-the-Better

n = -10 Log10 [mean of sum squares of reciprocal of measured data] (2)

(b) Smaller-the-Better

n = -10 Log10 [mean of sum of squares of measured data] (3)

The S/N ratios obtained by MINITAB 17 software for MRR, Surface Roughness and Hardness are
shown in table 3.

Table 3. MRR, Hardness and Surface Roughness for S/N Ratio.


Coded Surface
values MRR Hardness roughness
Exp
no Ton Toff Ip SV (mm3/min) S/N HV S/N m S /N
1 -1 -1 -1 -1 0.0658 -23.6355 33 30.3703 2.695 -8.61118
2 -1 0 0 0 0.1976 -14.0843 34 30.6296 3.497 -10.8739
3 -1 1 1 1 0.2045 -13.7861 32 30.103 3.855 -11.7205
4 0 -1 0 1 0.2272 -12.8718 34 30.6296 3.8 -11.5957
5 0 0 1 -1 0.0946 -20.4822 33 30.3703 2.8 -8.94316
6 0 1 -1 0 0.3073 -10.2487 34 30.6296 3.32 -10.4228
7 1 -1 1 0 0.3246 -9.77303 34 30.6296 3.45 -10.7564
8 1 0 -1 1 0.3719 -8.59148 34 30.6296 3.82 -11.6413
9 1 1 0 -1 0.1515 -16.3917 29 29.248 3.82 -11.6413

S/N Ratio response for MRR, Hardness and Surface Roughness are shown in Table 4, 5 and 6.

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Table 4. S/N Ratio Response for MRR.


Level Ton Toff Ip SV
1 -17.17 -15.43 -14.16 -20.17
2 -14.53 -14.39 -14.45 -11.37
3 -11.59 -13.48 -14.68 -11.75
Delta 5.58 1.95 0.52 8.8
Rank 2 3 4 1

Table 5. S/N Ratio Response for Hardness.


Level Ton Toff Ip SV
1 30.37 30.54 30.54 30
2 30.54 30.54 30.17 30.63
3 30.17 29.99 30.37 30.45
Delta 0.37 0.55 0.37 0.63
Rank 3.5 2 3.5 1

Table 6. S/N Ratio Response for Surface Roughness.


Level Ton Toff Ip SV
1 -10.402 -10.321 -10.225 -9.732
2 -10.321 -10.486 -11.37 -10.684
3 -11.346 -11.262 -10.473 -11.652
Delta 1.026 0.94 1.145 1.921
Rank 3 4 2 1

Mean of S/N ratios versus input parameters viz. Ton, Toff, Ip and SV for MRR, Hardness and Surface
Roughness are shown in figs. 2, 3 and 4 respectively.

Fig. 2. S/N Plot for MRR.

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Fig. 3. S/N Plot for Hardness.

Fig. 4. S/N Plot for Surface Roughness.

ANOVA and Regression analysis.


The first and second order polynomial responses have been accomplished, consequently the analysis
of variance are shown in tables 7, 8 and 9. Because of its adequacy, second order regression has been
shown. Regression analysis was performed on the values of measured responses and the values of the
different regression coefficients of second order polynomial mathematical equation have been
estimated. The mathematical model has been developed by utilizing test results obtained through the
entire set of experiments by using Minitab 17 software using multi-linear regression analysis method.
The relation between EDM process parameters with a variety of machining criteria and output
response were drawn as shown in eqns (4), (5) and (6) and residual plots for MRR, Hardness and
Surface Roughness are shown in figs. 5, 6 and 7.

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Table 7. ANOVA for MRR.


Source DF Adj SS Adj MS F-Value P-Value
Regression 7 0.109763 0.01568 4.97 0.333
Ton 1 0.005727 0.005727 1.81 0.407
Toff 1 0.001163 0.001163 0.37 0.653
Ip 1 0.004505 0.004505 1.43 0.444
SV 1 0.004419 0.004419 1.4 0.447
Ton Toff 1 0.003123 0.003123 0.99 0.502
TonIp 1 0.000273 0.000273 0.09 0.818
ToffIp 1 0.002373 0.002373 0.75 0.545
Error 1 0.003158 0.003158 - -
Total 8 0.112921 - - -

Regression Equation:

MRR 0.5 (mm3/min) = 0.4512 + 0.0467 Ton + 0.0263 Toff - 0.0518 Ip+
+ 0.0718 SV- 0.0732 TonToff+ 0.0217 TonIp - 0.0451 ToffIp (4)

Fig. 5. Residual Plots for MRR.

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Table 8. ANOVA for Hardness


Source DF Adj SS Adj MS F-Value P-Value
Regression 7 0.173503 0.024786 38.31 0.124
Ton 1 0.029607 0.029607 45.76 0.093
Toff 1 0.057268 0.057268 88.51 0.067
Ip 1 0.021452 0.021452 33.15 0.109
SV 1 0.009562 0.009562 14.78 0.162
Ton Toff 1 0.016458 0.016458 25.44 0.125
TonIp 1 0.021376 0.021376 33.04 0.11
ToffIp 1 0.026474 0.026474 40.92 0.099
Error 1 0.000647 0.000647 - -
Total 8 0.17415 - - -

Regression Equation:

Hardness0.5 = 5.74288 - 0.1062 Ton - 0.1846 Toff - 0.1130 Ip - 0.1056 SV -- 0.1680 TonToff -
0.1914 TonIp - 0.1506 ToffIp (5)

Fig. 6. Residual Plots for Hardness.

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Table 9. ANOVA for Surface Roughness.


F- P-
Source DF Adj SS Adj MS Value Value
Regression 7 0.11053 0.01579 1.62 0.542
Ton 1 0.00777 0.00777 0.8 0.536
Toff 1 0.01928 0.01928 1.98 0.394
Ip 1 0.01427 0.01427 1.46 0.44
SV 1 0.04841 0.04841 4.96 0.269
Ton Toff 1 0.01475 0.01475 1.51 0.435
TonIp 1 0.00799 0.00799 0.82 0.532
ToffIp 1 0.00016 0.00016 0.02 0.919
Error 1 0.00976 0.00976 - -
Total 8 0.12029 - - -

Regression Equation:

Surface roughness0.5 = 1.8540 + 0.0544 Ton + 0.1071 Toff + 0.0921 Ip + 0.238 SV


+ 0.159 TonToff + 0.117 TonIp + 0.0117 ToffIp (6)

Fig. 7. Residual Plots for Surface Roughness.

Results and Discussions


Observations on MRR.

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From S/N ratios graph in fig. 2, it is observed that MRR is linearly varying with Ton, Toff and Ip whereas
non-linearly varying with SV. Ton has 30.19 % contribution to MRR. ANOVA (Table 7) and
Regression equation (eq. 4) shows the significance of process parameters. Higher MRR
(0.3719 mm3/min) was obtained at Ton (110 s), Toff (59 s), Ip (10 amps) and SV (90 V). Adequacy
of the regression model developed can be checked using values of S and R2. R2 value measures the
amount of reduction in the variability of response obtained by using the variability of response
obtained by using regression variables in the model [15]. R2 of 97.00% and S of 0.056 indicates that
it has good fit. More influencing factor from the regression model can be found by F value. Larger F
value obtained at Ton (1.81).
Observations on Hardness.
Fig. 3 shows the S/N ratios obtained by MINITAB 17 software from the set of Hardness values. It is
observed that Hardness does not linearly vary with any parameters. Toff has 37 % contribution to
Hardness. Higher Hardness (34 HV) was obtained at same input parameters where higher MRR was
obtained. Regression equation relating hardness with input parameters are shown in eq. (5) and values
obtained by R2 and S are 99.63% and 0.0254 respectively. This model also has good fit. Higher F
value was obtained at Toff (88.51).
Observations on Surface Roughness.
S/N ratio plots calculated using set of surface roughness values are shown in fig. 4. It is observed that
servo-voltage (SV) is varying linearly with surface roughness where other three input parameters Ton,
Toff and Current Ip are non-linearly varying. SV (48.66 %) has higher contribution to Surface
Roughness. Less surface roughness (2.695 m) was obtained at Ton (100 s), Toff (55 s), Ip (10 amps)
and SV (10V). R2 and S values are 91.89% and 0.098 respectively which indicates that model
developed (eq. 6) has good fit. SV has higher F value of 4.96.
Summary. Higher MRR (0.3719 mm3/min) and Hardness (34 HV) was achieved at Ton (110 s), Toff
(59 s), Ip (10 amps) and SV (90 V). Lower Surface Roughness (2.695 m) was obtained at Ton (100
s), Toff (55 s), Ip (10 amps) and SV (10V). Most influencing factor for MRR, Hardness and Surface
Roughness are Ton, Toff and SV. Relation between input and output parameters was drawn using
regression model developed by MINITAB 17 software.
Acknowledgement. All authors contributed equally.
References
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of Process Parameters in Wire EDM of HCHCr Material Using Taguchis Technique, Mater. Today
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[6] A. M. Matz, D. Kammerer, N. Jost, and K. Owald, Machining of Metal Foams with Varying
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[7] F. Klocke, L. Hensgen, A. Klink, L. Ehle, and A. Schwedt, Structure and Composition of the
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[8] Y. Zhu, T. Liang, L. Gu, and W. Zhao, Machining of Micro Rotational Parts with Wire EDM
Machine, Procedia Manuf., vol. XXX, pp. 18, 2016.
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[9] K. Zakaria, Z. Ismail, N. Redzuan, and K. W. Dalgarno, Effect of Wire EDM Cutting Parameters
for Evaluating of Additive Manufacturing Hybrid Metal Material, Procedia Manuf., vol. 2, no.
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[10] A. Torres, C. J. Luis, and I. Puertas, EDM machinability and surface roughness analysis of TiB2
using copper electrodes, J. Alloys Compd., vol. 690, pp. 337347, 2017.
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Reflection Enhancement Using TiO2/SiO2 Bilayer Films Prepared by Cost-


Effective Sol-gel Method3

R. Ajay Kumar1, R. S. Dubey1, a , V. Ganesan2

1 Advanced Research Laboratory for Nanomaterials and Devices, Department of Nanotechnology, Swarnandhra
College of Engineering and Technology, Seetharampuram, Narsapur (A.P.), India
2 UGC-DAE Consortium for Scientific Research, Indore, (M.P.), India
a rag_pcw@yahoo.co.in

DOI 10.2412/mmse.84.67.762 provided by Seo4U.link

Keywords: TiO2, SiO2, TiO2/ SiO2, thin films, sol-gel spin coating method, refractive index, reflection.

ABSTRACT. Multilayer dielectric thin film structure has been demanded for its application in optoelectronic devices
such as optical waveguides, vertical cavity surface-emitting devices, biosensors etc. In this paper, we present the
fabrication and characterization of bilayer thin films of TiO2/SiO2 using sol-gel spin coating method. Ellipsometer
measurement showed refractive index values 1.46, 2.1 corresponding to the SiO2 and TiO2 films respectively. The FTIR
transmittance peaks observed at ~970 cm-1, ~1100 cm-1 and ~1400 cm-1 are attributed to the Ti-O-Si, Si-O-Si and Ti-O-
Ti bonds respectively. Maximum reflectance is observed from two bilayer film structure which can be further optimized
to get the high reflection to a broad wavelength range.

Introduction. Presently, nanomaterials have been demanded due to their several applications in
electronics, optoelectronics, sensors and much more. A multilayer structure of dielectric films also
known as the one-dimensional photonic crystal is an essential passive component for the optical
applications. By tuning the refractive index and thickness of its dielectric layers, the desired band of
reflection can be obtained. One-dimensional photonic crystal is composed of distinct dielectric layers
of quarter-wavelength thickness which possesses a forbidden band of a specified wavelength within
that the propagation of light is completely prohibited. For the fabrication of such multilayer thin film
structures, various combination of dielectric materials has been investigated such as TiO2/SiO2,
SiN/SiO2, ZrO2/ZnO etc.
During the fabrication of multilayer film structure, the refractive index and thickness of the films can
be tuned to get the desired range of reflection/stop band. The fabrication of multilayer thin films has
been explored by using the Plasma Chemical Vapor Deposition, Sputtering, Molecular Beam Epitaxy,
Metal Organic Chemical Vapour Deposition, Hydrothermal Method, Sol-gel Spin Coating etc.
Among these methods, the sol-gel spin coating method is one of the easiest and cost effective method.
Several literature have been reported on the fabrication of TiO2/SiO2 bilayer films by using sol-gel
spin coating method. The sol-gel method is mainly involved two steps, hydrolysis and condensation
[1].
The quality of the film can be controlled by the solution aging, spin time and spin speed. In this paper,
we present the fabrication of TiO2/SiO2 bilayer film structure onto silicon and glass substrates by
using sol-gel spin coating method. With two bilayer film structure, a reflection band from 500-670
nm is observed. Section second describes the experimental details and results are discussed in Section
third. Finally, Section fourth summarizes the paper.

3
2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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Experimental Details. For the deposition of TiO2 and SiO2 films, Ethanol (AR 99.9%), Acetic acid
(Sd fine), Titanium butoxide (Fluka).and Tetraethyl orthosilicate (Aldrich) were used. The solutions
of TiO2 and SiO2 were prepared by the sol-gel method, as described here The solutions for TiO2 and
SiO2 were prepared by the using the precursors Titanium butoxide (TBOT) and Tetraethyl
orthosilicate (TEOS) respectively. Ethanol was used as the solvent and acetic acid (Sd Fine) as the
chelating agent. At first, required amounts of ethanol and acetic acid were stirred with the help of
magnetic stirrer up to 15 minutes in a beaker. The precursor was slowly added drop by drop to the
above solution under the vigorous stirring condition upto 1 hour in order to get the clear and
transparent solutions. With vigorous stirring of TiO2 solution, the light transparent yellow color was
observed while SiO2 solution was clear and transparent. Both the solutions were without precipitation
and further, solutions were kept for 24 hours aging to get enough viscous solution. Before deposition,
silicon substrates were cleaned separately in trichloroethylene, acetone and methanol by boiling upto
10 minutes and dried in nitrogen gas flow.
In a similar way, glass substrates were cleaned using soap solution and ultrasonicated with ethanol
and DI water to remove the surface impurities. For the deposition of TiO2 and SiO2 films, spin coating
technique was employed with 3000 RPM and 30 seconds spinning time. The annealing temperatures
were 300 0C and 500 0C for TiO2 & SiO2 films respectively. After preparation, samples were
characterized for transmittance and reflection using UV-1800 (Shimadzu). The thickness and
refractive index were measured using Ellipsometer (Phillips 1000) and FTIR transmittance spectrum
was recorded by using FTIR spectroscopy (Nicolet 380).
Results & Discussion. Using sol-gel spin coating method four samples were prepared and named
as A:SiO2 film,B:TiO2 film,C:1-bilayer(TiO2/SiO2) and D:2-bilayer.

Fig. 1. UV- Vis transmittance spectra of sample A, B, C and D prepared onto glass substrates.

Fig. 1 shows the transmittance spectra of sample A, B, C and D after annealing. As can be seen in the
figure, sample A shows the highest transmittance while low transmittance is observable for the sample
B. With comparison to the samples A and B, reduced transmittance is observed for the samples C
and D with the appearance of few small peaks. As the number of bilayers is increased the
transmittance is found to be decreased [2]. We have also prepared some samples onto the silicon
substrates to measure the refractive index and thickness of the TiO2 and SiO2 films using

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Ellipsometer. The measured refractive indices of TiO2 and SiO2 films were 2.1 and 1.46 with
thicknesses 161.2 and 361.9 respectively.

Fig. 2. FTIR transmittance spectra of sample C and D.

Fig. 2 depicts the FTIR spectra of samples C and D. The transmittance peak at ~945 cm -1 is
corresponding to the TiO2-O-SiO2 band. A strong transmission peak at ~1065 cm-1 can be observed
which is attributed to asymmetric vibration of Si-O-Si bonds.
A small peak at 1399 cm-1 is attributed to the Ti-O-Ti bonds while peak 1637 cm-1 is corresponding
to the alkoxide OH groups. A broad peak approximately from 3100 to 3500 cm-1 represents the OH
stretching vibrations of Si-OH [4], [5].

Fig. 3. UV-Vis reflectance spectra of sample C and D.

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Figure 3 shows the reflectance of samples C and D prepared onto glass substrates. The reflection
curve of sample C shows a small reflection band centered at 440 nm. However, an enhancement in
reflection with a shift in a higher wavelength is observed for the sample D. This enhancement in
reflection is due to the reflected light after striking onto the four layers of TiO2 and SiO2 respectively.
A shifting in the reflection band to a higher wavelength centered at 570 nm shows the tunability of
sample D. Accordingly, N-number of bilayers can give high reflectance within a specified wavelength
range with the optimization of the fabrication process parameters. In this way, a filter can be tailored
and fabricated for the use as a back reflector in solar cells in which unabsorbed light coming from the
thin active region can be folded back via reflections.
Summary. Single layer and bilayer films of TiO2/SiO2 have been prepared using Sol-gel spin coating
method and characterized for the study of their optical and structural properties. FTIR analysis
showed the desired peaks of Ti-O-Ti and Si-O-Si and found good in matching with others reported
works. It is found that as the number of bilayers is increased the reflectance is also increased. The
maximum reflectance was observed through 2-bilayer film structure.
By doing optimization of fabrication parameters, a specified forbidden/reflection/stop band can be
obtained which is demanded for its application in waveguides, vertical cavity surface emitting diodes
and solar cells.
Acknowledgment. The financial support provided by UGC-DAE CSR, Indore, INDIA is highly
acknowledged.
References
[1] S. J. Bull and A. M. Jones (1996), Multilayer coatings for improved performance, Surf. Coat.
Technol., 78, DOI:10.1016/0257-8972(94)02407-3.
[2] M. Nocu, S. Kwany, J. Zontek (2011), Optical properties of SiO2/TiO2 thin layers prepared by
solgel methodOptica Applicata, Vol. XLI, No. 4.
[3] K. Han, J. H. Kim, (2011), Reflectance modulation of transparent multilayer thin films for energy
efficient window applications, Material letters Vol. 65, 2466-2469,
DOI:10.1016/j.matlet.2011.05.006.
[4] X. Wang, G. Wu, B. Zhou and J. Shen, Thermal Annealing Effect on Optical Properties of Binary
TiO2-SiO2 Sol-Gel Coatings, Materials 2013, 6(1), 76-84; doi:10.3390/ma6010076.
[5] C. Huang, H. Bai, Y. Huang, S. Liu, S. Yen and Y. Tseng International Journal of Photoenergy,
Volume 2012 (2012), Article ID 620764, DOI: 10.1155/2012/620764

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Green Biosynthesis of Silver Nanoparticles using Aqueous Urginea Indica Bulbs


Extract and Their Catalytic Activity Towards 4-NP4

R. Manigandan1, S. Praveen kumar1, S. Munusamy1, T. Dhanasekaran1, A. Padmanaban1,


K. Giribabu1, R. Suresh2, V. Narayanan1,a

1 Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai, India


2 SRM University, Bharathi Salai, Ramapuram, Chennai, India
a vnnara@yahoo.co.in

DOI 10.2412/mmse.64.70.791 provided by Seo4U.link

Keywords: Urginea indica, Ag0 Nps, 4-nitrophenol, aqueous, catalysts, reduction.

ABSTRACT. A simple, green method is described for the synthesis of silver nanoparticles by reaction of the aqueous
solution of Urginea indica (U. I.) bulbs extract and AgNO3. In this process, colloidal metallic silver nanoparticles (Ag0
Nps) were of a particular interest due to its haunting physicochemical properties. The formation of Ag 0 Nps nanoparticles
was proved by the significant color change during the preparation. The formation process and color variations by the
impact of pH and concentration of extract were analyzed by UV-VIS spectrophotometer. Functional groups present in the
extract and Ag0 NPs was characterized by FT-IR spectroscopy. The crystal structure, lattice parameter and crystallite size
of synthesized silver NPs was confirmed by X-ray diffraction technique. The X-ray diffraction analysis of the sample
showed the formation of nanoparticles with cubic silver structure. Elemental composition and morphology of the metallic
silver was widely investigated by FESEM-EDX.

Introduction. The unique physicochemical properties of nanomaterials are attractive for use in a
variety of technologies due to the factors such as conductivity, magnetic property and optical
sensitivity by the characteristics such as small size, shape, surface structure, chemical composition
[1]. Modifying the properties of nanoscale materials generally involves control over the
physicochemical features of the material. Noble metal nanostructures have concerned attention due
to their extensive applicability in various domains [2].
A wide number of synthetic protocols such as electro-spinning method, micro-chemical method,
chemical vapor deposition and hydrothermal method have been formulated for the preparation of Ag
nanoparticles [3]. However, the synthesis of silver nanoparticles by the conventional methods has
many limitations. Plants provide a better platform for nanoparticles synthesis as they are free from
toxic chemicals as well as provide natural capping agents [4]. In this work, silver nanoparticles were
synthesized using Urginea indica bulbs extract as both capping/reducing agents. This study
particularly deals with the synthesis of Ag0 nanoparticles, involving green chemical reduction of their
respective inorganic metal ions using water as a solvent. Urginea indica (Indian squill) is a commonly
available plant and an excellent source of biomolecules such as polyphenols, flavonoids, quercetin
and apigenin glycosides. It also contains trace metals as well as carbohydrates, protein and powerful
antioxidants. Main objective of this present study is to synthesize Ag0 nanoparticles using aqueous
Urginea indica extract as both capping/reducing agents and to reveal its excellent catalytic activity
toward 4-NP.
Experimental section

4
2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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Materials. 4-Nitrophenol, sodium borohydride and silver nitrate were of analytical grade and used
as obtained from SRL India. Bulbs of Urginea indica was collected from Tamilnadu, India.
Preparation of U.I. Extract and Preparation of Silver Nanoparticles. Extraction of dried and
powdered plant (4.5 kg) of U. indica was done by cold extraction. U. indica bulbs extract is prepared
by simple soaking of fine powdered material in the aqueous meduim and the homogenates are kept
for 2 h at room temperature with shaking. Plant materials were cold extracted with distilled water and
after that the fraction was evaporated to cum-like colloidal nature by roto-dryer at low temperature
(4050 C) and dried crude extracts were stored in refrigerator. The crude extract was diluted at the
further stage of preparation. Aliquots of an aqueous AgNO3 solution (103 M) are added to the reaction
vessels containing plant extracts (10 % v/v) and the resulting mixtures were allowed to stand for 24
h at room temperature. The reduction of the Ag+ ions by plant extract in the solutions was monitored
by sampling the aqueous component (3 mL) and measuring the UV/Vis spectrum of the solutions.
The pH of the solution was adjusted by NaOH. All samples were diluted three times with distilled
water.

Fig. 1. visible observation of silver nanoparticles biosynthesis: 1:ratio of U. I. extract and 1 M


AgNO3 solution at different time interval [i) 0 min, ii) 30 min, iii) 1h, iv)1d (colour change).

Catalytic Reduction of 4-nitrophenol. Silver nanoparticles aqueous suspension (5mL, 0.25 g/L)
was added to NaBH4 aqueous solution (5 mL, 0.3 M) and the mixture was stirred for 10 min at room
temperature. 4-nitrophenol (5 mL, 0.003 M) was then added to the mixture, which was stirred until
the bright yellow gradually changed to colorless. The reaction progress was monitored by measuring
UV-vis absorption spectra. To study the catalyst durability, the catalyst was centrifuged after reaction
for 60 minutes and the clear supernatant liquid was decanted carefully.
Result and Discussions
UV-Vis Spectral analysis. In order to understand such reaction path and the surface Plasmon
resonance of Ag NPs was continuously monitored using UV-visible spectroscopy. Fig. 2 shows the
UVVis absorption spectra of 1 103 M silver nitrate solution in extract obtained from different
solvents a) Ethanol, b) Hexane, c) DMF and d) Ethyl acetate. Solvent also can reduce the silver ion
to metallic NPs and forms bigger sized particle [5]. Due to the large aggregate, the sample doesnt
produce any SPR peaks. To avoid this self-reduction of Ag0 during the course of preparation, we have
used water as the solvent.

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Fig. 2. UVVis absorption spectra recorded to the extract with 1 103 M silver nitrate solution in
different solvents a) Ethanol, b) Hexane, c) DMF and d) Ethyl acetate.

Fig. 3. Visible photograph and UVvis spectra recorded for different pH [6-10 (a-e)].

To examine the pH effects on the formation of silver nanoparticles were carried out. The colour of
the mixture turned from colourless to yellow through the way of brownish yellow. In the present
studies, silver NPs were synthesized by reacting various ratio of 0.001 M AgNO3 concentrations with
fixed amount of obtained U. I. extract to monitor the excitation spectrum of Ag0 NPs. In UVVis
spectrum, a strong broad peak located between 420 nm to 430 nm was observed (Fig. 4). The obtained
peaks corresponds to the SPR of silver nanoparticles prepared using the extract supernatant.
According to the reports, UV-vis spectrum of Ag NPs synthesized in aqueous medium consists of a
peak in the region of 410-450 nm that is characteristic of size effect, which makes surface Plasmon
resonance band (SPR) particularly on the for Ag NPs [6].
To check the concentration effects, synthesis was carried out in the different ratio of silver nitrate and
extract. The UV-Vis absorption spectra of Ag NPs, thus synthesized Ag NPs showed maximum
absorbance at 422 nm, which increased with the time of growth of silver NPs with the biomass (Fig.
4i-iv). Observation of this peak is well-matched with the earlier reports for various metal
nanoparticles with sizes ranging from 2 nm to 100 nm [7].

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d)
i) d) ii)
2.0
2.0
c)

Absorbance (a.u.)
c) b)
1.6

Absorbance (a.u.)
b)
1.5
a)
1.2
a)
1.0
0.8

0.5
0.4

400 450 500 550 400 450 500 550


Wavelength (nm) Wavelength (nm)
d) d)
iii) iv)
2.0
c)
1.5 c)

Absorbance (a.u.)
b)

Absorbance (a.u.)
b)
1.5
a)
1.0 a)
1.0

0.5 0.5

400 450 500 550 400 450 500 550


Wavelength (nm) Wavelength (nm)

Fig. 4. UVvis spectra recorded for different concentration (a) 0.5 :1, (b) 1:1, (c) 1:2 (d) 1:3
[Extract:AgNO3 (1103 M)] The samples were collected at different time intervals of growth.

FT-IR spectral analysis. Functional groups present in the extract were analyzed using FTIR
spectroscopy. Fig. 5a shows the FTIR spectrum of U. I extract obtained in water and Fig. 5b for the
silver NPs formed in extract. Spectrum evidences the presence of OH group, phenyl ring -CH group,
amide and thio groups in the extract. The presence of biomolecules in the extract is act as the reducing
as well as the stabilizing agents for efficient stabilization of nanoparticles. After the addition of Ag
ions in extract for 24 h, we can see the absence of some peaks in the FTIR spectrum (Fig. 5b).

Fig. 5. FTIR spectra of a) U. I aqueous extract and b) Ag ions with the extract at 24h.

Fig. 6. XRD Pattern of Ag0 NPs.

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X-ray diffraction analysis. The XRD patterns of the Ag NPs are shown in Fig. 6. The XRD pattern
shows four intense peaks in the whole spectrum of 2 values ranging from 20 to 80. XRD spectra of
pure crystalline silver structures and pure silver nitrate have been published by the Joint Committee
on Powder Diffraction Standards (le nos. 04-0783 and 84-0713). The peaks at values of 37.84 Silver
nanoparticles were synthesized from 1 mM silver nitrate-U. I. extract at room temperature. The
samples were collected at 24th hour, sonicated, air-dried and XRD pattern was observed with position
37.84, 43.97, 64.25 and 77.19 corresponding to (1 1 1), (2 0 0), (2 2 0) and (311) planes of face
centered cubic structure of metallic silver with space group of Fm-3m, respectively. The full width at
half maximum (FWHM) values measured for (1 1 1), (2 0 0), (2 2 0) and (311) planes of reection
were used with the Scherrer equation to calculate the average crystallite size of the nanoparticles.
From these the average particle size was found to be around 25-30 nm.
Morphological analysis.
FESEM and EDAX. FESEM determinations of the above-mentioned sonicated sample showed the
formation of nanoparticles, which were conrmed to be of silver by EDAX. As shown in Fig. 7, well-
dispersed nanoparticles could be seen in the samples treated with silver nitrate. The particle present
in the image was well arranged with smaller size. The obtained images shows the spherical shaped
particles with approximately 25 nm in scale EDAX analysis also showed a peak in the silver region,
conrming the formation of silver nanoparticles (Fig. 7).

Fig. 7. FESEM and EDAX of the 1 103 M silver nitrate with U. I. extract showing with higher
resolution (scale bar at 100 nm).

Catalytic reduction. The reduction reaction of 4-nitrophenol can be easily monitored by UV-vis
spectroscopy as shown in Fig. 8. The decrease in the strong absorption peak at 400 nm can be readily
monitored by UV-vis spectroscopy. It can be seen that the absorption associated with p-nitrophenol
at 400 nm decreases with a concomitant increase of the absorption at 300 nm due to the p-
aminophenol as the reduction reaction proceeded [8].

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Fig. 8. a) Time-dependent UV-visible spectra, b) Plots of (At/A0) vs time and c) efficiency plot for
the catalytic reduction of 4-NP.

Summary. A simple one-pot green synthesis of stable silver nanoparticles using U. indica bulbs
extract at room temperature was reported in this study. Synthesis was found to be efficient in terms
of reaction time as well as stability of the synthesized nanoparticles which exclude external
capping/reducing agents. Therefore, this reaction pathway satisfies all the conditions of a 100% green
chemical process. The formations of Ag0 NPs by U. I. bulb extract with respect to the pH variation,
concentration variation and time duration was examined.
References
[1] Christophe Petit, Patricia Lixon, Marie Paule Pileni. In situ synthesis of silver nanocluster in AOT
reverse micelles, J. Phys. Chem., 1993, 97 (49), pp 1297412983 DOI: 10.1021/j100151a054
[2] Md. Harunar Rashid and Tarun K. Mandal. Synthesis and Catalytic Application of Nanostructured
Silver Dendrites, Polymer Science Unit and Centre for Advanced Materials, Indian Association for
the Cultivation of Science, Jadavpur, Kolkata, 700 032, India, J. Phys. Chem. C, 2007, 111 (45), pp
1675016760, DOI: 10.1021/jp074963x
[3] Yugang Sun, Yadong Yin, Brian T. Mayers, Thurston Herricks, Younan Xia, Uniform Silver
Nanowires Synthesis by Reducing AgNO3 with Ethylene Glycol in the Presence of Seeds and
Poly(Vinyl Pyrrolidone), Department of Chemistry and Department of Materials Science and
Engineering, University of Washington, Seattle, Washington 98195, Chem. Mater., 2002, 14 (11), pp
47364745, DOI: 10.1021/cm020587b
[4] Collera-Zuniga, O., F.G. Jimenez and R.M. Gordillo. 2005. Comparative study of carotenoid
composition in three Mexican varieties of Capsicum annuum L. Food Chem. 90: 109-114
[5] S. Li, Y. Shen, A. Xie, X. Yu, L. Qiu, L. Zhang, Q. Zhang, Green synthesis of silver nanoparticles
using Capsicum annuum L. extract, Green Chem., 2007,9, 852-858, DOI 10.1039/B615357G
[6] M. Forough, K. Farhadi, Turkish J. Eng. Env. Sci. 34 (2010) , 281 287, DOI10.3906/muh-1005-
30
[7] L. Kang, P. Xu, D. Chen, B. Zhang, Y. Du, X. Han, Q. Li, H.L. Wang, J. Phys. Chem. C (2013).
[8] S. Agnihotri, S. Mukherji, S. Mukherji, Size-controlled silver nanoparticles synthesized over the
range 5100 nm using the same protocol and their antibacterial efficacy, DOI: 10.1039/C3RA44507K
(Paper) RSC Adv., 2014, 4, 3974-3983

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Synthesis, Morphological Characterization and Photocatalytic Property of


Silver Molybdate5

S. Muthamizh1, S. Munusamy1, S. Praveen Kumar1, V. Narayanan1,a

1 Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai, India


a vnnara@yahoo.co.in

DOI 10.2412/mmse.94.18.722 provided by Seo4U.link

Keywords: Ag2MoO4, microcubes, photocatalyst.

ABSTRACT. Silver molybdate (Ag2MoO4) microcubes were synthesized by simple and cost effective precipitation
method by reacting 1:1 mole ratio of silver acetate and ammonium molybdate. The synthesized nanoparticles were
characterized byXRD, Raman and DRS-UV spectroscopy, morphology of the Ag2MoO4 was investigated by FE-SEM
analysis. The XRD pattern reveals that the synthesized Ag2MoO4 has cubic structure. In addition, by using the XRD data
lattice parameter values also calculated. The Raman analysis of Ag2MoO4 confirms the presence of Ag-O and Mo-O
bonds in synthesized microcubes. FE-SEM analysis revels that the synthesized Ag2MoO4 has cube like morphology. The
optical property of Ag2MoO4 microcubes were carried out by DRS UV-Visible spectroscopy. The synthesized Ag2MoO4
was utilized for the degradation of organic dye under visible light irradiation.

Introduction. Transition metal-based molybdates nanostructures (M = Fe, Ni, Co, Ag, Mn etc., ) are
considered as an important inorganic material which are widely explored in various applications such
as Li-ion storage batteries, [1] supercapacitors, [2] optical fibers, [3] photoluminescence, [4]
photocatalyst, [5] humidity sensors, [6] magnetic properties and catalysts. [7] However, low
dimensional metal molybdates have attracted more interest in recent years. In particular, silver
molybdate (Ag2MoO4) has attracted considerable attention because of its unique properties such as,
photoluminescence environmental friendly, excellent antimicrobial activity, high electrical
conductivity, good photocatalytic activity and extraordinary electrochemical energy storage
performance. Due to these properties, the Ag2MoO4 is potentially used in several applications
including ion-conducting glasses, gas sensor, antibacterial material, photo switches and ceramics. In
photocatalysis, Ag2MoO4 has paid significant attention owing to its photosensitivity which make this
material with high photocatalytic activity under UV or visible-light irradiation. Recent literature is
reported based on Ag2MoO4 and its composite that act as a photocatalyst for the degradation of
organic dyes into the wastewater. [8] The photocatalytic activity mainly depends on the crystal and
electronic structures of materials that affect the energy band structure and the efficiency of charge
carrier transfer. Moreover, to improve their physicochemical properties of the photocatalyst,
researchers have developed a number of attempt to obtain the different morphologies of Ag2MoO4
including nanoparticles, nanorods, nanowires, wire-like nanostructures, nanoclusters, broom-like,
flower-like microstructures and microcrystals.
Experimental.
Reagent. Silver nitrate, ammonium molybdate and methylene blue were purchased from Qualigens
and used as received. Other chemicals used were of analytical reagent grade. Double distilled water
was used thought the experiment. All chemicals were used without further purification.

5
2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

Synthesis of Ag2MoO4 nanoparticles. Ag2MoO4 microcubes were prepared via co-precipitation


reaction in aqueous media by addition of Ag+ solution, in molybdate solution under vigorous stirring.
When the mixing process was completed, the formed Ag2MoO4 suspension was ltered and washed
with distilled water and ethanol for three times and then dried in oven at 90 C for 2 h. In order to
form crystalline Ag2MoO4 particles, the prepared samples were annealed at 600 C.
Instrumentation. The XRD pattern of the synthesized sample was analyzed by using Rich Siefert
3000 diffractometer with CuK1 radiation ( =1.5406 ). Raman spectrum was recorded using laser
Raman microscope, Raman-11 Nanophoton Corporation, Japan. DRS UVVis absorption spectrum
was recorded using a PerkinElmer lambda 650 spectrophotometer. The morphology of synthesized
Ag2MoO4 was analyzed by HITACHI SU6600 Field Emission Scanning Electron Microscopy (FE-
SEM) coupled with EDAX.
Result and discussion.
XRD analysis. Synthesized Ag2MoO4 was subjected to XRD analysis in order to conrm the phase,
crystal structure and the lattice parameter of the sample. The obtained XRD pattern is shown in Fig.
1it is well matched with cubic phase of JCPDS Card No 00-08-0473 with space group of Fd-3 m
(227).The sharp peaks indicate the high crystalline nature of the sample without any impurities.

Fig. 1. XRD pattern of Ag2MoO4 microcubes.

Raman analysis. Ag2MoO4 was subjected to Raman analysis, which is shown in Fig. 2. The band
region from 872-926 cm1 with high intensity is due to the symmetric stretching of MoO bond in
[MoO4]. Asymmetric bending mode of MoO4 falls under the region of 357372 cm1. 357372 and
282297 cm1 are corresponds to Asymmetric and symmetric bending of MoO4 in Ag2MoO4. [9]

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Fig. 2. Raman spectrum of Ag2MoO4 microcubes.

DRS-UV. Synthesized Ag2MoO4 was subjected to DRS-UVVis analysis to examine the optical
property and to nd out the band gap of the material. Observed spectrum is shown in Fig. 3 and the
inset shows the band gap plot of Ag2MoO4. The band gap value (Eg) of micro cubes was determined
by using Tauc's plot.

(h)1/n=A (h-Eg)

where h Planck's constant, frequency of vibration, absorption coefficient, Eg band gap, A


proportional constant. n = 2 (for direct band gap), or n = 1/2 (for indirect band gap).
The synthesized Ag2MoO4 showed band gap of band gap of 2.87 eV which is shown in Fig. 3.

Fig. 3. DRS-UVVis spectrum of Ag2MoO4 micro cubes. Inset shows the Tauc's plot.

Morphological analysis. Synthesized Ag2MoO4was subjected to FE-SEM analysis in order to


conrm the shape and size of the particles. Fig. 4 shows the image of Ag2MoO4 which resembles the
cubes shape with size in micro meter.

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Fig. 4. FE-SEM image of Ag2MoO4 microcube.

Photocatalytic activity. The photocatalytic activity of the fabricated pure Ag2MoO4 investigated on
the degradation of organic dyes Methylene blue (MB) shown in Fig. 5. 25 mg of photocatalyst was
taken and transferred into a beaker which contains 100 mL of 1 105 M MB solution. Prior to light
exposure, the mixture of dye and photocatalyst was kept under dark in order to attain adsorption
desorption equilibrium between the photocatalyst and dye. After 30 min the reaction mixture is
exposed to visible light under constant magnetic stirring. The reaction mixture was collected every
10 min and subjected to UVVis analysis. It can be seen that the intensity of the absorption peaks
decreased as the reaction progressed with Ag2MoO4 microcube as the catalyst.

Fig. 5. Absorption spectra of aqueous MB solution at 60 min during photodegradation by using


Ag2MoO4 microcube as a photocatalyst.

Summary. Ag2MoO4 microcube were synthesized by simple precipitation method. The phase and
crystal structure of the Ag2MoO4 microcube nanoparticles was characterized byXRD and Raman
spectroscopy. The optical property of Ag2MoO4 examined by DRS-UV spectroscopy. The
morphology of the Ag2MoO4 microcube was confirmed by FE-SEM analysis. The synthesized micro
cubes were employed for the degradation of methylene blue dye.
References

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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

[1] N. Chen, Y. Yao, D. Wang, Y. Wei, X. Bie, C. Wang, G. Chen and F. Du., LiFe(MoO4)2 as a Novel Anode
Material for Lithium-Ion Batteries, ACS Appl. Mater. Interfaces, 2014, 6 (13), pp 1066110666, DOI:
10.1021/am502352c
[2] M.C. Liu, L. Kang, L.B. Kong, C. Lu, X. J. Ma, X. M. Li and Y. C. Luo., Facile synthesis of
NiMoO4xH2O nanorods as a positive electrode material for supercapacitors, RSC Adv., 2013,3, 6472-6478,
DOI: 10.1039/C3RA22993A
[3] A. P. de Moura, L. H. de Oliveira, I. L. V. Rosa, C. S. Xavier, P. N. L. Filho, M. S. Li, Felipe A. L. Porta,
E. Longo and J. A. Varela., The Scientific World Journal. DOI:10.1155/2015/315084.
[4] Y. S. Luo, X. J. Dai, W. D. Zhang, Y. Yang, C. Q. Sunb and S. Y. Fu., Controllable synthesis and
luminescent properties of novel erythrocyte-like CaMoO4 hierarchical nanostructures via a simple surfactant-
free hydrothermal route, Dalton Trans. 2010 Mar 7;39(9):2226-31. DOI: 10.1039/b915099d.
[5] Y. Ding, Y. Wan, Y. L. Min, W. Zhang and S. H. Yu., General synthesis and phase control of metal
molybdate hydrates MMoO4.nH2O (M = Co, Ni, Mn, n = 0, 3/4, 1) nano/microcrystals by a hydrothermal
approach: magnetic, photocatalytic, and electrochemical properties, Inorg Chem. 2008 Sep 1;47(17):7813-23.
DOI: 10.1021/ic8007975.
[6] R. Sundaram and K.S. Nagaraja, Solid-state electrical conductivity and humidity sensing studies on metal
molybdatemolybdenum trioxide composites (MNi2, Cu2 and Pb2), Sens. Actuators B 101 (2004), pp.
353360 DOI: 10.1016/j.snb.2004.04.005.
[7] V. Umapathy, Manikandan, S. A. Antony, P. Ramu, P. Neeraja., Structure, morphology and opto-magnetic
properties of Bi2MoO6 nano-photocatalyst synthesized by solgel method, Transactions of Nonferrous Metals
Society of China 25(10), March 2015, DOI: 10.1016/S1003-6326(15)63948-6
[8] D. Xu, B. Cheng, J. Zhang, W. Wang, J. Yu and W. Ho., J. Mater. Chem. A, 2015, 3, 20153.
[9] M. T. Fabbro, C. C. Foggi, L. P. S. Santos, L. Gracia, A. Perrin, C. Perrin, C. E. Vergani, A. L. Machado,
J. Andrs, E. Cordoncillo and E. Longo., Synthesis, antifungal evaluation and optical properties of silver
molybdate microcrystals in different solvents: a combined experimental and theoretical study, Dalton Trans.,
2016, Vol. 45, 10736-10743, DOI 10.1039/C6DT00343E

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Electrocatalytic and Photocatalytic Application of Carbon Nitride Ag Hybrid


Nanocomposite6

S. Munusamy1, R. Suresh1, K. Giribabu1, R. Manigandan1, S. Preenkumar1, S. Muthamizh1,


T. Dhanasekaran1, A. Padmanapan1, G. Ganamoorthy1, A. Stephen2, V. Narayanan1, a

1 Department of Inorganic Chemistry, Guindy Campus, University of Madras, Chennai, India


2 Department of Nuclear Physics, Guindy Campus, University of Madras, Chennai, India
a vnnara@yahoo.co.in

DOI 10.2412/mmse.14.20.385 provided by Seo4U.link

Keywords: carbon nitride Ag, hydroquinone, methylene blue.

ABSTRACT. In this paper, a carbon nitride Ag hybrid nanocomposite is synthesized. Carbon nitride Ag hybrid
nanocomposite was synthesized by chemical oxidative polymerization method. The hybrid was characterized by UV-
Visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and field emission
scanning electron microscopy (FE-SEM). The electrochemical oxidation of hydroquinone was inspected by cyclic
voltammetry (CV). The Carbon nitride Ag hybrid modified GCE (hybrid nanocomposite /GCE) showed enhanced
electrocatalytic oxidation of hydroquinone than GCE. The hybrid showed better photoccatalytic degradation of methylene
blue within 180 mins.

Introduction. Diverse polymeric carbon nitrides, which differ in their atomic sizes, have been
reported by thermal condensation of organic monomers. One of the most applicable is the polymeric
form melon, H3C6N9, a major architecture which is a significance of an incomplete condensation of
carbon nitride precursors. [1] Bojdys et al. reduce the hydrogen contented to a sensible C3N4
formulation by condensation of dicyandiamide in a salt melt of lithium and potassium chloride [2].
The results designate that graphitic allotropes are the most stable phases under ambient situations for
the C3N4 composition. Carbon nitrides and connected compounds are of great engineering attention
as possible materials for microelectronic devices, optical, magnetic and tri bological applications [3,
[4], [5], [6]. Graphitic carbon nitrides container also be an energetic support, Lewis-base character,
for the dispersal of metal particles in heterogeneous catalysis. [10] Recently, Wang et al. have
measured g-C3N4 as a plentiful photocatalyst for hydrogen construction from water [11]. In adding to
mentioned perspectives, in the past decades, studies on the most stable polymorphs of C 3 N4 were
interested by a special attention for the synthesis of new low-compressible materials [12], [13].
Synthesis of carbon nitride-Ag hybrid nanocomposite. The graphitic C3N4-silver hybrid
nanocomposites were synthesized using urea-silver acetate poly-condensation methods. In 95:5%
amounts of urea- silver acetate were taken in alumina crucibles with covered and calcined at 550o C
for 5 h at a heating rate of 50 C min -1.
Result and Dissuasion
UV-Visible spectroscopy. The UV-Visible absorption spectrum of the silver- carbon nitride
nanocomposite is showed in Fig. 1. The broad peaks in the range of 600 nm were corresponding to
-transition of electronic states are contributions from carbon nitride [14]. The UV-Visible
absorption spectrum of the silver nanoparticles is one broad peak in the range of 410 nm. The result

6
2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
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hybrid was confirm the absorption peak at 600, 410 nm of carbon nitride-silver nanocomposite. In
the carbon nitride silver hybrid composite there is a small shift in the band edge position to a higher
wavelength its suggesting that the recombination rate of the electron hole pair was successfully
reduced in the hetero structured carbon nitride- silver composite hybrid nanocomposite.
FT-IR spectroscopy. The FT-IR spectrum of the carbon nitride-silver hybrid nanocomposite is
showed in Fig. 2. The fourier transform infrared spectroscopic measurement, which implies the
existence of condensed aromatic carbon nitride hetrocycles. The stretching vibration near at 1546 and
1620 cm-1are attributed to C=N stretching, while the three bands at 1217, 1304 and 1409 cm-1 to
aromatic C-N stretching [15] . The peak at 808 cm-1 belongs to triazine ring mode, which correspond
to condensed CN heterocyclic. A broad band near at 3150-3500cm-1 correspond to the stretching
modes of NH2 or =NH groups, are mostly due to typical vibrations of C-N that contain C-N
hetrocycles and are generally associated with skeletal stretching vibration of these aromatic ring,
which are uncondensed amine groups in agreement with the result. The FTIR a spectrum of the silver
nanoparticles was confirm as expected at stretching vibration modes at 573 cm-1. In the result was
confirming in the strong interaction between Ag-carbon nitride stretching vibration position to a lower
wavenumber.

Fig. 1. UV-Visible spectroscopy of carbon nitride-silver nanocomposite.

Fig. 2. FTIR spectroscopy of carbon nitride-silver nanocomposite.

Raman Spectroscopy. The Raman spectrum of the carbon nitride-silver nanocomposite is showed
in Fig. 3. The Raman peaks observed at 786 and 1016 cm-1 are attributed to the different types of ring
breathing modes of s-triazine unit, was confirm carbon nitride structure [16]. The above result is in

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good agreement with the FTIR result. The Raman spectra of the silver were confirming nanoparticles
as expected peak at 1650 nm. All the characteristic bands were observed in the hybrid nanocomposite.
XRD: The X-ray diffraction pattern of carbon nitride-silver nanocomposite is shown in Fig. 4. The
2 peak were observed at 27.740 corresponds to the in-plane structural packing motif of tristriazine
units is corresponding to (002) plane. These plane (002) corresponding to the hole-to-hole interaction
of carbon nitride and the presence of uncondensed amino groups [17]. The silver nanoparticle was
confirm to the 2 = value (JCPDS-25-922). All the characteristic peaks were observed hybrid
nanocomposite.

Fig. 3. Raman spectroscopy of carbon nitride-silver nanocomposite.

Fig. 4. XRD of carbon nitride-silver hybrid nanocomposite.

FE-SEM. The surface of morphology of the hybrid was investigated by FE-SEM. The FE-SEM
images of carbon nitride are shown in Fig. 5 (a-b). The grain size of g-C3N4 was distributed from 300
to 500 m. The layered shape morphology is clearly shown in Fig. 5 (b). The layered was
agglomerated sheet like morphology of carbon nitride-Ag. The nanoparticles calcined at 5500c for 4h
at this temperature the nanoparticles walls were converted to nanosheets. The dispersed Nano spheres
will have potential applications in photo catalysis due to larger available surface areas. The energy
dispersive spectroscopy (EDS) shows that they consist of C, N and Ag only Fig. 2 (c) is consistent
with good agreement with XRD results.

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Fig. 5. FE-SEM and EDAX image of carbon nitride-silver nanocomposite.

Fig. 6. CV analysis of (a) bare pH=4, (b) Hydroquinone/GCE, (c) Ag-carbon


nitride/GCE/Hydroquinone.

Electrochemical sensing of mebendazole by Carbon nitride-Ag hybrid nanocomposite.


Cyclic voltammetry. Fig. 6 shows CV of bare/GCE (a) and GaN/carbon nitride-Ag/GCE in the
presence of 1 mM hydroquinone in 0.1 M PBS buffer (pH 4) at the scan rate of 50 mV/s. It shows an
reversible behaviour at bare GCE with the anodic peak potential (Epa) at 0.6961mV, with an anodic
peaks current (Ipa) of 1.1685 A and cathode peak potential (Epc) at -0.1373mV, with an cathode
peaks current (Ipc) of -1.1378 A. The modified GaN/carbon nitride-Ag/GCE exhibits well-known
redox hydroquinone anodic peak potential (Epa) at 0.4005mV, with anodic peak current (Ipa) of 1.6564
A and cathode peak potential (Epc) at -0.1544mV, with an cathode peaks current (Ipc) of -1.1452 A.
The redox peak current is enhanced compared to bare GCE with negative shift of 0.45 mV. The result

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suggests that the GaN/carbon nitride-Ag/GCE has improved the electron transfer kinetics due to
enhanced conducting nature.

Fig. 7. CV analysis hydroquinone of scan rate 50-150mVs-1 using Ag-carbon nitride/GCE.

Fig. 8. DPV analysis of hydroquinone concentration of 0.01-0.07 M using Ag-carbon


nitride/GCE/Hydroquinone and calibrate plate.

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Fig. 9. Calibration plot.

Fig. 7 shows the cyclic voltammograms of 1 mM hydroquinone at Ag-carbon nitride/GCE in the scan
rate effective range of 50 to 150mVs-1. At scan rate were increasing, were corresponding to the
current response increasing is good catalytic ability of the hydroquinone.
The differential pulse voltammetry. The Fig. 8 shows the differential pulse voltammograms of
hydroquinone at carbon nitride-Ag/GCE in different concentration. A successive addition of
hydroquinoneto 0.1 M PBS (pH 4) produces a significant increase in the current with slight shift in
peak potential. The calibration plots were found to be linear and the correlation equation of I (A) =
4.2905 + 0.09780 (Vs-1) (r 2= 0.9937). The calibration plot of carbon nitride-Ag/GCE is shown as
inset in Fig. 9. The linear response is in the range from 0.4x10-6 ~ 1x10-7 M corresponding with a
sensitivity of 0.095 A/mM shows that the carbon nitride-Ag/GCE is sensitive towards the
mebendazole. The limit of detection (LOD=3/s) is found to be 1.110-7 M. On the basis of our
results, we expect that it is possible to use the hybrid have incredible advantages for constructing
electrochemical sensor towards such other analytes.
Photocatalytic degradation of MethyleBlue. Photocatalytic activity of the carbon nitride-silver
hybrid was examined by using degradation of methylene blue (MB) as the model organic pollutant.
Fig.10 shows the absorption spectrum of 510-5 M MB solution during different time intervals in
presence of carbon nitride-silver nanocomposite respectively. The visible light irradiation of aqueous
dye solution in presence of carbon nitride-silver nanocomposite nanoparticles showed decrease in
absorption maximum with shift in absorption maximum ( = 663 nm). It suggests that the complete
decolourization of MB solution was purely due to the photocatalytic degradation ability of carbon
nitride-silver nanocomposite. Further, absorbance of carbon nitride-silver nanocomposite showed a
maximum value of 0.45before irradiation and decreased to a value of 0.045 after 180 min. It should
be mentioned that the continued irradiation of visible light for another 35min did not give any
decrease in absorbance at 663 nm. Therefore, the photocatalytic efciency and the rate constant
values were calculated with that carbon nitride-silver value of absorbance and the degradation time
of 180 min respectively. It can be seen that the carbon nitride-silver hybrid nanocomposite exhibits
maximum efficiency towards the photocatalytic degradation of MB.

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Fig. 10. Photocatalytic degradation of methylene blue.

C3N4/Ag +h c3N4/Ag+ + e CB-


C3N4/Ag+ C3N4/Ag +hB+
e CB-+ O2 O2.-
hB++ H2O (H++OH-)H+ +OH.
Dye+OH. oxidation products.

Summary. The synthesized of silver-carbon nitride hybrid nanocomposite was characterized by UV-
visible, FT-IR spectroscopy, Raman, XRD. The particle size and morphology were observed by FE-
SEM. The above characterization methods show strong evidence for the formation of Ag-carbon
nitride nanocomposite and the interaction happened between Ag and carbon nitride. TheFE- SEM
images show the nanosphere like morphology of the Ag-carbon nitride. The electrochemical sensing
properties of hybride nanpcomosite were investigated by using hydroquinone as an analyte. The
detection limit and sensitivity of Ag-carbon nitride/GCE is found to be 1.110-7M and 0.095A/mM
respectively.
References
[1] B. V. Lotsch, M. Doblinger, J. Sehnert, L. Seyfarth, J. Senker, O. Oeckler and W. Schnick,
Unmasking Melon by a Complementary Approach Employing Electron Diffraction, Solid-State
NMR Spectroscopy, and Theoretical CalculationsStructural Characterization of a Carbon Nitride
Polymer, Chem. Eur. J., 2007, Vol. 13, Iss. 17, 4969-4980, DOI: 10.1002/chem.200601759
[2] M. J. Bojdys, J.-O. Muller, M. Antonietti and A. Thomas, Ionothermal Synthesis of Crystalline,
Condensed, Graphitic Carbon Nitride, Chem. Eur. J., 2008, Vol. 14, 8177-8182. DOI:
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[3] T. W. Scharf, R. D. Ott, D. Yang and J. A. Barnard, Structural and tribological characterization
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[6] Y. Zhao, Z. Liu, W. Chu, L. Song, Z. Zhang, D. Yu, Y. Tian, S. Xie and L. Sun Adv. Mater.,
2008, 20, 1777.
[7] F. Goettmann, A. Fischer, M. Antonietti and A. Thomas, Chemical synthesis of mesoporous
carbon nitrides using hard templates and their use as a metal-free catalyst for Friedel-Crafts reaction
of benzene. Angew Chem Int Ed Engl. 2006 Jul 3;45(27):4467-71, DOI: 10.1002/anie.200600412
[8] A. Thomas, A. Fischer, F. Goettmann, M. Antonietti, J.-O. Muller, R. Schlogl and J. M. Carlsson,
Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free
catalysts, Journal Of Materials Chemistry, 2008,18, 4881-4881, DOI: 10.1039/B816709P
[9] A. Thomas, F. Goettmann and M. Antonietti, Chem. Mater., 2008, 20, 738.
[10] M. Kim, S. Hwang and J.-S. Yu, Novel ordered nanoporous graphitic C3N4 as a support for Pt
Ru anode catalyst in direct methanol fuel cell, J. Mater. Chem., 2007,17, 1656-1659, DOI:
10.1039/B702213A
[11] X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. M. Carlsson, K. Domen and
M. Antonietti, A metal-free polymeric photocatalyst for hydrogen production from water under
visible light, Nature Materials, 2009 Jan; 8(1):76-80. DOI: 10.1038/nmat2317
[12] J. E. Lowther, Relative stability of some possible phases of graphitic carbon nitride, Phys. Rev.
B, 1999, 59, 11683.
[13] P. G. Li, M. Lei, H. Z. Zhao, H. L. Tang, H. Yang and W. H. Tang, Materials Chemistry and
Physics, 59, 11683 (1999), DOI 10.1103/PhysRevB.59.11683
[14] A. Y. Liu and M. L. Cohen, Prediction of new low compressibility solids, Science, 1989, 245,
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[15] E. Kroke and M. Schwarz, Novel group 14 nitrides, Coord. Chem. Rev., 2004, 248, 493.
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DOI:10.1038/338291a0

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Variation in Structural and Optical Properties of Al Doped ZnO Nanoparticles


Synthesized by Sol-gel Process7

Vanaja Aravapalli1, Seshu Kalakatla1, G. K. S. Prakash Raaju2, Srinivasa Karumuri3

1 Asst. Professor, Dept. of AS&H, Tirumala Engineering College, Jonnalagadda, India


2 Research fellow, CMET (Govt. of India), Hyderbad, India
3 Professor, Dept of ECE, KL University, Vaddeswaram, India

DOI 10.2412/mmse.23.89.710 provided by Seo4U.link

Keywords: aluminum nanoparticles, ZnO, XRD, SEM, UV-Vis, PL.

ABSTRACT. This article focuses on analyzing structural and optical properties of Al doped ZnO (AZO) synthesized
with two different precursors aluminum chloride and aluminum nitrate. The nanoparticles were successfully fabricated
and characterized at room temperature by sol-gel process. The objective of improving properties of ZnO nanoparticles by
introducing dopants was successful with formation of nanoparticles having different crystalline sizes, optical absorption
and luminescence properties. The two different sources influenced properties of ZnO. The particles with less crystalline
size obtained from aluminum nitrate. Change in morphology from spherical to bar like morphology proved from SEM
spectra. Presence of functional groups predicted from FTIR spectra. PL spectra proved UV emission and visible emission
for AZO nanoparticles synthesized using dopant sources aluminum chloride and aluminum nitrate respectively. The
obtained properties prove successful utilization of AZO nanoparticles as building materials in fabrication of
optoelectronic devices.

Introduction: Recent days ZnO nanoparticles widely utilized in fabrication of various optoelectronic
devices including photodetectors, solar cells, LEDs etc due to characteristics of large and direct band
gap, high melting point, thermal conductivity, mobility, inexpensive, luminescence etc. Introducing
dopants in ZnO lattice helps in tuning the properties of ZnO nanoparticles [1]. Transition metal ions
can be easily penetrated into ZnO lattice because they have ionic radius which is very close to ZnO.
In present work, AZO nanoparticles are synthesized by choosing different dopant sources aluminum
chloride and aluminum nitrate. AZO is also a promising material for high temperature thermo
electronic material. ZnO nanoparticles obtained by replacing Zn2+ with high valence electrons like
Al, Ga, In etc regarded as promising materials for optoelectronic device fabrication [2]. AZO
nanoparticles is also highly promising as a potential high-temperature thermoelectric material. Al ion
can be easily incorporated into ZnO lattice due to its ionic radius near to that of ZnO [3]. AZO
nanopowders can be utilized as transparent conductive pastes because of their properties of
transparency and conductivity in visible region. ZnAlO is a wide band gap material (Eg~3.8eV). Top
down and bottom up approaches were reported in literature for synthesizing nanoparticles. Bottom
up methods were more preferred because of their less wastage, high purity etc. [4]. With the
development in field of nanoresearch various bottom up techniques like co precipitation,
hydrothermal method, laser ablation etc were developed for nanoparticle synthesis [5]. In this work
sol-gel method is used for synthesis of AZO nanoparticles. This method is simple, inexpensive,
environment friendly. By this method it is possible to control particle size, morphology, high degree
of crystallinity, higher nucletion rates etc. The sol-gel process is carried out at room temperature [6].
In this work, AZO nanoparticles were prepared by sol-gel process employing ZnCl2, NaOH,
Aluminium nitrate, Aluminium chloride and ethanol as starting materials. The particles were

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2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
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synthesized without involving any external parameters like pH, temperature etc. The crystal structure,
surface morphology, chemical composition, particle size, optical absorption and luminescence
properties were characterized byXRD, SEM, FTIR, UV-Vis and PL. The results were compared to
determine the influence of Al precursor on structural and optical properties of AZO nanoparticles.
Experimental Work
Materials Required. Zinc Chloride (ZnCl2), Sodium hydroxide (NaOH), Aluminium chloride (Al
(Cl)2), Aluminium nitrate (Al (NO3)2, Ethanol. All the chemicals are A.R grade purity and they are
utilized without further purification. (Al (Cl)2) and (Al (NO3)2 served as dopant sources for synthesis
process.
Apparatus Used. Magnetic stirrer (REMI, MLH), Glass jars, Centrifuge Mission (REMI), Micro
oven (VSE 230 A/C), High Precision Balance (INFRA), Measuring jars, Centrifuge test tubes.
Synthesis Procedure: For synthesizing AZO nanoparticles using aluminium chloride precursor, At
first the glass beakers, test tubes were washed and dried. The aqueous ethanol solution of ZnCl 2 is
prepared by stirring the chemical ZnCl2 (0.2 M) in ethanol (60 ml) solution using magnetic stirrer for
2 hours. Aqueous ethanol solution of NaOH (0.2 M) is also prepared in same way by dissolving
NaOH (0.2 M) in ethanol (60 ml) using magnetic stirrer. After complete dissolution, aqueous solution
of NaOH added to ZnCl2 solution. The resulting mixture constantly stirred for one hour till the
solution turns milky. The aqueous ethanol solution of (Al (Cl)2) (0.2 M) is prepared and added to
mixed solution of (ZnCl2) and NaOH. The transparent sol was sealed and allowed to stay overnight
at room temperature to complete the gelation and hydrolysis process. During this process white
precipitates of ZnO crystallized and settled down. The resultant white precipitate so formed was taken
into test tubes and centrifuged. The resultant solution washed with ethanol to remove the unwanted
impurities. The obtained gel kept in an oven and dried at 70C and finally ground using hands to
obtain fine powder of AZO. The powder collected and preserved in an air tight container. In similar
manner AZO nanoparticles with Al nitrate as dopant source was synthesized. The obtained
nanopowders were further characterized.
The samples synthesized are:
1. AZO nanoparticles using Aluminum chloride
2. AZO nanoparticles using Aluminum nitrate.
Characterization: Structural properties including crystalline size, lattice strain were obtained from
XRD spectra. The XRD patterns of the powdered samples were recorded using XRD (Rigaku)
diffractometer with a Cu K radiation (=1.5406 Ao). The crystallite size estimated using Debye-
Scherer equation of the high intense XRD peak. Morphological properties obtained from SEM
micrographs recorded from SEM (Carl Zeiss SUPRA-55) spectroscopy. UV- Vis spectra of samples
were recorded using UV-VIS Spectrophotometer (Perkin Elmer Spectrum). The powdered sample
were dispersed in ethyl alcohol and mounted in the sample chamber while pure ethyl alcohol was
taken in the reference beam position. The essential information about the physical properties of
materials at molecular levels, including shallow and deep level defects and band gap state for energy
level were determined using PL spectroscopy (Bruker S4 Pioneer).
Results and Discussions.
XRD Analysis: The XRD spectra of AZO nanoparticles synthesized with precursors (Al (Cl)2) and
Al (NO3)2 are shown in Fig. 1 (a) and Fig. 1 (b).The XRD peaks clearly indexed to hexagonal
wurtzite structure (JCPDS 89-0510) with high purity. Wurtzite structure of ZnO is not influenced due
to variation in dopant sources. Shift in position of diffraction peaks is noticed due to variation in Al
precursor. The crystalline size calculated using Scherrers formula is found to be 28.419 nm and 58.54
nm respectively. AZO nanoparticles with different crystalline sizes influence optical absorption and
luminescence properties.

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(a) (b)
Fig. 1. XRD spectra of AZO nanoparticles synthesized using (a) Al (NO3)2 (b) (Al (Cl)2).

SEM Analysis

(a)

(b)
Fig. 2. SEM spectra of AZO nanoparticles synthesized using (a) Al (NO3)2, (b) (Al (Cl)2).

Fig. 2 (a) and 2 (b) represent SEM micrographs of AZO nanoparticles synthesized using Al (NO3)2
and (Al (Cl)2) respectively. The micrographs reveal the formation of nanoparticles. Fig. 2 (a) confirms
the formation of approximate round shape morphology. Fig. 2 (b) shows the prepared nanoparticles
have nanoflake like morphology converted to bar like when observed at different magnifications. The
dopant source has proved nanoparticle synthesis with different suface areas.
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FTIR Analysis. The structural properties of nanoparticles further confirmed from FTIR
spectroscopy. Fig. 3 (a) and Fig. 3 (b) represent FTIR spectra of AZO nanoparticles obtained from
different precursors Al nitrate and Al chloride respectively. The position and number of absorption
bands varies with chemical composition.
In Fig. 3 (a) the absorption bands around 3500 cm-1, 1400 cm-1 attributed to presence of O-H
stretching and carbonate molecules. In Fig. 3 (b) the broad and weak absorption peaks centered at
3642 cm-1, 1655 cm-1 attributed to O-H bending and stretching. The week absorption bands found
near 2815 cm-1, 1360 cm -1 indicate the presence of C-H and C-O functional groups. Below 700 cm- 1
in Fig. 3 (a) two peaks were observed where as in Fig. 3 (b) the spinels display stretching bands in
the 500900cm1 range, associated with the vibrations of metaloxygen, aluminium oxygen and
metaloxygenaluminium from spectra it is clear that the doped samples show minimum two peaks
for all the nanomaterials that is assigned to formation of metal aluminates.

(a) (b)
Fig. 3. FTIR spectra of AZO nanoparticles synthesized using (a) Al (NO3)2 (b) (Al (Cl)2).

UV-Vis Analysis

(a) (b)
Fig. 4. UV-Vis spectra of AZO nanoparticles synthesized using (a) Al (NO3)2 (b) (Al (Cl)2).

The room temperature UV-Vis spectra of AZO nanoparticles were shown in Fig. 4 (a) and Fig. 4 (b)
respectively. An excitonic absorption peak around at 217 nm is noticed in AZO nanoparticles
synthesized using precursor Al nitrate. The peak lies much below band gap wavelength of 388 nm
corresponding to bulk ZnO. The peak at ~214 nm is due to interband transition of electron from deep
level of valence band. In Fig. 4 (b) two peaks at 238 nm and 303 nm are observed in UV region. This
shown AZO nanoparticles obtained using Al chloride as dopant have enhanced UV absorption
characteristics. The shift in absorption peak may be due to transition of electrons from inner shell to
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Mechanics, Materials Science & Engineering, May 2017 ISSN 2412-5954

outer shell.
PL Analysis: PL spectra of AZO nanoparticles synthesized with different precursors aluminum
nitrate and aluminum chloride recorded at room temperature on irradiating at wavelength 320 nm by
a xenon lamp are shown in the Fig. 5 (a) and Fig. 5 (b) respectively. In Fig. 5 (a), The PL spectra
show broad luminescence in UV region ranging from 300 - 400 nm. The effect of Al chloride doping
into ZnO lattice shows visible emission. This visible PL emission can be attributed to different
intrinsic defects. The visible luminescence centered around 451 nm corresponding to green
luminescence. Broadening of the band gap due to quantum confinement effect was observed upon Al
doping. It was reported that the oxygen vacancies responsible for the green emission are mainly
located at the surface.

(a) (b)
Fig. 5. PL spectra of AZO nanoparticles synthesized using (a) Al (NO3)2 (b) (Al (Cl)2).

Summary. The comparative study on AZO nanoparticles synthesized using different sources is very
useful to identify the potentiality of dopant source in enhancing the properties of ZnO nanoparticles.
AZO nanoparticles were successfully synthesized by sol-gel process. The AZO nanoparticles of
crystalline sizes are formed with the precursors Aluminium chloride and Aluminium nitrate
respectively. Morphology determined from SEM spectra proved the variation in morphology from
nanorod to nanobar like morphology. The variation in the crystalline size and lattice parameters
proved significant variation in presence of absorption peaks in FTIR spectra. The powders show
optical absorption in UV region. The PL spectra with significant UV luminescence noticed in spectra
of AZO nanoparticles obtained from Al nitrate. The ZnO nanoparticles prepared from (Al (Cl)2) show
intense green luminescence. The UV luminescence and green luminescence properties can be further
utilized in LEDs fabrication. Further increasing dopant concentration may enhance properties of
nanoparticles.
References
[1] Soosen Samuel M, Lekshmi Bose, George KC, Optical Properties of ZnO Nanoparticles,
Academic Review 2009, P.No 57-65.
[2] Ziaul Raza Khan, Mohd Arif, Arun Singh, Development and study of the structural and optical
properties of hexagonal ZnO nanocrystals, International Nano Letters 2012, 2:22, DOI 10.1186/2228-
5326-2-22
[3] P. M. Aneesh, K. A.Vanaja, M. K. Jayaraj, Synthesis of ZnO nanoparticles by hydrothermal
method Proc. of SPIE 2007, Vol. 6639, 66390J-1, DOI 10.1117/12.730364
[4] Marivone Gusattia, Gilvan Srgio Barroso, Carlos Eduardo Maduro de Campos, Effect of
Different Precursors in the Chemical Synthesis of ZnO Nanocrystals, Materials Research. 2011, 14
(2): 264-267, DOI 10.1590/S1516-14392011005000035
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[5] A.Alkahlout, N.AlDahoudi, I.Grobelsek, M.Jilavi, P.W.deOliveira, Synthesis and


Characterization of Aluminum Doped Zinc Oxide Nanostructures via Hydrothermal Route, Hindawi
Publishing Corporation Journal of Materials 2014, Article ID 235638.
[6] Anne Aimable, Tomasz Strachowski, Ewelina Wolska, Witold Lojkowski, Paul Bowen
Comparison of two innovative precipitation systems for ZnO and Al-doped ZnO nanoparticle
synthesis, Processing and Application of Ceramics 4 2010, 107114, DOI 10.2298/PAC1003107A

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Synthesis of SnS Nanoparticles by a Green Hydrothermal Route8

L. Ansel Mely1, P. Annie Vinosha1, M. Mary Jaculine2, Rudhra Nivedita Nathan3, S. Jerome Das1, a

1 Department of Physics, Loyola College, Chennai, India


2 Department of Physics, Velammal Engineering College, Chennai, India
3 PG Department of Physics, Women's Christian College, Chennai, India
a melyansel@gmail.com, jerome@loyolacollege.edu

DOI 10.2412/mmse.48.4.664 provided by Seo4U.link

Keywords: tin sulphide, semiconductor nanoparticles, hydrothermal, photoluminescence.

ABSTRACT. The IVVI semiconductor nanoparticle tin sulphide (SnS), has sparked rigorous interest in the scientific
commune because of the array of promising applications it offers such as in photovoltaics, near-infrared detectors and
biomedical applications. In the present work, phase pure SnS nanoparticles were effectively synthesized by a green
hydrothermal technique using the precursors tin chloride pentahydrate and thiourea. The as-prepared nanoparticles were
subjected to various characterizations in order to analyze their optical, structural and transport properties. The Powder X-
ray Diffraction (XRD) measurements revealed the purity and crystalline nature of the SnS nanoparticles. The average
crystallite size of 10.65 nm, calculated by the Scherrer's formula was in good agreement with the observations from the
Transmission Electron Microscope (TEM) micrographs. The transport properties of the synthesized nanoparticles were
studied using dielectric analysis. Further, the UV-visible spectroscopy (Uv-vis) and Photoluminescence spectroscopy
(PL) results advocate that the primed SnS nanoparticles will be an appropriate applicant for photovoltaic and other light
emitting applications.

Introduction. In recent years there is considerable interest in semiconductor nanoparticles due to


their optical and electrical properties being different from those of their bulk counterparts, due to the
quantum confinement effect [1]. Synthesis and application of IV- VI semicondctor nanoparticles have
become the research hotspot of research among which nanoparticles tin sulphide (SnS) has gained
substantial attention in the recent years owing to its multitude of merits such as exhibiting p and n
type behaviour, narrow band gap; bulk direct band gap of 1.3 eV and indirect bandgap of 1.1 eV; high
optical absorption coefficient for photons and high photoelectric conversion efficiency of up to 25%,
ampleness of raw material and meagre toxicity. Tin sulphide and can be extensively used in areas of
electronics non-linear optics, luminescence, energy storage and conversion and many more [2], [3].
Due to the versatile coordinating characteristic of SnS, it shows a variety of phases such as SnS, SnS2,
Sn2S3, Sn3S4 and Sn4S5 [4]. Further it adopts a strongly distorted NaCl structure with double layers of
tightly bound Sn-S atoms with the bonding between layers of Vanderwaal type [5]. In the present
effort, the structural and optical properties of hydrothermally prepared SnS nanoparticles were
investigated for potential optical applications.
Materials and methods
Materials used. In the present work, tin chloride pentahydrate (SnCl2.5H2O) and thiourea
(NH2CSNH2) were purchased from Merck and used without further purification. The tin slphide
(SnS) nanoparticles were synthesized by a scrupulous hydrothermal method using a cylindrical
Teflon-lined stainless steel autoclave of 200 ml capacity. Double distilled water was served as solvent
for the experiment.

8
2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
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Experimental. SnS nanoparticles were synthesized by an impeccable hydrothermal method using the
tin and sulphur precursors in the molar ratio 1:3. The precursor solutions for tin and sulphur
respectively were prepared by separately dissolving appropriate measured amount of tin chloride
pentahydrate and thiourea in 80 ml of double distilled water. Clear solutions were obtained with the
aid of magnetic stirring. Subsequently, the thiourea solution was added drop-wise to the tin solution
under constant magnetic stirring inorder to get a homogenous mixture. The solution thus obtained
was filled upto 80% volume of the autoclave and placed in a muffle furnace for 12 h at 180 C. After
cooling down of the autoclave at ambient temperature, the obtained yellow precipitate was collected
and centrifuged with distilled water and ethanol. The obtained products were dried using a hot air
oven and then ground well to gain SnS nanoparticles.
Results and Discussion
Structural and morphological analysis

Fig. 1. XRD pattern of the synthesized SnS nanoparticles.

Fig. 1 exhibits the powder X-ray diffraction (XRD) spectrum of the prepared SnS nanoparticles as
measured by using Bruker AXS D8 Advance instrument with CuK radiation (=1.540598 ) in the
angular range 20-70. The sharp and severe peaks with major diffraction peaks accredited to (120),
(021), (101), (040), (131), (210), (141), (211), (112), (231), (042) and (080) planes unveil the
formation of phase pure SnS nanoparticles as the indexed peaks match incredibly well with the
standard JCPDS card number 39-0354 with no characteristic peaks of SnS2 and SnO2. The pattern
shows the formation of orthorhombic phase herzenbergite SnS nanoparticles with Pbnm space group.
Using Scherrer's formula the crystallite size (D) of the synthesised nanoparticles was estimated to be
10.65 nm corresponding to the major diffraction peak at (040) plane. Subsequently, the
dislocation density () and strain () were estimated to be 8.8165 x 1021 m and 0.1632 lin-2 m-4
from the formulae:

1
= 2 (1)

= (2)
4

where is the full width at half maximum and is the diffraction angle.

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Fig. 2. TEM micrographs of the synthesized SnS nanoparticles.

The morphology and particle size of the synthesized SnS nanoparticles were studied using TEM
analysis by Joel/JEM 2100 Transmission Electron Microscope. The images (Fig. 2 a - b) disclose that
most of the SnS nanoparticles have nearly spherical morphology with little agglomeration and the
particle size varies from 6 to 10 nm.
Dielectric Analysis. The variation of dielectric constant and dielectric loss with frequency for the
SnS nanoparticles are shown in Fig. 3.a and b. The powder sample was pelletized and coated with
silver paint on the surface and placed between two copper electrodes. It can be observed from the
Fig.s that the dielectric constant and loss decrease respectively with corresponding increase in
frequency which can be attributed to the space-charge polarization.

a)

b)
Fig. 3. a) The variation of dielectric constant Vs log frequency, b) The variation of dielectric loss
Vs log frequency.

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Optical Analysis

a)

b)

c)
Fig. 4. a) Uv-vis absorption spectrum of the synthesized SnS nanoparticles, b) plot of (h)2 versus
h showing direct band gap of SnS nanoparticles, c) plot of (h)1/2 versus h showing indirect
band gap of SnS nanoparticles.

The UV-visible absorption (UV) spectra were determined using VARIAN in the wavelength span of
250 800 nm. The absorbance spectra shown in Fig. 4,a indicates that the synthesized SnS
nanoparticles can be used for solar cell applications since it has a strong absorption in the visible light
region. The absorption edge of the as-synthesized SnS nanoparticles show a blue shift in comparison
to its bulk counterpart, which has an absorption onset at 953 nm [4].
The bandgap being a vital characteristics of a semiconductor, was studied by UV and estimated using
Tauc's law

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( ) = ( ) (3)

where, , , and are the absorption coefficient, photon energy, proportionality constant and
direct band gap respectively.
Based on the type of electronic transition the value of can be assmed to be 2 or 1/2, i.e. for direct
and indirect transitions respectively. By extrapolating the linear part of the plots in Fig.s 4.b and 4.c,
the direct and indirect optical band gaps were estimated to be 1.54 and 1.13 eV. It is known that in
semiconductor nanoparticles, the band gap increase with decrease in particle size which can be
attributed to quantum confinement of particles. The obtained band gap values project that the
synthesized nanoparticles can be used for photovoltaic applications.
The Photoluminescence (PL) spectrum of the synthesized nanoparticles, shown in Fig. 5, shows two
emission peaks wherein the 484.02 nm peak signifies blue emission which is dissimilar from that of
SnS2 (570 nm) and bulk SnO2 (360 nm). The sturdy peak at 543.97 nm can be credited to a high level
transition in SnS semiconductor nanocrystallites. From literature, it is clear that, this kind of band
edge arises from the recombination of excitons and/or shallowly trapped electron hole pairs. The PL
spectrum suggests that the synthesised SnS nanoparticles can be used as blue and UV light emitters
[5-8].

Fig. 5. PL spectrum of the synthesized SnS nanoparticles.

Summary. Summing up, tin sulphide nanoparticles were effectively prepared by an impeccable
hydrothermal method. The structural and optical properties of the synthesized material were studied
wherein the structure and phase purity were confirmed by the powder X-Ray diffraction pattern. The
crystallite size was estimated to be 10.65 nm using Scherrer's formula. The direct and indirect band
gaps of the synthesized nanoparticles were found to be 1.54 and 1.13 eV from the Uv-visible
absorption spectroscopy, which propose the synthesised SnS nanoparticles as a prospective material
for photovoltaic applications.
Acknowledgements. The authors are grateful to the management of Loyola College, Chennai - 34
for awarding the project (3LCTOI14PHY002) under Loyola College TOI-Scheme.
References
[1] S. Sohila, M. Rajalakshmi, Chanchal Ghosh, A.K. Arora, C. Muthamizhchelvan, Optical and
Raman scattering studies on SnS nanoparticles, J. Alloys Compd. 509, 5843 (2011), DOI
10.1016/j.jallcom.2011.02.141
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[2] Jiajia Ning, Kangkang Men, Guanjun Xiao, Li Wang, Quanqin Dai, Bo Zou, Bingbing Liu and
Guangtian Zou, Facile synthesis of IVVI SnS nanocrystals with shape and size control:
Nanoparticles, nanoflowers and amorphous nanosheets, Nanoscale, 2, 1699-1703 (2010), DOI
10.1039/C0NR00052C
[3] Xing-Long Gou, Jun Chen, Pan-Wen Shen, Mater. Chem. Phys., 93, 557 (2005)
[4] Masoud Salavati-Niasari, Davood Ghanbari, Fatemeh Davar, J. Alloys Compd. 492, 570 (2010)
[5] K.G. Deepa, J. Nagaraju, Growth and photovoltaic performance of SnS quantum dots, Mater. Sc.
Eng., B 177, 1023-1028 (2012), DOI 10.1016/j.mseb.2012.05.006
[6] S. Velumani, Sa. K Narayandass, D. Mangalaraj, Structural characterization of hot wall deposited
cadmium selenide thin films, Semicond. Sci. Technol. 13, 1016 (1998), DOI 10.1088/0268-
1242/13/9/009
[7] D.J. Vidhya Raj, C. Justin Raj, S. Jerome Das, Synthesis and optical properties of cerium doped
zinc sulfide nano particles, Superlattices Microstruct. 85, 274 (2015), DOI
10.1016/j.spmi.2015.04.029
[8] Yanbao Zhao, Zhijun Zhang, Hongxin Dang, Weimin Liu, Synthesis of tin sulfide nanoparticles
by a modified solution dispersion method, Mater. Sc. Eng., B, Vol. 113, 175-178 (2004)

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Kinetics of Corrosion Rate of Carbon Steels in Different Acidic Media9

Ashok Kumar1,a

1 Assistant Professor in Physics, Y.S.R. Engineering College of Yogi Vemana University, Proddatur, India
a drashok.yvuce@gmail.com

DOI 10.2412/mmse.25.49.44 provided by Seo4U.link

Keywords: carbon steels, corrosion, acid media, concentration variation, weight loss.

ABSTRACT. The corrosion properties of carbon steels in various acidic media sulfuric acid, nitric acid, hydrochloric
acid and hydrofluoric acid has been studied. This paper also discussed about the corrosion behavior of mild steel in two
different concentrations. Carbon steels were exposed to different acid environments in different intervals of time and
corrosion rates were evaluated using weight loss method. It was evident from the results that the corrosion rate of the
carbon steels in all the acidic media are increased with time of exposure. The carbon steels shows higher corrosion rates
in nitric acid medium than compared to other acidic media. This can be attributed to strong oxidizing property of nitric
acid and larger potential to break down the passivating film formed on the surface of the sample. The mild steel sample
was also exposed to different concentrations of nitric acid medium. The results shows that the corrosion rate was increased
with increase of concentration possibly attributed to increase in the rate of reaction on the surface of the sample which
further reduces the energy barrier.

Introduction. Carbon steel is known to be the best preferred materials for industry as it has many
industrial applications. It is easy availability, excellent physical properties, stronger and more
workability than cast iron, low cost, uncomplicated fabrication made it to use in different applications
like pipeline materials in oil and gas industry water pipe lines [1, 2], cooling water systems [3], boilers
etc. However, the acids containing chloride, sulphide and so on introduces different forms of
corrosion. Among the different acids, hydrochloric acid is the most difficult to handle from the
keeping in view of corrosion and materials of constructions. Extreme care is required in the selection
of materials to handle the acid by itself, even in relatively dilute concentrations or in process solutions
containing appreciable amount of hydrochloric acid. This acid is very corrosive to most of the
common metals and alloys [4].
Corrosion of metal components has been recognized as a major problem in many engineering
applications. Failure of engineering systems due to corrosion is a common failure due to mechanical
causes such as brittle fracture and fatigue. Steel is one of the major construction material, which is
extensively used in chemical and allied industries for the handling of acid, alkali and salt solutions.
Selection of materials plays a key role in handling the acid even in relatively very low concentrations.
The acids are very corrosive to most of the common metals and alloys. Metals are exposed to acids
in many different ways and for many different reasons like acids pickling, acid descaling, industrial
acid cleaning and oil well acidizing in order to stimulate of oil well [5]. The corrosive nature of acids
also has its applications include chemical cleaning and processing, acid treatment of oil wells and
other applications.
To control the corrosion, good understanding of the effect of operating conditions such as different
types of acids, concentrations and different heat treatment procedures on the corrosion behavior is
required. Therefore, this work aims to study free corrosion behavior of different carbon steels under
different dilute acidic solutions like sulfuric acid (H2SO4), hydrochloric acid (HCl), nitric acid

9
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(HNO3) hydrofluoric acid (HF). In this paper, the weight loss technique is used to measure the
corrosion rate.
Materials and Experimental Procedure. In the present work, we used different carbon steels such
as Low carbon, medium carbon and high carbon steels of 2mm thick plates with 1cm2cm dimension.
To study the uniform corrosion resistance of different carbon steels, four different environments such
as H2SO4, HF, HCl, HNO3 was used. Samples were abraded in sequence under running tap water
using emery paper of grade number 220, 320, 400 and 600, then washed with running tap water
followed by distilled water. The samples were exposed to the acid environments in different time
intervals. After each exposure time the coupons were removed from the cells, properly cleaned in
distilled water, dried with cotton wool and then reweighed to determine the mass loss. These results
were analysed further to understand the kinetics of corrosion rate and its effects on selected carbon
steel samples.
Methodology. Initially different carbon steels such as low carbon, medium carbon and high carbon
steels are considered for the experiment and initial weights were noted. In this work, four different
types of acidic environments such as HNO3, H2SO4, HF, HCl were taken with 1mole concentration.
The samples were dipped in the acids for 1 hour interval upto 7 hrs and cumulated reduction in weight
was calculated for each interval.
Determination of Corrosion Rate.The most common method for estimating a corrosion rate from
mass loss is to weigh the corroding sample before and after exposure and the difference in weight
was noted as the weight loss in grams
To provide minimum uncertainty in the corrosion rate, this method implicitly assumes: the corrosion
rate does not vary with exposure time, the area does not change, as mass is lost to corrosion, the
projected and actual surface areas are the same, the penetration rate is uniform over the entire surface,
the weight is unaffected by corrosion product removal. Even assuming that the above criteria are
fulfilled, errors can still be propagated because of the uncertainty in the measurement of time, mass
and dimensions [6].
Results and Discussion.
Corrosion Behavior of Carbon Steels in Acidic Media. Corrosion can be defined as the
deterioration of a material resulting from chemical attack by its environment. Most corrosion of
materials involves the chemical attack of metals by electrochemical cells. By studying equilibrium
conditions, the tendencies of pure metal to corrode in a standard aqueous environment can be related
to the standard electrode potential of the metals. However, since corroding systems are not at
equilibrium, the kinetics of corrosion reactions must be studied. Some examples of kinetic factors
affecting corrosion reaction rates are the polarization of the corrosion reactions and the formation of
passive films on the metals. Corrosion can be controlled or prevented by many different methods. To
avoid corrosion, materials that are corrosion-resistant for a particular environment should be used
where feasible. For many cases corrosion can be prevented by the use of metallic, inorganic, or
organic coatings. The proper engineering design of equipment can also be very important for many
situations, for some special cases, corrosion can be controlled by using cathodic or anodic.
Corrosion and its progress often are controlled by the corrosion products formed on the metal surface.
The ability of these films to protect metal depends on how they form when the metal is originally
exposed to the environment. Thin, hard, dense, tightly adherent films afford protection, whereas thick,
porous, loose films allow corrosion to proceed without providing any protection. As an example, the
iron oxide film that usually forms on iron pipe in contact with water is porous and easily washed
away to expose more metal to corrosion. The effective use of corrosion inhibitors in many cases
depends on the type of film it forms on the surface to be protected.
The observed corrosion rate of carbon steels in H2SO4 is shown in Fig.1 (a). From the Fig. it is evident
that the carbon steels shows little effect of corrosion in this acidic medium. But as time of exposure
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increases the corrosion rate approximately by seven folds in all carbon steels, possibly due to the
increase in conductance of the solution as a result of continuous inclusion of Fe2+ ions caused by the
corrosion of carbon steel [7].
Fig. 1 (b) gives the details of the corrosion of carbon steels in HNO3 acidic environment. The graph
shows that, the carbon steels in this environment indicates highest corrosion rate when compared with
the other acidic media due to strong oxidizing property of nitric acid. When the surface of the carbon
steel exposed to the acidic medium, the possible chemical reaction leads to the formation of nitrogen
(II) oxide which modifies the color of the solution. Further this reduction process produces H+ ions
into the solution rather than hydrogen evolution[8].
The corrosive properties of carbon steels in HCl environment is shown in Fig. 1 (c). All concentrations
of hydrochloric acid will attack stainless steels since the acid readily destroys their passivity. The
corrosion rate is found to be very less than compared to all other media possibly due to chloride
aggressiveness and also the iron dissolution in HCl solutions depends on H+ ion more than the Cl- ion.
As the hydrogen forms, it tends to inhibit further corrosion by forming a very thin gaseous film at the
surface of the metal. This film can be effective in reducing metal to water contact and thus reducing
corrosion rate. [9]
The corrosion properties of carbon steels in hydrofluoric acid environment is mentioned in the Fig. 1
(d). When nonoxidizing acids like Hydroflouric acids corrode steel, atomic hydrogen is formed which
combines to form gaseous molecular hydrogen or may be observed into the steel. The corrosion rate
is higher than compared to HCl acidic medium possibly due to a change of the physical structure and
chemical composition of the corroding metal surface and a change in the composition of the solution,
particularly in the vicinity of the surface [10]. Strongly reducing acids such as hydrochloric and
hydrofluoric acids readily breakdown the passive layer of steels with little chance of repassivation
[11].

(a) (b)

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(c) (d)
Fig. 1. Corrosion behavior of carbon steels in different acidic media.

Corrosion Behavior of Mild Steel with varying concentration of acidic medium.


Fig. 2 shows the rate of corrosion of mild steel when exposed to different concentrations of HNO3.
The result shows increase in corrosion rate with the increase of concentration of acidic medium,
which is similar to the earlier reports [8-10]. Increase in corrosion rate with increasing in acid
concentration can be attribute to the energy barrier of corrosion reaction decrease as the increase in
the concentration of hydrochloric acid [12].
The corrosion rate of mild steel increases with increasing HNO3 acid concentration, which shows the
first order corrosion reaction without changing the reaction mechanism. This can be attributed to the
increase in the concentration of oxygen close to the metal surface by eddy transport [5] can also be
due to increase in the rate of chemical reaction with increasing concentration [13].

Fig. 2. Corrosion behavior of mild steel in different concentrations of in HNO3.

Summary. Uniform corrosion is easier to predict compared to localized corrosion. The studied
carbon Corrosion steels shows significant corrosion behavior in various acidic media and time
exposure. The corrosion rate of all carbon steels increases with the increase in the time of exposure.
The corrosion rate was maximum in nitric acid medium due to its oxidizing property. The studies also
shows that the increase of corrosion rate of mild steel with the increase in concentration of nitric acid

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which can be attributed to increase in reaction rate and breaking down the passivating layer on the
surface of the sample.
References
[1] R. E. Melchers, R. Jeffery, Early corrosion of mild steel in seawater, Corrosion Science, Volume
47, Issue 7, July 2005, Pages 16781693, DOI 10.1016/j.corsci.2004.08.006
[2] Robert Jeffrey and Robert E Melchers. (2003) Bacteriological influence in the development of
iron sulphide species in marine immersion environments. Corrosion Science 45:4, 693-714, DOI
10.1016/S0010-938X(02)00147-6
[3] G. Saha, N. Kurmaih, N. Hakerman, Inhibition of acid dissolution of metals. i. some general.
observations, J. Physis. Chem., 59 (8), 1955, 707-710. DOI: 10.1021/j150530a007
[4] M.G. Fontana, Corrosion Engineering. 3rd Edition, McGraw-Hill Book Company, New York, 346,
1987.
[5] S. Samar Hussein, A. Ali Naseer and O. Hasan Basim, Corrosion of carbon steel in flowing
Sulfuric acid, International Journal of Current Engineering and Technology, 6 (1), 2016, 277-283.
http://inpressco.com/category/ijcet/vol-6-no-1-feb-2016/
[6] R. A. Freeman, D. C. Silverman, Error Propagation in Coupon Immersion Tests, Corrosion, 48
(6), 1988, 463-466. DOI: http://dx.doi.org/10.5006/1.3315961
[7] S.K. Singh and A.K. Mukherjee Kinetics of Mild Steel Corrosion in Aqueous Acetic Acid
Solutions, J. Mater. Sci. Technol., 26 (3), 2010, 264-269. DOI: 10.1016/S1005-0302 (10)60044-8
[8] E. Osarolube, I. O. Owate, I. O. and N. C. Oforka, Corrosion behaviour of mild and high carbon
steels in various acidic media, Scientific Research and Essay, 3 (6), 2008, 224-228.
http://www.academicjournals.org/journal/SRE/article-abstract/9D02F7014290
[9] Chinwko Emmanuel Chuka, B. O. Odio, J. L. Chukwuneke, J. E. Sinebe, Investigation Of The
Effect Of Corrosion On Mild Steel In Five Different Environments, International Journal of
Scientific & Technology Research, 3 (7), 2014, 306-310. http://www.ijstr.org/research-paper-
publishing.php?month=july2014
[10] X. G. Zhang, Corrosion and Electrochemistry of Zinc, Plenum, New York, 1996.
[11] Hand book of stainless steels, Outokumpu Oyj, 2013.
[12] Anees A. Khadom, Aprael S. Yaro, 1Abdul Amir H. Kadum, Ahmed S. AlTaie and 1Ahmed Y.
Musa, The Effect of Temperature and Acid Concentration on Corrosion of Low Carbon Steel in
Hydrochloric Acid Media, American Journal of Applied Sciences 6 (7), 2009, 1403-
1409.http://thescipub.com/PDF/ajassp.2009.1403.1409.pdf
[13] BI Ita, OE Offiong. Inhibition of Steel Corrosion in Hydrochloric Acid by Pyridoxal, 4-
methylthiosemicarbazide, pyridoxal- (4- methylthiosemicarbazone) and its Zn (II) complex.
Mat.Chem. Phy., 48, 1997, 164-169.

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Exploring the Properties of NiO Nanoparticles Prepared by Reflux Method10

A. Dhayal Raj1,a, A. Albert Irudayaraj1, A. Reenaarul Vani1

1 Department of Physics, Sacred Heart College, Tirupattur, India


a dhayalraj03@gmail.com

DOI 10.2412/mmse.25.82.979 provided by Seo4U.link

Keywords: NiO nanostructures, pH, SEM, XRD, reflux method.

ABSTRACT. Admirable nanoparticles of nickel oxide have been synthesized by Reflux method. Required amount of
nickel nitrate was dissolved in 200ml of Ethylene Glycol (EG).To the above solution 50ml of PEG was added and stirred
well. The pH of the solution was adjusted as 8, 10 and 12 using HCl in order to investigate the effect of pH on the
properties of the prepared NiO nanoparticles. The precipitate was collected, washed several times and was calcinated at
500oC for 1 hr. The samples were subjected to various characterizations such asXRD, SEM, UV and FTIR, inorder to
study its structure, morphology, optical properties and functional group. The results show that pH plays a key role in the
synthesis of NiO nanostructures. The morphology of the prepared samples holds substantial promise for applying NiO as
a potential gas sensing material.

Introduction. Nickel oxide (NiO) nanoparticles have been received considerable attention due to
their wide range of applications in various fields included the fabrication of catalysis [1-4], electro
chromic films [4-6], fuel cell electrode and gas sensors [6-9], battery cathodes [10-11], magnetic
materials [12-13], photovoltaic devices and electrochemical super capacitors, smart windows and
dye-sensitized photocathodes [14]. Therefore, NiO became one of the most important transition metal
oxides. However, most of these applications require particles with a small size and a narrow size
distribution. The reduction in size leads to the volume effect, the quantum size effect and the surface
effect which in turn improves the properties of NiO nanoparticles.
One of the major challenges, the world recently facing is energy consumption and demand. To meet
the energy requirements of this modern generation, an ideal energy storage device is needed at present
to provide high energy in short time. Especially, the device should store more power and deliver high
energy output for various applications. Among all energy storage devices, electrochemical capacitors
exhibit high power density than other electrochemical devices, such as batteries, photo-voltaic
devices, etc. and high energy density than conventional capacitors because of unique charge storage
mechanisms. Transition metal oxides have been studied to obtain high specific capacitance and high
charge/discharge ability in electro-chemical capacitors. Among the transitional metal oxides
available, nickel oxide is an attractive material in electrochemical devices. In this research work,
nanocrystalline nickel oxide nanoparticles have been prepared by reflux method. The prepared
samples are found to have uniform particle size distribution and excellent morphological
characteristics. The obtained results were discussed and presented in this research article.
Experimental. Required amount of nickel nitrate was added to 200ml of ethylene glycol. To the
above solution 50 ml of PEG was added and stirred well. The pH of the resultant solution was altered
to the required value (10 and 12) using dilute HCL. The final solution was refluxed for 5 hours under
constant stirring. The precipitate was collected, washed several times with double distilled water and
ethanol. Then it was dried and calcinated at 500C for 1 hour. The samples were subjected to various

10
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characterizations in order to investigate the effect of pH on the properties of the prepared NiO
nanoparticles.
Results and Discussion. Structural Analysis

Fig. 1. XRD pattern for the NiO nanoparticles a) pH10 b) pH12.

Fig. 1 (a - b) shows the XRD pattern for the NiO nanoparticles prepared by reflux method. The sharp
peaks obtained in the XRD patterns show the crystalline behavior of the materials due to high
temperature heat treatment carried out at 500C. The obtained XRD patterns were compared with the
reported standard JCPDS data for NiO (JCPDS card No: 89-7131). The XRD patterns obtained for
NiO (calcined at 500C for 1 h) reveal the formation of well-crystallized single phase face centered
cubic (FCC) geometry as reported. The XRD patterns of each sample exactly agree with the JCPDS
data without any collateral peaks, indicating high purity of the prepared samples. The crystallite size
of the particles, determined with Scherrers formula, was found to be in the range of 10-20 nm.
3.2 Morphological Analysis

a b

Fig. 2. HR-SEM images for the NiO nanoparticles a) ph 10, b) ph 12.

The SEM images of the NiO nanoparticles prepared by reflux method are shown in Fig. 2 (a and b).
From the SEM images, it was understood that all NiO grains are spherical in shape. From the Fig.s,
it was found that the grains are present in the range of 22nm and 34 nm for the samples prepared with

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pH values 10 and 12 respectively. However, the presence of bigger grains in the samples may be due
to the high temperature treatment procedure adopted during calcination.
Functional group analysis. Spectra of the pH10 and pH12 products NiO nanoparticles after
calcination. A narrow and strong band at 3420 cm1 relating to the (OH) stretching vibration. The
broad and intense band centered at 2919cm1 is assigned to the OH stretching vibration of the
interlayer water molecules and of the Hbound OH group. The peak observed at 1644 cm1 is assigned
to the bending vibration of water molecules. Calcination, the FT-IR spectra of NiO nanoparticles
shows strong band at 425 to 800 cm1 corresponds to the vibration of NiO bond. It could be seen
from Fig. 2 that the broad absorption band attributable to the band OH stretching vibrations, due to
the fact that the calcined powders tend to physically absorption of water due to KBr (Fig. 3).

Fig. 3. Transmittance vs. wavenumber.

Optical analysis. Spectra of pH 10 and pH 12 NiO nanoparticles are shown in Fig. 4. The Fig. 4
shows that the broad and less symmetric absorption peaks were observed at 350nm, due to blue shifted
as compared to the bulk material. The blue shifting of effects are caused due to the quantum size
effect where as the broadening and as symetricity are due to the huge size distribution of synthesized
materials and it was also conformed to our SEM results. The band gap energy (Eg) of the nano
particles was calculated using the formula Eg=h/. This absorption spectrum of chosen nanomaterial
gives the good relation between the particle and band gap obtain value of particle size is 3.37eV and
3.55eV respectively (Fig. 4).

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Fig. 4. Absorption vs. wavelength.

Summary. The NiO nanoparticles have successfully prepared by reflux method with different pH
values. The phase and purity of both the samples was confirmed by X-ray diffraction analysis. The
size of the nano-crystallites was 10nm and 20 nm, as evaluated by the well-known Sherers formula
for samples prepared with pH values 10 and 12 respectively. SEM revels that the samples show
spherical morphology as shown and the size has been increased with increasing the pH value. It is
clear show that pH is plays a vital role in controlling the size of the particle. From the FTIR spectra
irrational peaks around 743cm-1 and 828cm-1 to confirm the formation of NiO. The band gap of NiO
was calculated from the absorption spectra and was found to be 3.1eV and 3.4eV respectively.
Reference
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Ni) Oxide Nanocrystals via a Simple and General Approach, Chem. Mater., 16, 2004, 3931- 3935.
DOI 10.1021/cm049221k
[2] W. Wei, X. Jiang, L. Lu, X. Yang and X. Wang, Study on the catalytic effect of NiO nanoparticles
on the thermal decomposition of TEGDN/NC propellant, J. Hazard. Mater., 168, 2009, 838-842.
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[3] N. R. E. Radwan, M. S. El-Shall and M. A. Hassan, Synthesis and characterization of nanoparticle
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[5] X.W. Lou, D. Deng, J.Y. Lee, J. Feng and L.A. Archer, Self-Supported Formation of Needlelike
Co3O4Nanotubes and Their Application as Lithium-Ion Battery Electrodes Adv. Mater., 20, 2008,
258 -262. DOI 10.1002/adma.200702412
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sensor applications, Vacuum 58, 2000, 300-307. DOI 10.1016/S0042-207X (00)00182-2
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1712-1715. DOI 10.1021/cg060732o

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[8] Q. Zhao, Z. Zhang, T. Dong and Y. Xie, Facile Synthesis and Catalytic Property of Porous Tin
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Effect of Precursor Concentration of MgO Nanostructure by using Sol-Gel


Method11

V.T. Srisuvetha1, 2 ,a, S.L. Rayar2, G. Shanthi1, A. Dhayal Raj3, S. Karthikeyan4

1 Depatment of Physics, Research Center Womens Christian College, Nagercoil.K.K. (DT), Tamilnadu, India
2 Depatment of Physics, St.Judes College, Thoothoor, K.K. (DT), Tamilnadu, South India
3 Depatment of Physics, Sacred heart college, Tirupattur, Vellore (DT), Tamilnadu, India
4 Department of Physics Periyar University PG Extension Centre, Dharmapuri, India
a srisuvetha16@gmail.com

DOI 10.2412/mmse.76.30.166 provided by Seo4U.link

Keywords: magnesium oxide, sol-gel method, oxalic acid, XRD, SEM, UV, FTIR, EDS.

ABSTRACT. MgO thin flims have been prepared on substrates by a novel and simple sol-gel method using magnesium
nitrate and collusion as starting material.The MgO nano catalyst with good sensor crystallization were obtained after
annealing at 100C Magnesium oxide was prepared by sol-gel method. The method involves the hydrolysis of magnesium
alkoxide in the presence of acid or basic catalysts followed by a Oxalic acid reaction. The synthesized solids were
characterized by IR spectroscopy X-ray diffraction electron microscopy. Ultraviolet visible absorbance measurement
photoluminescence and Raman scattering spectra. X-ray diffraction (XRD) characterization showed the formation of
smaller particles after sol gel irradiation the structure and morphology of the MgO particles were analyzed byXRD. These
articles were used for FTIR spectroscopic measurement and spectra were collected. In EDS we calculated the peak
intensity the SEM the images of metal oxide.UV (Ultra Violet) refers to adsorption spectroscopy optical properties of
assorption, band gap energy.This means if use light in the visible and adjacent ranges.

Introduction. MgO is highly ionic insulating crystalline solid with structure, which has excellent
properties such as chemical inertness, electrical insulation, optical transpare high temperature
stability, high thermal conductivity and secondary electron emission.
In the present investigation the sol gel method was adopted to achieve a homogeneous disperation of
MgO and the effects of MgO on mulltization sinterability& physical properties were investigated
manganese works as luminescence centers in oxide& non-oxide materials, studies of green, orange,
red phosphors containing manganese have been performed for a long periods. Magnesium oxide is a
versatile oxide material with respect to its wide range of utilization such as in catalysis, hazardous
waste treatment, anti microbial materials and refractory materials.Recently MgO has attracted
tremendous attention on account of these immense application. Particularly in the field of catalysis,
MgO has become promising materials in the roles of both catalyst and catalyst support in many
organic reactions.
Methods
Sol Gel. In materials science, the sol-gel process is a method for producing solid materials from small
molecules. The method is used for the fabrication of metal oxides, especially the oxides of silicon
and titanium. The process involves conversion of monomers into a colloidal solution (sol) that acts
as the precursor for an integrated network (or gel) of either discrete particles or network polymers.
Typical precursors are metal alkoxides.

11
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In this chemical procedure, the 'sol' (or solution) gradually evolves towards the formation of a gel-
like diphasic system containing both a liquid phase and solid phase whose morphologies range from
discrete particles to continuous polymer networks[39]. In the case of the colloid, the volume fraction
of particles (or particle density) may be so low that a significant amount of fluid may need to be
removed initially for the gel-like properties to be recognized. This can be accomplished in any number
of ways.
Experimental.
Magnesium acetate tetrahydrate

150 ml ethanol

Stirr half an hr

Oxalic acid

Stir half an hour

Ageing overnight (24hr)

Dried at 100c for 24 hrs

Motor & piston 1 hr

Magnesium Oxide (MgO) is an important oxide material that used in many application such as gas
sensor, catalysis supports, toxic wastes remediation, refractory materials and adsorbents.The
commercial MgO particles have been prepared via thermal decomposition of Magnesium salts or
magnesium hydroxide. The resulting MgO has large particle size and small surface area, which are
disadvantages for use in some applications, Therfore, Many synthesis methods have been developed
to prepare nano sized of MgO with large surface area with controlled morphology as reported in. A
Sol-gel method is one of the promising approaches due to its simplicity, Cost-effective, high yield of
final product and low reaction temperature.
The organic salts such as magnesium methoxide and magnesium ethoxide are rare used in sol-rel
reaction for formation of MgO nanoparticles and these discussed in a few reports.As an alternative,
inorganic magnesium salts are reacted with different complexing agents and give various precursors
before decomposed to MgO.However, the sol-gel method used is usually caused agglomeration of
MgO particles, which hinder its wide applications
The controlled synthesis for MgO with specific morphology, small crystallite size and large surface
area are challenging aspects to be studied.Magnesium acetate tetrahydrate added with 150ml ethanol
stirred with half an hour and just added polyethylene glycol and once again stirred with half an hour
and ageing overnight and dried at 100C for 24hrs.
Results and Discussion.

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SEM Morphology. SEM images it was found that both of the nano structure represent sphere like
and rounded morphology. According to these results it can be mentioned that SEM results are in good
agreement with particles size distribution and surface area. MgO nano scale particles interconnected
with each other such that no clear bound aries exist between one another. The average range of the
particle for pure polyethylene glycol is 18nm. Fig. 1 (a). The average range of the particle for with
calcination polyethylene glycol is 25nm. Fig. 1 (b). The average range of the particle for without
calcinations polyethylene glycol is 28nm. Fig. 1 (c). The Morphology of the Mgo particles is in
nanoscale range. Due to sol gel method, the sizes of these particles are in the range.

a) b) c)
Fig. 1. (a) Pure polyethylene at 100C, (b) without calcinations 100C, (c)with calcinations 100C.

a) b) c)
Fig. 2. (a) Pure polyethylene at 100C, (b)without calcinations at 100C, (c)with calcinations at 100C.

EDS
Depicts the EDS analysis of insulated powders after heating at a temperature 100C for 24 hr which
consists of magnesium, oxygen and iron peaks with respect to the analyzed depth, the comparision
between the intensity of magnesium oxygen and under laying iron peaks reveals that the insulating
layer in thin. The Mgo present in polyethylene glycon at 100C
FTIR
FTIR spectroscopy was used to identify the functional group in the synthesized MgO nanoparticles.
Functional group with the strong dipole give rise to strong absorption in the region. Different
molecular groups present in the MgO are identified with the Vibrational frequencies.The IR spectrum
of MgO was recorded with a BRUKER.Fourier transform Infrared spectrometer in the range of 600-
4000cm-1.The observed spectrum of synthesized MgO is present in Fig. (a and b)corresponding to
samples prepared with Ph values respectively.The strong absorption peaks in the metal-oxide
vibrations.Thus can be correlated to Mg-O vibrations. The Mg-Ovibrations around 890cm-1 are in
agreement with the earlier reports.The FTIR spectra of coated powders before the final heating it has
been proposed that the preparation of metal oxide by sol-gel methods to high hydroxylated materials.

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Thin insulation leads to the densities of the MgO insulated samples and uncoated compacts to be
close to each other.Also the nature of the insulating layer can be assessed by FTIR analysis.

b)
a) c)
Fig. 3. (a) Pure polyethylene at 100C, (b)without calcinations at 100C, (c)with calcinations at
100C.

Summary. EDS and X-ray analysis, FTIR spectra and density measurements showed that the
particles surface layer contained a MgO insulating layer with uniform coverage of the powder
surfaces after sol-gel processing. The MgO worked effectively on band gap engineering irrespective
structure.In this work, the sol-gel methods for heat treated soft magnetic composites with a thin MgO
insulation layer.MgO insulating has higher thermal stability than polyethylene glycol. The produced
nanostructure particles were characterized to determine particle size distribution, surface properties.
It is well known that various factors, such as crystalline size, morphology. Further more the nano
structure particles can be easily produced through sol gel method technique in one-step, whereas it is
unable with sol-gel method that this conditions influences production cost. The importance of the
present articles lies is establishing that MgO supports can be obtained by the sol-gel method. The
effects of these MgO supports on catalytic activity will be dealt with in future work.
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[2] Cline, C.F. and Newkirk, H.W.: 'Electrical transport processes in BeO, Chem. Phys., 1968, 49,
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[9] D. Gabriel, H.H.J. Cox, M.A. Deshusses, Conversion of full-scale wet scrubbers to biotrickling
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Synthesis, Structural, Optical and Photocatalytic Studies of Nanostructured


Cadmium Doped ZnO Nanorods by Hydrothermal Method12

P. Logamani1, G. Poongodi2, R. Rajeswari3,a

1 Department of Chemistry, Bharathiyar University, Coimbatore, India


2 Department of Chemistry, Quaid-e-Millath Govt. College for Women, Chennai, India
3 Department of Physics, Quaid-e-Millath Govt. College for Women, Chennai, India
a rajikanna99@yahoo.co.in

DOI 10.2412/mmse.37.62.535 provided by Seo4U.link

Keywords: cadmium doped ZnO, nanorods, hydrothermal method, FESEM.

ABSTRACT. Nowadays, considerable attention has been paid to the eradication of hazardous substances in the
environment especially in the wastewater. The photocatalytic reaction is used to mineralize the hazardous recalcitrant
pollutants in to simple and harmless compounds and has been enhanced by the application of nanoparticles. Zinc oxide
(ZnO) is a nontoxic wide band gap semiconductor photocatalyst, having unique properties such as high mobility, excellent
chemical and thermal stability, high transparency and biocompatibility. To enhance its photocatalytic activity in the
visible region ZnO can be doped with metals and non-metals. In the present work, pure and cadmium doped ZnO nanorods
were prepared by hydrothermal method and characterized by X-ray diffraction, field-emission scanning electron
microscopy with EDAX and UVVis spectroscopy. The XRD results showed that the grown nanorods were well
crystalline with hexagonal wurtzite structure. FESEM images confirm the nanorod structure. UV-Vis transmission spectra
show that the substitution of Cd in ZnO leads to band gap reduction. The Cd doped ZnO nanorods were found to exhibit
improved photocatalytic activity for the degradation of methylene blue dye under visible light in comparison with the
undoped ZnO.

Introduction. Semiconductor photocatalysts have been extensively studied to remove harmful


organic pollutant as well as energy production, since the photocatalytic splitting of water on TiO2
electrode has been reported by Fujishima et al (1972) [1]. The semiconductors as photocatalysts have
shown excellent utility in the complete mineralization of various environmental pollutants such as
dyes, detergents and volatile organic compounds [2]. In recent years, ZnO has been studied as
photocatalyst, for the destruction of wide range of organic pollutants [3]. One of the main limitations
of ZnO is the photo-instability in aqueous solution, when it is exposed to UV irradiation, the
photocatalytic activity of ZnO gets decreased [4]. Several efforts have been made to reduce the
instability of ZnO, among which transition metal doping is the simple and efficient technique to
reduce photoinstability. Furthermore, the optical absorption and photocatalytic performance of ZnO
can be improved by transition metal dopants [5, 6]. In particular, cadmium is considered as a potential
material for its abundant electron states and large solubility into ZnO matrix [7]. During the
photocatalytic reaction, cadmium in ZnO matrix acts as an electron sink to enhance the separation of
photo-excited electrons from holes, which favors the photocatalytic activity. In this study, the
nanostructured pure and Cd doped ZnO nanorod samples were prepared by hydrothermal method.
The influence of cadmium doping on the structural, optical and photocatalytic properties of ZnO has
been studied.
Experimental detail

12
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Nanostructured Cd doped ZnO powder was prepared by hydrothermal method. All the reagents were
of analytical grade purity. All the reagents were of analytical grade purity. Aqueous solutions of 0.1
M zinc chloride and 0.01 M cadmium chloride were mixed under continuous stirring for 45 min at
room temperature. After stirring, aqueous solution of 0.1 M hexamethylenetetramine (HMTA) was
added in the previous solution and the resultant solution was again stirred for 30 min. The pH of the
solution was maintained to 8.0 by adding few drops of ammonium hydroxide. The final solution was
again vigorously stirred for 30 min and consequently transferred to Teflon lined autoclave which was
then sealed and heated up to150 for 5 h. and the same procedure was repeated without cadmium
chloride for pure ZnO. After terminating the reaction, the autoclave was allowed to cool at room-
temperature and the obtained products were washed several times with deionised water and ethanol.
Finally the prepared products were dried at 60.
Characterization. The nanocrystalline structure of Cd doped ZnO powder was investigated byXRD.
The surface morphology and elemental confirmation of nanorods were studied using FEI Quanta FEG
200 model FESEM operated at 30 kV equipped with an energy-dispersive X-ray (EDAX) detector.
The optical transmission spectra were recorded using LABINDIA T90+ UV-Vis spectrophotometer
in the wavelength range 300-800 nm. The photocatalytic activity of pure and Cd doped ZnO was
carried out by degradation of methylene blue (MB) (110-5 M) in aqueous solution. The absorption
spectra of MB at different irradiating intervals using pure and Cd doped ZnO samples as photocatalyst
were recorded by using UV-Vis spectrophotometer. The photocatalytic degradation was evaluated by
measuring the absorbance of MB solution at 665 nm. The degradation efficiency of MB was
calculated using the relation [8],

Degradation (%) = (C0 Ct)/C0 x 100 = (A0 At)/A0 x 100

where C0 is the initial concentration;


Ct is the concentration after t min;
A0 is the initial absorbance;
At is the absorbance after t min. reaction of MB solution at the characteristic absorption
wavelength of 665 nm.
Result and discussion
Structural studies. The crystal structures of pure Cd doped ZnO samples were confirmed by XRD
analysis.

Fig. 1. XRD patterns of pure and Cd doped ZnO.

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Fig. 1 shows the powder XRD patterns of Cd doped ZnO samples. All the diffraction peaks of grown
samples were indexed and found to be Wurtzite hexagonal structure (JCPDS No.36-1451). It is
evident from the XRD data that no extra peaks related to cadmium metal, other oxides phase were
detected, which illustrates that the obtained are of single phase. But a small lower angle shift was
obseved for Cd doped ZnO sample when compared to pure sample which may be caused by the
substitution of Cd in ZnO (inset of Fig.1). This slight variation indicates that the incorporation of
cadmium ion into the ZnO lattice. Fig. 2 shows the FESEM image of the prepared Cd doped ZnO
sample. The morphology of Cd doped ZnO sample was one dimensional rod structure. The typical
length of the nanorods is in the range of 500550nm, while the diameters are in the range of 50-80
nm.

Fig. 2. FESEM image of Cd doped ZnO.

The EDAX analysis was performed to confirm the presence of Cd in ZnO sample. The EDAX spectra
of pure and Cd doped ZnO samples are shown in Fig.s 3. The results showed that the samples consist
of Zn, Cd and O, which confirms the substitution of cadmium in ZnO.

Fig. 3. EDAX Spectra of pure and Cd doped ZnO.

Optical studies
The optical UV-Vis transmittance spectra of pure and Cd doped ZnO samples were recorded in the
wavelength range 300 800 nm are shown in Fig. 4. The optical band gap energy values (Eg) were
calculated by extrapolation of the linear part of (h)2 versus h plot as shown in inset of Fig.4. It was

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observed that the band gap values of pure and Cd doped ZnO samples are 3.18eV and 3.14eV. The
reduction in the band gap is likely to originate from the sp-d exchange interaction between the
localized d-electrons of Cd+ ions and band electrons of ZnO as well as the lattice expansion [9]. This
band gap narrowing is expected to find important application in photocatalysis, since more solar
energy might be effectively used for photocatalytic reaction.

Fig. 4. Optical transmission spectra of pure and Cd doped ZnO (Inset: Tauc plot between Eg and
(h)2).

Photocatalytic activity.
The photocatalytic activity of pure and Cd doped ZnO samples were investigated using MB
degradation under visible light irradiation. The result reveals that the Cd doped ZnO sample exhibit
higher photocatalytic activity than pure ZnO (Fig.5). The presence of Cd in ZnO is attributed to
improve the absorption in visible range and the large content of oxygen vacancies or defects act as
trapping centers for the photogenerated electrons. This can lead to a reduction in the recombination
of photo-generated electron pairs [10], there by promoting an interfacial charge transfer and hence,
the rate of degradation of MB was significantly increased.

Fig. 5. Photocatalytic activity and degradation efficiency of MB with pure and Cd doped ZnO.

Summary. Nanocrystalline pure and Cd doped ZnO nano powder samples were prepared by
hydrothermal method. The XRD studies revealed that the prepared samples exhibit hexagonal
wurtzite structure. FESEM image showed that the Cd doped ZnO sample consist of nanorod structure.
EDAX spectra confirmed the presence of Cd in ZnO. The optical studies revealed that the band gap
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energy was reduced, indicating that Cd doping influences the energy band structure of ZnO. Cadmium
doping in ZnO enhances the photocatalytic activity of ZnO by inhibiting electron hole recombination.
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[6] V. Etacheri, R. Roshan, V. Kumar, Mg-doped ZnO nanoparticles for efficient sunlight-driven
photocatalysis, ACS Appl. Mater. Interfaces 4 (2012) 2717-2725, DOI 10.1021/am300359h
[7] S. Mondal and P. Mitra, Preparation of cadmium-doped ZnO thin films by SILAR and their
characterization, Bull. Mater. Sci. 35 (5), (2012), 751-757, DOI 10.1007/s12034-012-0350-2
[8] K. Thongsuriwong, P. Amornpitoksuk, S. Suwanboon, Corrigendum to Structure, morphology,
photocatalytic and antibacterial activities of ZnO thin films prepared by solgel dip-coating
method, Adv. Powder Technol. 24(1) (2013) 275280, DOI 10.1016/j.apt.2015.05.001
[9] S. Kumar, R. Kumar, D.P. Singh, Swift heavy ion induced modifications in cobalt doped ZnO
thin films: Structural and optical studies, Appl. Surf. Sci. Vol. 255 (2009) 8014-8018, DOI
10.1016/j.apsusc.2009.05.005
[10] C. Xu, L. Cao, G. Su, W. Liu, X. Qu, Y. Yu, Preparation, characterization and photocatalytic
activity of Co-doped ZnO powders, J. Alloys Compd. 497 (2010) 373-376, DOI
10.1016/j.jallcom.2010.03.076

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Fabrication of Ni/Pd/Ni Multilayer by Pulsed Electrodeposition13

T.A. Revathy1, T. Sivaranjani1, K. Dhanapal1, V. Narayanan2, A. Stephen1,a

1 Department of Nuclear Physics, University of Madras, Guindy Campus, Chennai, Tamil Nadu, India
2 Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai, Tamil Nadu, India
a stephen_arum@hotmail.com

DOI 10.2412/mmse.99.96.980 provided by Seo4U.link

Keywords: multilayers, anisotropy, pulsed electrodeposition.

ABSTRACT. In the recent years, much interest has been aroused in ultrathin metallic layered magnetic structures. In
particular, the sandwich of non-magnetic element between the magnetic elements is a key for the production of structures
that exhibits magnetic anisotropy, it shows technologically significant application in perpendicular magnetic and
magneto-optic recording. The pulsed electrodeposition method was employed for the deposition of pure nickel, nickel
palladium (Ni/Pd) bilayer and nickelpalladiumnickel (Ni/Pd/Ni) trilayer films. Since pulsed electrodeposition is found
to be a powerful tool for producing multilayers and alloys [1]. The X-ray diffraction pattern confirms the formation of
fcc structure for both nickel and palladium. The cross sectional view of high resolution scanning electron microscopy
shows the layer by layer deposition of nickel and palladium in Ni/Pd and Ni/Pd/Ni films. Vibrating sample magnetometer
was employed to study the magnetic behavior of fabricated trilayer.

Introduction. Magnetic nanopattern multilayers establish a new refinement of materials unveiling a


wide variety of application such as single electron device, optical media and high-density magnetic
memory devices because of its unique property raised due to electron confinement produced in the
interfaces of thin layers [2]. Nanopattern multilayered magnetic recording media provide adequate
number of advantages than conventional continuous magnetic recording media, including better and
higher recording density. Recently research has been made with various forms of magnetic
nanopattern structures in order to attain the high recording density and multilayers with large
magnetocrystalline anisotropy, high magnetization and chemical stability are found to be more
suitable for these recording media [3]. Actually, the magnetic anisotropy of the elements are modified
due to the hybridization effects and strain at the interfaces of multilayers comprising of ferromagnetic
and non-ferromagnetic elements with periodic repetition[4]. Anisotropy of the film also depends upon
the thickness of the layer. The structure, growth condition and layer composition profiles the magnetic
property. Fabrication of layer by layer assembly of ferromagnetic nickel and nonferromagnetic
palladium multilayers are done by several technique such as sputtering, evaporation, chemical vapor
deposition, other vacuum deposition processes and electrodeposition.
Among them Pulsed electrodeposition (PED) is the less expensive and simple method for depositing
the films since PED has three parameter which can control the nature of the deposit like smoothness,
film formation, crystallinity, etc., In this work, our aim has been to fabricate Ni, deposit pure nickel,
nickelpalladium (Ni/Pd) bilayer and nickelpalladiumnickel (Ni/Pd/Ni) trilayer so as to study the
behaviour of nickel and palladium when they are in layered nature and reported the investigation of
structural, morphological and magnetic properties of layered films.
Experiment

13
2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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Multilayer films were fabricated by pulsed electrodeposition method using the standard two electrode
system. The stainless steel of grade 316L was used as cathode which is the working electrode while
graphite sheet served as an anode. The electrodes were cleaned by conventional method. The area of
the working electrode is 10 cm2. The electrolyte was prepared using double distilled water. The bath
composition and experimental conditions are given in Table 1. The Ni/Pd and Ni/Pd/Ni layered film
were deposited one by one from their respective electrolyte bath.

Table 1. Bath and experimental condition of Pure Ni, Ni/Pd, Ni/Pd/Ni films.
Applied Duration of
Bath composition Ton and Toff pH
current deposition
0.5 M of NiSO4
Nickel
0.1 M of boric 0.25A 20 min 2 ms and 9 ms 3
layer
acid
Palladium 0.05 M of
0.2A 5 min 2 ms and 9 ms 3
layer Palladium acetate

After the deposition, the layered film was subjected to various characterization. The structural
information were examined using X-ray diffraction (XRD), the formation of layered nature was
observed by employing field emission scanning electron microscopy (FE-SEM) and magnetic
behaviour was examined using vibrating sample magnetometer (VSM).
Results and discussion
XRD analysis
The deposited films were investigated for structural information by XRD (GE-XRD 3003 TT) in
standard - geometry with Cu K radiation of wavelength 1.5406 . The XRD pattern of pure Ni,
Ni/Ag and Ni/Ag/Ni film are shown in Fig. 1.

Fig. 1. XRD patterns of Pd, Ni, Ni/Pd, Ni/Pd/Ni layers.

The peaks at 40.150, 46.700 and 68.190 were attributed to the (111), (200) and (220) planes of fcc
phase of Pd respectively and the peaks at 44.550, 551.890 and 76.450 were corresponds to the fcc
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planes of Ni (111), (200) and (220) respectively. In the case of Ni/Pd film, both palladium and nickel
are in crystalline nature, which is confirmed by sharp intense peaks. On the other hand, intensity of
nickel is decreased as palladium layer was coated over it. The intensity of Ni peaks was again
increased in Ni/Ag/Ni film and palladium peak intensity decreased when compared to the Ni/Pd film.
FE-SEM analysis
The layered nature of the films were inspected by HRSEM. The cross sectional view of all the Ni,
Ni/Pd, Ni/Pd/Ni were shown in Fig. 2. The cross sectional view of pure Ni film is shown in Fig. 2 (a)
and found to be a smooth layer with the thickness of ~7.3 m. Fig.2 (b) reveals the formation of
layered nature with palladium on to the nickel layer with the thickness of ~3.1 m and ~3.5 m
respectively. The thickness of the layers was calculated using ImageJ software. The cross sectional
view of Ni/Pd/Ni was shown in Fig. 2 (c), the image revealed the formation of Ni/Pd/Ni trilayer film
in such a way that the Pd layer is sandwiched in between the two Ni layers. In the trilayered film, Ni
layer is found to be dominant with the thickness of first layer to be~0.6 m and third layer with
thickness of ~7.6 m, respectively. The thickness of sandwiched Pd layer was estimated to be ~0.57
m.

(a) (b)

(c)

Fig. 2. (a) Cross sectional FESEM image of pure Ni film, (b) Cross sectional FESEM image of Ni/Pd
film, (c) Cross sectional FESEM image of Ni/Pd/Ni film.

Magnetic property analysis


The magnetic behaviour of the deposisted films were examined using VSM (Lakeshore VSM 7410).
The hysteresis behaviour of pure nickel, Ni/Pd and Ni/Pd/Ni films are shown in Fig. 3

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Fig. 3. Hysteresis behaviour of Ni, Ni/Pd, Ni/Pd/Ni layers.

The saturation magnetization values of Pure Ni, Ni/Pd and Ni/Pd/Ni is foung to be 104.60 emu/cm 2,
26.1 emu/cm2 and 137.2 emu/cm2 respectively. value decreases for Ni/Pd layer when compared to
pure nickel which is because of non-ferromagnetic palladium. The increase in saturation
magnetization for Ni/Pd/Ni layer compared to Ni/Pd layer is due to the presence of third layer nickel.
The loop reveals that the coercivity value for all the three films are almost same, which indicates that
the magnetic field required for demagnetization, is same for all the films.
Summary. The pure Ni, Ni/Pd and Ni/Pd/Ni films were deposited fabricated by simple pulsed
electrodeposition method. The XRD pattern unveils the formation of fcc structure for both palladium
and nickel in Pure Ni and layered films. The layered nature of Ni/Pd, Ni/Pd/Ni and film nature of
pure Ni were determined using cross sectional HRSEM and found that layers are formed with sharp
interface. The magnetic behaviour of all the films are determined using VSM which shows that
saturation magnetization of Ni/Pd/Ni trilayer is greater than that of pure nickel film.
Acknowledgements. One of the authors T.A.R acknowledges UGC-UPE-Phase II for its financial
assistance in the form of fellowship.
References
[1] K. Dhanapal, T.A. Revathy, M. Anand Raj, V. Narayanan, A. Stephen, 2014. Magnetic anisotropy
studies on pulsed electrodeposited Ni/Ag/Ni trilayer, Applied Surface Science, DOI:
10.1016/j.apsusc.2014.06.058
[2] K.R. Pirota, D. Navas, M. Hernndez-Vlez, K. Nielsch, M. Vzquez, 2004. Novel magnetic
materials prepared by electrodeposition techniques: arrays of nanowires and multi-layered
microwires, Journal of Alloys and Compounds, 2004, 18-26 DOI: 10.1016/j.jallcom.2003.09.040
[3] Guillermina Gmez, Gabriela F. Cabeza, Patricia G. Belelli, 2009. Electronic and magnetic
properties of Pd-Ni multilayers: Study using density functional theory, Journal of Magnetism and
Magnetic Materials, 3478-3482, DOI: 10.1016/j.jmmm.2009.06.059
[4] J.W. Feng, Magnetic anisotropy of sputtered Ni/Ag multilayers, Journal of Magnetism and
Magnetic Materials, 1996, 27-32 DOI: 10.1016/0304-8853(95)00445-9

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Polymer Composites for Thermal Sensing Application14

Isha Pandey1, D. Arthisree2, A. Sivakumar1, Girish M. Joshi2, a

1 Department of chemistry, School of Advanced Sciences, VIT University, Vellore-632014, TN, India
2 Polymer Nanocomposite Laboratory, Centre for Crystal growth, School of Advanced Sciences, VIT University,
Vellore-632014, TN, India
a girish.joshi@vit.ac.in

DOI 10.2412/mmse.2.26.724 provided by Seo4U.link

Keywords: hydroxypropyl methylcellulose (HPMC), conducting carbon black (CCB), phase angle, composite.

ABSTRACT.Carbon black (CCB)/Hydroxypropyl methylcellulose (HPMC) composites were useful for the sensor
applications. Easily available Carbon black was preferred for the modification of polymer moieties. Due to an excellent
coloring agent, printing inks, resin coloring, paint, and toners. Further, CCB is also used in various electrical conducting
agent, antistatic film, fibers and floppy disk. In the present investigation we demonstrated the successful preparation of
Hydroxypropyl methylcellulose with (CCB) composites. We have observed the linear phase relation as a function of
temperature for the sample 1wt% loading of CCB. The linearity of phase measurement based on temperature is useful for
various engineering applications.

Introduction. Development of electrically conducting organic carbon based polymer composites


prepared by fusion of nanofillers such as flakes [1], carbon black [2], graphite [3] have attracted
researchers for decades due to their extraordinary properties like high stiffness, low weight and high
electrical conductivity in the range of 10-1-102(ohm cm-1) [4]. CCB are used in various electrical,
mechanical and thermal properties [5]. Property of the polymer may change by loading the
concentration of filler [6]. Due to these unique properties of carbon we have chosen to prepare
polymer composite using CCB as filler.
Generally, polymers are non-conducting in nature; to optimize its conductivity was more challenging
research interest. They possess low weight, decompose-resistant materials which are used in a wide
variety of industrial and military, sensor applications [7]. Hydroxypropyl methylcellulose (HPMC) is
a different grade cellulose polymeric family, a natural carbohydrate that holds continuous glucose
structural units. It is hydrophilic polymer with wide useful properties like fluid retention purpose,
lubricants, natural gum and emulsifiers, used as thickener, film former, and excellent drug delivery
component in oral medication [8]. Inflexible hybrid composite film using Carbon black/rubber have
been prepared and used in engineering applications [9], But there may some technical difficulty in
casting composite with rubber. Using Carbon black with PET and PMMA a composite was prepared
and their surface investigations were studied [10], polymer used in particular work is highly costly.
In our present study we prepared polymer composites using HPMC/CCB and disclosed their phase
angle response. Where HPMC is cheaper material and easy to casting the film.
Experimental Procedure
Chemicals and reagents

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Hydroxypropyl methylcellulose is an analytical grade reagent, viscosity is in the range of 2600-


5600(CP), and 2% soluble in water at 20oC, Molecular weight is 86 Kilodalton purchased from Sigma
aldrich. Conducting Carbon black was provided by Timcal Graphene and Carbon, ENSACO 250 g.
Synthesis of HPMC/CCB composites
Five different concentration of HPMC is mixed with water in the ratio of 3:200, and kept on stirring
for almost 56hrs continuously. When the solution is uniform, it is divided into three equal parts. One
portion of the each solution is mixed with 1% of CCB by wt/wt of HPMC, other portion with 5%
CCB by wt/wt of HPMC. All the mixtures with CCB added in it are stirred for another 45mins. Then
the mixtures are poured evenly in a Petri dish and are allowed to dry overnight. After the mixture is
completely dried up, the corners are cut with the help of a sharp blade, and the film is genteelly peeled
off the Petri dish.
Results and discussion
The electrical properties of polymers were applicable for electrical, electronic engineering
applications. Basically the polymer moieties were highly sensitive for external stimuli such as
pressure, humidity, temperature, radiations, electrical field. In the present work we exposed the
polymer HPMC and HPMC/CCB composite as function of temperature. The phase angle as function
of temperature is shown in figure 1 and 2. The principle involved in measurement of voltage and
current ideally expected uniform provided the 900 phase. However the electrical signal propagated
through the sample demonstrated the current voltage phase variation. It may be due the chemical
moieties of polymers. Compare to the pure sample of CA the small amount of 1% composition of
CCB demonstrate the effect of temperature on phase behavior. The trend of phase separation was
directly proportional to the applied temperature. This property of composite enable to detect the
increase in the temperature (tested in the range of 30 to1200). The phase angle based testing was much
applicable in the domains of bio impedance analysis, power-electrical, potentiometric property in
electronic devices.

35

30
30
40
25 50
60
20 70
Phase angle ()

80
15 90
100
10 110
120
5

-5
200Hz 1kHz 10kHz 100kHz 1MHz
Frequency (Hz)

Fig. 1. Phase angle () as a function temperature of HPMC film.

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90

80

70 30
40

Phase angle ()
60 50
60
50 70
80
40 90
100
30
110
120
20

10

400Hz 4kHz 60kHz 1MHz


frequency (Hz)

Fig. 2. Phase angle () as a function of temperature of HPMC/CCB composite film.

Summary. We demonstrated the successful preparation of polymer nanocomposite by reinforcing


CCB with HPMC host system. It exhibits decrease in impedance as function of CCB loading.
However, the criteria voltage and current phase enable record the temperature difference.
Furthermore, this property of phase difference as function of temperature may be developed as
thermal sensor for engineering devices.
References
[1] Tsuguyori Ohana, Takako Nakamura, Akihiro Tanaka, Tribological properties of polymer
composites with diamond-like carbon flakes, National Institute of Advanced Industrial Science and
Technology, DOI 10.1016/j.diamond.2010.02.020
[2] I. Burmistrov, N. Gorshkov, I. Ilinykh, D. Muratov, E. Kolesnikov, S. Anshin, I. Mazov, J.-P.Issi,
D. Kusnezov, Improvement of carbon black based polymer composite electrical conductivity with
additions of MWCNT, DOI 10.1016/j.compscitech.2016.03.032 0266-3538
[3] Raquel Verdejo, M. Mar Bernal, Laura J. Romasanta and Miguel A. Lopez-Manchado, Graphene
filled polymer nanocomposites, DOI 10.1039/c0jm02708a
[4] Michael E. Spahr, Raffaele Gilardi, Daniele Bonacchi, 2014, Carbon Black for Electrically
Conducting Polymer Applications, Springer, DOI 10.1007/978-3-642-37179-0_32-1
[5] Suchilipsa Das, Patnala Ganga Achary, Nimai C. Nayak, Ram Narayan Prasad Choudhary,
Dielectric Response of Conducting Carbon-Black-Filled EthyleneOctene Copolymer Microcellular
Foams, DOI 10.1002/pc.23538
[6] B.P.Sahoo, K.Naskar, R.N.P. Choudhary, S. Sabharwal, D.K. Tripathy, 2011, Dielectric
Relaxation Behavior of Conducting Carbon Black Reinforced Ethylene Acrylic Elastomer
Vulcanizates, DOI 10.1002/app.35049
[7] Dipti Phadtare, Ganesh Phadtare, Nilesh B, Mahendra Asawat, 2014, Hyprmollose- A choice of
polymer in exended release tablet formulations.

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[8] Premamoy Ghosh, Amit Chakrabarti, 1999, Conducting carbon black filled EPDM vulcanizates:
assessment of dependence of physical and mechanical properties and conducting character on
variation of filler loading.
[9] Eshwaran Subramani Bhagavatheswaran, Meenali Parsekar, Amit Das, Hai Hong Le, Sven
Wiessner, Klaus Werner Stoeckelhuber, Gerd Schmaucks, Gert Herinrich, 2015, Construction of
Interconnected Nanostructured Carbon Black Network: Development of Highly Stretchable and
Robust Elastomeric Conductors, DOI 10.1021/acs.jpcc.5b06629.
[10] J. G.Malleite and A. Uquez, 2000, Carbon Black Filled PET/PMMA Blends: Electrical and
Morphological Studies.
[11] A. Sharma, M. Pandey, M. Khutia, G.M. Joshi, M. Teresa, 2016, Development of thermal sensor
by graphene nano platelets thermoplastic blends, Polymer-Plstic Tech. and Engg, DOI
10.1080/03602559.2016.1233272

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Resonance Frequency, Bandwidth and Quality factor of Varying Grades of Poly


(Tetrafluroethylene) Films15

Shantanu Dixit1, E. Dhanumalayan1, J. Anandraj1, Mayank Pandey1, Girish M. Joshi1, a,


N. Madhusudhana Rao2, S. Kaleemulla2, D.J. Shirale3, M. Teresa Cuberes4

1 Center for Crystal Growth, Polymer Nanocomposite Laboratory, VIT University, Veloore-6320214, TN, India
2 Center for Crystal Growth, Thin film Laboratory, VIT University, Vellore-632014, Tamilnadu, India
3 Department of Electronics, School of Physical Sciences, North Maharashtra University, Jalgaon 42500, India
4 Laboratory of Nanotechnology, University of Castilla-La Mancha, Plaza Manuel Meca 1, 13400 Almadn, Spain
a varadgm@gmail.com

DOI 10.2412/mmse.29.22.320 provided by Seo4U.link

Keywords: PTFE,Q-factor, resonance frequency, bandwidth.

ABSTRACT. Poly (terafluroethylene) commercially known as Teflon. The varying grades of PTFE demonstrate
interesting electrical properties. In the present investigation, we have measured the resonance frequency (fo), bandwidth,
and quality (Q) factor as a function of varying grades of PTFE films with impedance analyzer. The magnitude of resonance
frequency (50 Hz to 19 MHz), bandwidth (19-50MHz) and quality factor (900, 500 and 2.8) varies grade wise. All the
parameters were independent of temperature. under broadband frequency. This investigation feasible for the selection of
specific grade of PTFE for the microelectronics and electromagnetic shield coating applications.

Introduction. In the present era of an engineering thermoplastics and polymers were highly crucial
for domestic and industrial, space, defense and atomic energy domains. [1]. Polytetrafluoroethylene
(ptfe), polyvinylidene fluoride (ptfe) belongs to the class of fuloro polymers belongs to the class of
an engineering thermoplastic. Commercially PTFE known as the Teflon. It was widely used for the
coating,, medical and engineering applications due to low surface energy enable to achieve the barrier
property, best thermal, tensile strength, good dielectric property [2] motivates to select the varying
grades of ptfe films for the present work.
The processing temperature and recasting methods were influenced over the properties of different
grades of PTFE. It was classified based on the criteria of operating temperature, different nature of
form solid, liquid or powder product. Coating of nonporous membrane sustain at 2500C. The higher
toughness nonstick coating have domestic and industrial application suitable to the temperature range
of 2600C Teflon of water based liquid performs better at 2600C. The adhesion and abrasion resistance
were improved with the help of Teflon. It was the choice of engineering material community to test
the solvent based lubrication property at higher temperature and pressure criteria. It excites that
varying grades of PTFE exhibit interested properties and suitable for the various application.
However, previously we demonstrated the molecular weight co-related dielectric properties of
polymers [3].
We motivated to investigate the resonance frequency (fo), bandwidth (BW) and quality (Q) factor of
varying grades of PTFE. Generally, reports on dielectric constant, loss, impedance were reported for
in view of electrical properties of polymers, composites, blends. However, for implantation of

2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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electromagnetic interface property in electronic gazettes present investigation suggests to select the
perfect PTFE grade.
Materails and Exprimentals. Three different grades (15-5f-1, 15-5f-2, 32-5f-1) of ptfe films with
average thickness of 100 m were procured from cs hyde company, Illinois, USA. Electrical
properties were tested by using impedance analyzer make: n-4l, uk connected with fixture assembly
to impedance analyzer interfacing device. The across the broadband frequency ( 50 hz to 35 Mhz)
and temperature (30 150 0C).
Resonance frequency, Bandwidth and Quality factor of varying grades of PTFE films
The resonance frequency is the circuit reactance in the inductance or capacitance form. It may be both
tested as function of frequency dispersion. It is co-related to the Q-factor. However, Q-factor is
defined as the ratio of energy restored in capacitive or reactive per unit cycle of energy loss was equal
to the reactance divided by resistance. The bandwidth is mean difference of resonance frequency.
We have tested samples using an impedance analyzer as function of broadband frequency (50Hz to
35 MHz) and temperature 30 to 150 oC. The grades 15-5F-1and 2 is feasible to use it as the better
coating medium for electromagnetic shield applications. The physico-chemical properties of PTFE
depend on the fabrication conditions.

1000

30
800 40
50
60
600 70
80
Q-factor

90
400 100
110
120
200
130
140
150
0

50 100 500 1 K 10 K 50 K 100 K500 K 1 M 10 M 20 M 30 M 35 M

Frequency (Hz)

a)

600

550 30
3.0
500
40
2.8 30 50
2.6 40 450 60
2.4 50
2.2 60 400 70
2.0 70 350
80
1.8 80 90
Q-factor

300 100
90
Q-factor

1.6
1.4
100 250 110
110 120
1.2 200
120 130
1.0 130 150
0.8 140
140
0.6 100 150
150
0.4 50
0.2
0
0.0
-0.2 -50
50 100 500 1 K 10 K 50 K 100 K500 K 1 M 10 M 20 M 30 M 35 M 50 100 500 1 K 10 K 50 K 100 K500 K 1 M 10 M 20 M 30 M 35 M

Frequency (Hz) Frequency (Hz)

b) c)
Fig. 1. Q-factor as function temperatures across broad band frequency a) 15-5F-1, b) 15-5F-2, c)
32-5F-1 varying grades of PTFE films.

The Q- factor is evaluated by using the following relation, which is the ratio of energy stored and lost
per unit cycle operated across the sample under test.

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Q = 2 (Max instantaneous energy stored/Energy dissipated per cycle) i)

Higher magnitude of Q-factor is the dispersion of broadband frequency. The over damped, under
damped and critically damped mechanism co-related to the low, high and intermediate magnitude of
q-factor. It was demonstrated in Fig.1 a-c) Q factor of varying grades (15-5F-1,2 and32-5F-1) of
PTFE films. The resonance frequency varies from grade to grade and shown effect on the bandwidth.
The grade wise variation on Q-factor magnitude varies shown in Fig.2. The Q-factor was based on
the principle of LCR circuit tuned to radio frequency (in the shunt mode operation) as resonator
restricting the resistance of the inductor and narrowing the bandwidth [4-5].

Table 1. Comparative values of Q-factor, resonance frequency (f0), bandwidth of varying grades of
PTFE films.
PTFE grades Q-factor Resonance frequency (Hz) Bandwidth (Hz)
15-5F-1 900 10 MHz 19 MHz
15-5F-2 500 50 MHz 50 MHz
32-5F-1 2.8 10 MHz 19 MHz

1000

800

600
Q-factor

400

200

0
I II III

Varying grades of PTFE

FIG. 2. Q factor as a function of varying grades of PTFE.

Summary. In the present investigated we were mainly focused the evaluation of resonance frequency,
bandwidth and Q-factor as function of varying grades of PTFE. We found the Q-factor magnitude
decreases relative resonance frequency. The bandwidth influences grade wise. This investigation
suggests to select the specific grades of PTFE for microelectronic and EMI Teflon coating
application.
Acknowledgments.
Dr.D.J. Shiale would like to express special thanks to the DST Young Scientist (YS) Scheme Ref:
SR/FTP/PS-041/2012, New Delhi, India Dr.Girish M. Joshi would like to thanks Naval Research
Board, NRB, DRDO, India, new Delhi for availing the existed facilities under the project
No.256/Mat./11-12.
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References
J. G. Drobny, 2014 , Technology of Fluropoly, CRC Press, Taylor & Francis Group, LLC, ISBN -13:
978-1-4200-6317-2.
Q. Wang, F. Zheng, T. Wang, 2016, Tribological properties of polymers PI, PTFE and PEEK at
cryogenic temperature in vacuum, Cryogenics, 75, 19-25., DOI 10.1016/j.cryogenics.2016.01.001
O. Omelianovych, V.D. Dao, L. L. Larina, H.S, Choi, 2016, Optimization of the PtFe alloy structure
for application as an efficient counter electrode for dye-sensitized solar cells, Electrochmica Acta,
211, pp. 842-850, DOI 10.1016/j.electacta.2016.06.094
M. Khutia, G.M. Joshi, P.Tambe, 2016, Quality factor of Melt blend processed polypropylene/poly
(acrylonitrile-butadiene-styrene)/conducting carbon black blends, Int.J. Plast. Tech 2916. 19:2, 381-
387.
L. Wang, J. Liu, S. Li, X., 2016, Zhang, Materials & Design, Vol. 92, pp. 397-404.
, Vol 9.

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Optical Absorption Spectral Investigation of Dy2O3 Doped Zinc Strontium


Bismuth Borate Glasses16

D. Kothandan1, K. Chandra Babu Naidu2, R. Jeevan Kumar2

1 Department of Science and Humanities,Sreenivasa Institute of Technology and Management Studies, Chittoor. (A.P).
India
2 Department of Physics, S.K. University, Anantapur (A.P), India

DOI 10.2412/mmse.14.2.119 provided by Seo4U.link

Keywords: borate glasses, optical absorption spectrum, melt quenching method.

ABSTRACT. Borate glasses of (50-x) H3BO3-10SrF2-10Bi2O3-20ZnO-10SiO2-Mx (M = Dy2O3, x= 0.1) are prepared by


melt quenching method. The resultant sample is characterized using X-ray diffract meter in order to confirm the
amorphous nature. Further, the optical absorption spectrum is recorded to illustrate Judd-Ofelt (J-O) values and radiative
parameters. The allowed transitions are also reported.

Introduction. Borate glasses pertaining rare earth metal oxides have significant applications for solid
state, luminescent applications, laser hosts, lamp phosphors, broad band amplifiers, sensors, optical
data storage devices and optical fiber communication systems [1]. Moreover, J-O theory is an
important aspect to investigate the optical absorption spectrum. The J-O theory behind the optical
properties of glass materials is explained as follows.
Judd-Ofelt theory
According to J-O theory [2], [3] the intensity of the forbidden f f electric dipole transitions can arise
from the admixture of configurations of opposite parity (e.g., 4 f n 1n' d ' and 4 f n 1n' g ' ) into the 4fn
configuration. It was considered that the odd part of the crystal-field potential is the perturbation for
mixing states of different parity into the 4fn configuration. The experimental oscillator strength is
given by

f exp f ed f md (1)

The total oscillator strength of an absorption band is obtained from the expression

8 2 mv n 2 2
2

f exp J , ' J ' Sed J , ' J ' n3 Smd J , ' J ' (2)
3h2 J 1 9n

2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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where n is the refractive index of the medium, m is the electron mass, is the wave number of the
transition in cm-1, h is the Planks constant, (2J + 1) is the degeneracy of the ground state
2 S 1
Lj ,
n 2
2
2

is the Lorentz local field correction which accounts for dipole-dipole correction.
9
The intensitie3s of the magnetic dipole transitions which are weak are relatively independent of the
surrounding Ln ions. Therefore the experimental oscillator strengths are almost equal to the electric
dipole oscillator strengths.

f exp f ed
(3)

Hence the experimental oscillator strengths can be equated to the calculated oscillator strengths.

f exp J , ' J ' f cal J , ' J '



8 2 mv n 2 2
2

Sed J , ' J ' (4)


3h2 J 1 9n

The experimental oscillator strengths are evaluated from the obtained spectra and used to find the J-
O intensity parameters intensity parameters ( = 2, 4 and 6) by least square fit. The quality of the
fit is determined by the rms deviations between the measured and calculated oscillator strengths.
The intensity of f f transitions in rare earth complexes is ligand dependent. Hence many authors
tried to correlate the intensity parameters with the chemical nature of ion-ligand bond, with the
properties of the ligand itself or with the structure of the complex. 2 depend on the asymmetry of
the rare earth ligand field. 2 depends on the short-range effects i.e., the covalency of the ligand field.
It depends on the structural changes in the vicinity of the lanthanide ion. 4 and 6 follow the same
trend and mainly depend upon long-range effects. These parameters are related to the bulk properties
of the host material and the indicators of viscosity of the rare earth doped glasses. The spectroscopic
quality factor (), which is useful for predicting the stimulated emission in any laser active medium
and is given by

4

6 (4)

Radiative properties
The radiative properties of excited states of RE3+ ion are predicted by the J-O parameters using
refractive index. For the transition J ' J ' the radiative transition probability can be obtained
from the equation:

64 4v3 nn 2 2
2

AR J , ' J ' Sed J , ' J ' n3 Smd J , ' J '


3h2 J 1 9 (5)

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The total radiative transition probability is given by

AT J ' J ' AR J , ' J ' (6)

The radiative lifetime of an excited state is obtained from the expression

R J cal J
1
(7)
AT J
AR J , ' J '
R J , ' j ' (8)
AT J

The peak stimulated emission cross-section, p (J, J) between the states J and J can be
obtained from the equation

4p
p J , ' j ' AR J , ' J '
8cn 2 eff
(9)

Where P peak wave length of the transition and eff is its effective line width. The large values of
stimulated emission cross-sections indicate the good lasing transitions. A brief introduction to
theoretical models of J-O (Judd-Ofelt) theory to predict the radiative properties such as radiative
transition probabilities (AT), life times (R), branching ratios () and emission cross-sections (P) have
been discussed in this study.
Experimental Procedure
The glasses of general formula (50-x) H3BO3-10SrF2-10Bi2O3-20ZnO-10SiO2-Mx (M = Dy2O3 x =
0.1 have been prepared by mixing them in appropriate quantity with the help of digital electronic
balance. The chemicals of 99.9 % purity (Sigma Aldrich) are taken. All these compositions are mixed
together and stirred in a porcelain crucible. The mixture is melted by placing it in a programmable
furnace 11000C for 30min. The glass samples are taken out from the furnace and pour onto different
metal plates. The plate is again annealed for 3000C and as the result the glasses are obtained having
transparent, pure and amorphous in nature. The samples are characterized by using XRD (Bruker,
CuK=1.5418 ) and optical absorption spectrum for studying the structure and absorption spectrum.
Result and Discussions
The recorded XRD profile of Dy3+ doped zinc strontium bismuth borate glass (ZnSrBiB) is shown in
Fig. 1 [4]. It confirmed the amorphous nature without exhibiting any single or polycrystalline phases.

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Fig. 1. The optical absorption spectra of Dy3+ doped ZSBiB glasses.

Table 1. Experimental (fexp) & calculated (fcal) spectral intensities of Dy3+ doped ZSBiB glasses.
S.No Level Fexp Fcal

1 4F 1.6389 1.6296
3/2

2 4F 4.6100 4.6112
5/2

3 6F 0.3966 0.1074
7/2

4 6F 1.5550 1.5510
9/2

5 6F 1.2330 1.3311
11/2

6 6H 0.3051 0.2509
11/2

rms=0.127
2= 10.9110-20 4= 5.9810-20 6= 3.1110-20

Judd-Ofelt (J-O) Values of Dy3+ doped BiZnSr borate glasses


The experimental and calculated J-O spectral intensities are obtained for all the absorption bands of
Dy3+ ions in all the glass matrices. The experimental and calculated spectral intensities along with the
rms deviations in all the glass matrices are presented in Table.1. It is observed that there is a good
agreement between experimental and calculated values for all the transitions. Among these glass
matrices the higher spectral intensities are observed for 6F5/2 transition. This indicates that high
asymmetry [5-8] achieved for all the glass matrices in the present work. The J-O intensity parameters
2, 4 and 6 ( = 2, 4 & 6) are obtained from the experimental spectral intensities using the method
described in chapter I and the data is presented in Table.1. In order of magnitude of J-O intensity
parameter is 2> 4> 6 for all the Dy3+ based glass matrices of the present work.
Radiative parameters
The radiative parameters of samarium doped glasses are estimated with the help of J-O theory [9].
The radiative transition probability (Arad) of different transition of Dy3+ ions, branching ratios (R)
and radiative life time [10] of the excited states 6H15/2, 6H13/2 and 6H11/2. These values are tabulated in
Table 2. High branching ratio of 0.73 is obtained for the excited state of 6H13/2.

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Table 2. Radiative parameters of Dy3+ doped ZnSrBi borate glass.


S.No Transition Radiative transition Probability Branching ratio
6
1 H15/2 132 0.08
6
2 H13/2 1214 0.73
6
3 H11/2 317 0.19
Radiative lifetime 0.525 ms

Summary. Judd-Ofelt analysis has been successfully applied to evaluate the J-O experimental (Fexp),
calculated (Fcal) spectral intensities, intensity parameters (=2, 4 and 6). The intensity of emission
transitions of Dy2O3 is discussed. From these J-O parameters radiative properties such as radiative
transition probabilities (AT), radiative life times (R), experimental branching ratio () and peak
stimulated emission cross-section (P) are calculated at room temperature (RT). In case of Dy2O3
doped glasses the experimental (Fexp), calculated (Fcal) spectral intensities have been discussed for
the energy levels 4F3/2, 4F5/2, 6F7/2, 6F9/2, 6F11/2 and 4H11/2. The calculated radiative parameters are
presented for various transitions of 6H15/2, 6H13/2 and 6H15/2.
Acknowledgements. Authors express their thanks to Department of physics, Sri Krishnadevaraya
University, Anantapuramu, for providing laboratory facilities to carry out the present research work.
The financial support rendered by the UGC under SAP [No.F.530/8/DRS/2010 (SAP- I)] and
Department of Science and Technology under FIST [SR/FST/PSI-116/2007], New Delhi, are
gratefully acknowledged.
References
[1] M. Venkateswarlu, B. H. Rudramadevi, 2015, International Journal of ChemTech Research Vol.7,
No.2, pp. 607-612.
[2] J-o A. A. Bhaghat, E. E. Shaisha, A. I. Sabry, 1987, J. Master, Sci. Vol. 22, p. 3323.
[3] D. Kothandan, PhD. thesis S.K.University, Anantapur, A.P, 2016.
[4] D. Kothandan and R. Jeevan Kumar, 2016, Investigations on Electrical and Thermal Properties
of Rare Earth Doped BiZnSr Borate Glasses, Journal of The Australian Ceramic Society Volume 52,
156 166.
[5] K.Venkata Rao, PhD. thesis, S.V.University, Tirupathi, 2011.
[6] E. W. Omen, A. M. A. Van Dongen, 1989 J. Non-Cryst, Solids Vol. 111, p. 205.
[7] C.Rudowiez, P. Guntek, M. Kabowik, 2011, Opt. Master Vol. 33, p.1557.
[8] C. Gautam, A. Kumar Yadav and A. K. Singh, 2012, A review on infrared spectroscopy of borate
glasses with effects of different additives, ISRN Ceramics Volume 2012, DOI 10.5402/2012/428497.
[9] B. Karthikeyan, 2006, FTIR spectral analysis on heavy metal borate glasses, Modern Physics
Letters B, Vol.20 Issue 10, DOI 10.1142/S0217984906010688.
[10] S. G. Motke, S. P. Yawale, S. S. Yawale, 2002, Infrared spectra of zinc doped lead borate glasses,
Bull. Mater. Sci. Vol. 25, No.1, pp 75-78, DOI 10.1007/BF02704599

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An Assessment of Mechanical and Tribological Property of Hybrid Aluminium


Metal Matrix Composite17

R. Santosh Kumar1, R. Nishanth1, V. Seenivasan1, S. Sarath Sanmugam1, S. Johny James1, a

1 Department of Mechanical Engineering, Kingston Engineering College, Vellore, 632059, India


a johnyjames2002@yahoo.com

DOI 10.2412/mmse.30.1.536 provided by Seo4U.link

Keywords: composition of reinforcement, EDM, metal matrix.

ABSTRACT. Composite materials has huge requirement in the area of automobile, aerospace, and wear resistant
applications. This study presents the synthesis of composite reinforced with SiC and Al 2O3 using gravity stir casting. Stir
casting is the manufacturing process that is incorporated to produce the composite material because of its extreme bonding
capacity with base material. The composition of reinforcement with 6061 aluminium matrix is SiC-7.5% and Al2O3 -
2.5% respectively. The average size of reinforcement particle is 30-40 microns. The synthesised composite casting is
machined using EDM to prepare specimens for various tests. Microstructure study was carried and the microstructure
images prove the existence and dispersion of reinforcement particles in the metal matrix. There is no visible porosity is
observed. The hardness of the specimen is tested using Vickers hardness tester and found considerable increase when
compare with parent alloy Al 6061. Also mechanical and tribological properties of hybrid Aluminium metal matrix
composite were employed. The fortifying material, Silicon Carbide is composed of tetrahedral of carbon and silicon atoms
with strong bonds in crystal lattice along with its excellent wear resistance property and alumina have high strength and
wear resistance. To avoid enormous material wastage and to achieve absolute accuracy, wire-cut EDM process is
capitalised to engrave the specimen as per required dimensions. Three Tensile test specimens were prepared, in order to
achieve reliability in results as per ASTM- E8 standard, and the values were tabulated. Impact test was carried out and
the readings were tabulated. Wear test was carried out using pin on disc wear test apparatus and the results show
considerable increase in wear resistant property when compare with parent alloy Al6061.The above work proves the
successful fabrication of composite and evaluation of properties.

Introduction. The dawning of any component begins with the significant selection of material. In
the bygone days there is a lot of fascination towards materials that are having good mechanical and
tribological properties. This forms a collective term called composites. Composites are basically a
combination of different materials, it could be a metal, ceramics, [1].Aluminium metal matrix
composite emerged from the need of lighter weight, higher performance characteristics in aerospace,
automobile industries etc. Aluminium metal matrix composite replaces conventional aluminium
alloys due to its high wear resistance, lower thermal expansion and higher strength to weight
ratio[2].Silicon carbide is preferred because of its excellent refractory property and fatigue resistance.
In the work of Bhoopathi adding of silicon carbide results in increase of hardness and
density.[3]Among the various manufacturing process available for the production of discontinuous
metal matrix composite, stir casting is widely accepted due to its large flexibility, simplicity and
higher bonding ratio [4]. The various mechanical properties are available among which the tensile,
impact, hardness test are widely used. Wear test was carried out and increase in wear resistant
property was reported due to addition of SiC has been reported by SJ James. Tribological property is
studied to analyse the science behind two interacting surfaces. [5-7]. In this assessment an effort has
been taken to assess the mechanical and tribological properties of hybrid aluminium metal matrix
which is developed using stir casting mixing reinforcement SiC and Al2O3 respectively.

2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
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Experimental procedure. In this assessment, the hybrid aluminium metal matrix composite was
prepared by exploiting stir casting method. To carry out this process, we have chosen 90% of
aluminium alloy 6061, silicon carbide7.5% and alumina 2.5% were subjected to preheating process.
The preheating is done at a temperature of 2500c.The melting of aluminium alloy rod takes place at a
casting temperature of 6600c and the melt was stirred with the help of stainless steel stirrer which
rotates at 550rpm.The entire setup operates at a voltage of 214 V with a frequency of about 50.1 Hz.
The impurities were removed and magnesium was added with a proportion to increase wettability.
The molten composite is allowed to solidify in the mould to get the desired shape. The finished casting
product is later subjected to wire cut EDM to prepare test specimens. In order to perform
microstructure study specimens were polished and optical microscope was used to capture images.
The tensile test was carried out using Tensometer and the specimen dimension refers to ASTM E8
standard. The hardness test was carried out using Vickers hardness test containing pyramid shape
diamond intender. The ability of the component to withstand heavy blow without fracture is defined
as impact strength. The specimen size is mentioned as per the standard Charpy test. The length is of
55mm and 10mm width with 10mm thickness. The notch angle is about 450 with 0.25mm radius.
Two samples were taken into consideration to evaluate the mean impact strength. The resultant impact
strength was calculated in joules. This will indicate the maximum amount of energy it is absorbed
before deformation or failure. The wear or tribological behaviour is assessed using pin on disk
apparatus. The frictional force, coefficient of friction, wear rate are the parameters that are evaluated
in this section. The Linear Reciprocating Tribometer can accommodate a variety of sample
geometries to create point, line and area contacts. Customized sample holders can also be provided
for tests requiring conformal contacts.This system is computer controlled and includes a data
acquisition software that can be used to acquire, view and report results. Lubricant was applied during
the wear test.
Results &Discussion. This study of external force observation depicts the mechanical properties of
the composites. The characterization of the developed composite was carried using microstructure
study. The various mechanical properties include tensile behaviour, hardness, and Impact
characteristics. The tribological property of the developed composite was assessed by conducting
wear test.
Microstructure Study

Al203

Si
C

a) b)
Fig. 1. (a), (b) Micrograph of developed Composite.

Optical microscope has been used to plot the micrographs. The Fig. 1 (a) indicates the focal length of
50 micrometer and Fig. 1 (b) focal length of 20 micrometer. From Fig. 1 (b) shows the dispersed
reinforcements along the metal matrix. This study proves the existence of the reinforcements.

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Tensile Characteristics. Three test specimens were subjected to tensile test and the tensile strength
values of developed composite were tabulated in Table.1. The higher poisons ratio clearly indicates
that this material is completely brittle in nature. The variation in tensile strength values is due to the
uneven dispersion of reinforcements. The agglomeration of reinforcements during casting decides
high and low tensile strength. The developed composite exhibits a maximum tensile strength of 152
Mpa. The following gives the calculated tensile value. Fig 2 and 3 are the graphs plots from the values
obtained during tests.

Table 1. Tensile values of developed Composite Al6061/SiC/Al2O3.


S. no. Sample no. Tensile strength Elongation Poissons ratio
1 1 131 Mpa 2.47% 0.820
2 2 152 Mpa 3.26% 0.891
3 3 120 Mpa 2.11% 0.978

Maximum tensile value 152 MPa

The tensile strength is calculated by the expression:

Tensile strength=Breaking load/Cross sectional area


Tensile strength=4716/36=131N/mm2

The elongation is calculated by the equation:

(Final gauge length-Initial gauge length)/(Final gauge length)x100

The poisons ratio is calculated by the equation:

Poisons ratio=Lateral strain/longitudinal strain


Lateral strain=change in breadth/original breadth
Lateral strain=5/6=0.833
Longitudinal strain=change in length/original length
Longitudinal strain=101.5/100=1.015
Poisons ratio=lateral strain/longitudinal strain
Poisons ratio=0.833/1.015
Poisons ratio=0.820

The graphical representation is given in the figure 1 and figure 2.

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LOAD vs TENSILE STRENGTH

TENSILE STRENGTH [Mpa]


200

150

100

50 STRENGTH

0
471.6 547.2 432
LOAD [Kg]

Fig. 2. Graph-Tensile value of developed Composite Al6061/SiC/Al2O3.

ELONGATION vs LOAD
4.00%
ELONGATION(%)

3.00%

2.00%

1.00% elongation

0.00%
432 471.6 547.2
LOAD (Kg)

Fig. 3. Graph-Tensile value of developed Composite Al6061/SiC/Al2O3.

Hardness characteristic. Hardness in this assessment was done by Vickers micro hardness tester.
The test was carried out using a diamond -pyramid indenter. The hardness value of aluminium alloy
Al6061is 59.18 HRC. The mean value obtained after five tests were 91.98 HRC. The value obtained
is 64.35% greater than hardness value of parent metal alloy Al6061.The below Table 2 indicates the
mean hardness value of developed composite. The highest hardness value is due to the addition of
reinforcements. This is one of the peculiar properties of composites. These values are obtained before
doing the tempering operation; if heat treatment was done result would show higher values.
Impact characteristics.Two specimens were prepared and subjected to impact test. The values are
tabulated in Table 3. The resultant impact strength was calculated in joules. This will indicate the
maximum amount of energy it is absorbed before deformation or failure. The variation in the 2 distinct
values of the impact strength is probably due to the improper mixing of reinforcements with the base
metal.

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Table 2. Hardness values of developed Composite Al6061/SiC/Al2O3.

S.no. Position Hardness value Unit

1 P1 95.9 HRC
2 P2 79.6 HRC
3 P3 99.9 HRC
4 P4 101.6 HRC
5 P5 82.9 HRC
Mean value 91.98 HRC

Table 3. Impact test values of developed Composite Al6061/SiC/Al2O3.


Sample no Impact strength (joules)

1 16
2 6

Maximum value 16 Joules

Wear characteristics.The wear specimen is made as per the requirement 30X30X10 mm. The pin is
made up of mild steel and is 10mm in dia and 30mm in length. The load applied is 50N and time of
rotation is 60 min. The value of wear is measured in microns and its value is 9.918. The wear is
negligible due to the addition of reinforcements. The COF, frictional force, speed and wear is
tabulated in Table.4.
As the Coefficient of friction decreases the frictional force also decreases. The below Fig.4 indicates
the fluctuation in the coefficient of friction as the load varies. This clearly shows that frictional force
is directly proportional to coefficient of friction.

Table 4. Wear test values of developed Composite Al6061/SiC/Al2O3


Wear
S.no Cof Frictional force Time Temperature Load Speed
(micrometer)

1 0.121 6.169 54.018 35.026 50.877 609.337 9.918

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CO-EFFICIENT OF FRICTION vs FRICTIONAL FORCE

FRICTIONAL FORCE
10
8
6
4
2 FORCE
0

0.15

0.14
0.016

0.143
0.141
0.143

0.133
0.129
0.132
0.129
0.124
0.117
CO-EFFICIENT OF FRICTION

Fig. 4. Graph-wear test values of developed Composite Al6061/SiC/Al2O3.

Summary. The new composite was successfully designed and synthesised using stir casting route.
The specimens were cut as per requirement using wire EDM. Microstructure study proves the
existence of reinforcements in the metal matrix and agglomeration as well. The tensile test value
along with poisons ratio clearly shows that the material fracture is ductile-brittle mode. It also adds
that the maximum tensile value is 152MPa. The hardness value is nearly 64.35% greater than the base
metal hardness value. The impact test shows variation in values and is due to agglomeration. The
maximum impact value is 16 joules.The wear test value indicates the enhanced wear resistance
property of the developed composite with applied base oil lubricant. The maximum wear value is
9.918 micrometer. Excellent wear resistance property is achieved which is one of the unique property
of composites.
References
[1] Rajan H. M., Ramabalan S., Dinaharan I., & Vijay S. J. (2013). Synthesis and characterization of
in situ formed titanium diboride particulate reinforced AA7075 aluminum alloy cast
composites. Materials & Design, 44, 438-445.
[2] Alaneme K. K., Bodunrin M. O. (2013). Mechanical behaviour of alumina reinforced AA 6063
metal matrix composites developed by two step-stir casting process. Acta Technica Corviniensis-
bulletin of engineering, 6(3), 105.
[3] Boopathi M. M., Arulshri K. P., & Iyandurai, N. (2013). Evaluation of mechanical properties of
aluminium alloy 2024 reinforced with silicon carbide and fly ash hybrid metal matrix composites.
American journal of applied sciences, 10(3), 219.
[4] Suragimath M. P. K., Purohit G. K. (2013). A study on mechanical properties of aluminium alloy
(LM6) reinforced with SiC and fly ash. IOSR J. Mechanical and Civil Engg, 8, 13-18.
[5] Lloyd D. J. (1994). Particle reinforced aluminium and magnesium matrix composites.
International Materials Reviews, 39(1), 1-23.
[6] James S. J., Venkatesan K., Kuppan P., & Ramanujam R. (2014). Hybrid Aluminium Metal
Matrix Composite Reinforced with SiC and TiB 2. Procedia Engineering, 97, 1018-1026.
[7] Mistry J. M., & Gohil P. P. (2016). An overview of diversified reinforcement on aluminum metal
matrix composites: Tribological aspects. Proceedings of the Institution of Mechanical Engineers, Part
J: Journal of Engineering Tribology, DOI 10.1177/1350650116658572
[8] Poria S., Sahoo P., & Sutradhar G. (2016). Tribological Characterization of Stir-cast Aluminium-
TiB2 Metal Matrix Composites. Silicon, 1-9.

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Dielectric Loss Behavior of SrxZn1-xMnTiO5 (x = 0.1 to 0.9) Ceramics18

M. Maddaiah1,a, T. Sofi Sarmash1, T. Vidya Sagar1, T. Subbarao1

1 Ceramic Composite Lab, Dept. of Physics, S. K University, Anantapuramu, A.P., India


a venkateswararaoikp@gmail.com

DOI 10.2412/mmse.66.93.675 provided by Seo4U.link

Keywords: ceramics, titanate, dielectric loss, absorbers, microwave devices.

ABSTRACT. SrxZn1-xMnTiO5 (x = 0.1 to 0.9) ceramic samples were prepared by conventional solid state reaction
technique. The mixed powder was calcined in the temperature range of 1050-1150oC for 10 hours. Further, the pellets
were sintered finally in the temperature range 1150-1250oC for 2 hours in a crucible. The samples are characterized for
dielectric properties. Especially, the variation of dielectric loss as a function of temperature and composition is discussed.
The achieved results show that at room temperature all the samples reveal the low loss values, which are suitable for low
noise and microwave device applications. On the other hand, at high temperature all the samples perform the absorber
behavior as they express high dielectric loss values.

Introduction. Strontium manganese titanate compound is unique material revealing


antiferrodistortive elastic property, polar dielectric and spin glass magnetic behavior simultaneously
[1]. So far there is no through studies on the synthesis of SrxZn1-xMnTiO5 (x=0.1 to 0.9) by solid state
diffusion method and characterization by structural, dielectric, electrical and thermal properties. The
substitution of zinc and manganese ions to from (Zn, Mn) TiO3 solid solution, is adopted to improve
the thermal stability and dielectric properties. Strontium titanate-based ceramics were widely used to
fabricate some electronic components, such as grain boundary layer capacitors (GBLC) was
fabricated [1], it has been shown to have a great many merits, such as high-capacitance, low dielectric
loss, and small size for low-voltage circuitry [2-7]. This requires a dielectric material with both high
relative tunability nr (E) = [ (0) - (E)]/(0) (where (0) is the dielectric constant at zero field, and
(E) is the dielectric constant under applied field E), and very low dielectric loss at microwave
frequencies. High tenability offers a capability for broad-range adjustment of the working
frequencies, and low loss provides low noise, high selectivity and compatibility with cryogenic
electronics. Zinc titanate (ZnTiO3) has hexagonal structure of dielectric materials for microwave
applications such as mobile telephones and satellite communication systems. High performance with
low loss and stable temperature coefficient of resonance frequency (f) is basic requirement of
dielectric.
Alexander Tkach, Paula M. Vilarinho and Andrei L. Kholkin [8] studied the microstructuredielectric
tunability relationship in Mn-doped strontium titanate ceramic samples were prepared by the
conventional mixed oxide method. The grain size was found to differ marked between Sr1-xMnxTiO3
(variation from 20 to35 m) and SrT1-yMnyO3 ceramics (much finer grains from 0.6 to 0.8 m) were
observed), without clear dependence on Mn content. In the recent literature Naidu et al. [2], [9], [10],
[11], Kumar et al. [12] and Maddaiah et al. [1], [13] investigated the effect of various elements (La,
Mg, Mn, Cu, Zn & Bi) on electrical properties such as dielectric constant, loss, thermoelectric power,
ac-conductivity and dc-conductivity of SrTiO3 electro ceramic material. These researchers reported
that the Cu-doped SrTiO3 shows highest dielectric constant at room temperature (RT) [9]. In addition,
several researchers showed the addition of zinc improves the loss of ceramic materials [14], [15].

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Hence an attempt is made to study the dielectric properties for achieving high loss so as to provide
dielectric absorbers.
Sample Preparation. SrxZn1-xMnTiO5 (x=0.1 to 0.9) ceramic samples were prepared by
conventional solid state reaction technique. High Purity chemicals of MnCO3, ZnO, TiO2 and SrCO3,
(all from Aldrich of 99.9%) were used as the raw materials. These powders were mixed thoroughly
and ground to obtain fine powders. The powders were uniaxially pressed initially into a cylindrical
disc of 1.2 cm in diameter and about 2 mm of thickness. This mixed powder was calcined in the
temperature range of 1050-1150oC for 10 hours. The powders were uniaxially pressed initially into a
cylindrical disc of 1.2 cm in diameter and about 2 mm of thickness at a pressure of 10 tons. These
discs were sintered finally in the temperature range 1150-1250oC for 2 hours in a crucible. Further
the characterization is made using various LCR meter.
Results and Discussion. The structural, morphological properties and the variation of dielectric
constant as a function of temperature are reported in the authors previous work [1]. Figure 1-5 depict
the Dielectric loss versus temperature of SrxZn1-xMnTiO5 (x=0.1-0.9). From all these plots the
dielectric loss increases with increase of temperature but it decreases with increase of frequency. This
is a usual dielectric behavior as reported in the literature [16]. From all the plots the dielectric loss
were increased with increase of the temperature and decreased with the increase of the frequency
because of the Sr-composition in the sample which might be caused due to the increase of density.
The higher value of tan at high temperatures may be due to transport of ions with higher thermal
energy. The sharp increase in tan may be due to the scattering of thermally activated charge carriers
and some defects in the samples. At higher temperature the conductivity begins to dominate, which
in turn is responsible for the rise in tan that is associated with the loss by conduction i.e., tan . Also
at high temperature (paraelectric phase) the contribution of ferroelectric domain walls to tan
decreases, which is responsible for the rise in tan . These types of dielectric behavior were also
observed in some similar types of compounds. The increase of the tan peak in the ferroelectric
region is probably due to the increase in the domain populations instead of the grain sizes. Orientation
of the electric and elastic dipoles results in domain-wall pinning and thus a reduction of the dissipation
in the ferroelectric state. On the other hand, the presence of oxygen vacancies and defects will cause
larger losses at higher temperatures. These kind of larger loss values are useful for absorber
applications [17], [18].

Fig. 1. Shows the Dielectric loss Vs Temperature (K) of Sr01Zn0.9MnTiO5& Sr0.2Zn0.8MnTiO5.

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Fig. 2. Shows the Dielectric loss Vs Temperature (K) of Sr0.3Zn0.7MnTiO5 & Sr0.4Zn0.6MnTiO5.

Fig.3. Shows the Dielectric loss versus Temperature (K) of Sr0.5Zn0.5MnTiO5& Sr0.6Zn0.4MnTiO5.

Fig. 4. Shows the Dielectric loss versus Temperature (K) of Sr0.7Zn0.3MnTiO5 & Sr0.8Zn0.2MnTiO5.

Fig. 5. Shows the Dielectric loss Vs Temperature (K) Sr0.9Zn0.1MnTiO5.

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Summary. The strontium manganese zinc titanate ceramic materials were synthesized via
conventional solid-state reaction method. The obtained low loss values at room temperature and high
values at high temperature provide low noise device and dielectric absorber applications.
References
[1] M. Maddaiah, A. Guru Sampath Kumar, L. Obulapathi, T. Sofi Sarmash, K. Chandra Babu Naidu,
D. Jhansi Rani, T. Subba Rao, Digest Journal of Nano materials and Biostructures, 10 (2015) 155-
159.
[2] K. Chandra Babu Naidu, T. Sofi Sarmash, M. Maddaiah, P. Sreenivasula Reddy, D. Jhansi Rani,
T. Subbarao, Journal of The Australian Ceramic Society Volume 52(1), 2016, pp. 95 101.
[3] E. Elayaperumal, Girish M. Joshi, M. Malathi, International Journal of ChemTech Research Vol.
7, (2014-2015), 212-217.
[4] S. Prathap, K. Chandra Babu Naidu and W. Madhuri, AIP Conference Proceedings, 1731, 030019
(2016); DOI 10.1063/1.4947624.
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Vol. 9, (2016), 80-84.
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Research 6 (2014) 1929-1932.
[8] Alexander Tkach, Paula M. Vilarinho and Andrei L. Kholkin Acta Materialia, 53 (2005), 5061.
[9] K. Chandra Babu Naidu, T. Sofi Sarmash, M.Maddaiah, V.Narasimha Reddy and T.Subbarao,
AIP Conference Proceedings 1665, 040001 (2015); DOI 10.1063/1.4917614.
[10] K. Chandra Babu Naidu, T. Sofi Sarmash, M. Maddaiah, P. Sreenivasula Reddy, D. Jhansi Rani,
T. Subbarao, Journal of The Australian Ceramic Society Volume 52(1), 2016, 95 101.
[11] K. C. Babu Naidu, T.Sofi Sarmash, M. Maddaiah, A. Gurusampath Kumar, D. Jhansi Rani, V.
Sharon Samyuktha, L. Obulapathi, T.Subbarao, Journal of Ovonic Research 11, (2015), 79 84.
[12] S. Anil Kumar, K. Chandra Babu Naidu, International Journal of ChemTech Research, 9 (2016),
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[14] Chandra Babu Naidu K., Madhuri W, Materials Chemistry and Physics, 181 (2016), 432-443.
[15] K. Chandra Babu Naidu, W. Madhuri, International Journal of Applied Ceramic Technology, 13
(2016), 1030-1035.
[16] S. Prathap, K. Chandra Babu Naidu, and W. Madhuri, AIP Conference Proceedings 1731,
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Cite the paper
M. Maddaiah, T. Sofi Sarmash, T. Vidya Sagar, T. Subbarao, (2017). Dielectric Loss Behavior of SrxZn1-
xMnTiO5 (x = 0.1 to 0.9) Ceramics. Mechanics, Materials Science & Engineering, Vol 9. Doi
10.2412/mmse.66.93.675

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Effects of Manganese (Ii) Sulphate on Structural, Spectral, Optical, Thermal


and Mechanical Properties of L-Alanine Sodium Sulphate Single Crystals19

F. Praveena1, S.L. Rayar2

1 Department of physics, M.E.T.Engineering College, chenbagaramanputhoor, Tamilnadu, India


2 Department of physics, St.Judes college, Thoothoor, Kanyakumari, Tamilnadu, India

DOI 10.2412/mmse.56.71.446 provided by Seo4U.link

Keywords: LASS, FT-IR, TG-DTA, sodium sulphate single crystals.

ABSTRACT. New Non-linear Optical materials have been attracting in the research world for their potential applications
in emerging opto-electronic technology. The dipolar nature of amino acid leads to peculiar physical and chemical
properties, thus making a good candidate for NLO applications. Single crystals of manganese (II) sulphate doped L-
Alanine sodium sulphate(LASS) has been synthesized by slow evaporation technique. Structural property of the grown
crystals are characterized by X-ray powder diffraction,FT-IR spectral analysis conforms all the functional
groups.Thermogravity(TG) and differential themogravimetric(DTA) analysis have been performed to study the thermal
stability of the crystals. The second harmonic generation efficiency was measured by Kurtz-Perry powder technique. The
transmission and absorption of electromagnetic radiation is analysed through UV-VIS spectrum. Microhardness was
measured at different applied load to understand the mechanical stability of the crystal.

Introduction. Non-linear optical materials are used in several practical applications in


telecommunication, optical computing, optical data storage and processing, laser technology and in
many other fields. Today research is focused on searching new semi organic nonlinear optical (NLO)
materials, as they share the advantages of both inorganic (high thermal and mechanical stability) and
organic (broad optical frequency range and second harmonic conversion efficiency) materials.
Alanine is an amino acid, which is an important source of energy for muscle tissue, the brain and
central nervous system. L-alanine is an isomer of alanine with the chemical formula
CH3CHNH2COOH next to glycine. L-alanine molecule can exist in zwitterionic form and it can form
novel nonlinear optical (NLO) compounds [1-2].They contain proton donar carboxyl acid (-COO)
group and the proton acceptor amino (NH2) group in them [3]. These versatile behaviours of amino
acid based organic crystal attract the researchers towards crystal growth of NLO crystals. The
complexes of amino acids and salts are promising materials for optical second harmonic generation
(SHG) [4]. Recently also optical, spectral and second harmonic generation studies were carried out
on L-Alanine based materials [5-8]. In this work, the manganese (II) sulphate is introduced into the
lattice of L-alanine sodium sulphate crystals to alter the structural, spectral, thermal, optical and
mechanical properties of LASS crystal and analysed. Characterization studies such as powder XRD,
EDAX, FTIR were done. Kurtz and Perry SHG test confirms the NLO property of the grown
crystals.Hardness values are found out by Vickers hardness test.
Synthesis and growth of the crystal. Analytical reagent (AR) grade L-alanine, sodium
sulphate(Na2SO4) and manganese(II) sulphate monohydrate (MnSO4.H2O) were used along with
double distilled water (as a solvent) for the growth of single crystals by the slow evaporation method.
L-alanine and Sodium sulphate mixed in 1:1 molar ratio were dissolved in double distilled water and
stirred for four hours to obtain a homogeneous solution. The solutiobn was filtered and kept in a dust
free environment. Transparent and colorless single crystals of L-alanine sodium sulphate (LASS)

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with dimenions13.5x11x6 mm3 were formed at room temperature in a period of about 30 days as per
the reaction. LASS was added with MnSo4.H2O in the molar ratio 1:0.01. Mn2+ doped LASS crystals
of 11x8x4 mm3 were grown in a period of about 27 days similarly under identical conditions with the
pure LASS crystal growth. Fig. 1 (a), 1 (b) shows the photographs of pure and Mn2+ doped LASS
crystals respectively.

Fig. 1. (a) Photograph of pure LASS, (b) photograph of Mn2+ doped LASS.

Structural analysis
Powder XRD. The purified samples of grown LASS crystals are crushed to a uniform powder and
subjected to a powder X-ray diffraction using a Bruker AXS D8 advance powder X-ray
Diffractometer. The K-radiations (=1.5406 ) from a copper target are used for the diffraction
studies. The powdered sample is scanned in the range 1070C at a scan rate of 2 /min. The well
defined sharp peaks reveals the good crystalline nature of pure and doped LASS crystals.The position
of the peaks are slightly shifted and the intensity varied due to the dopant. The XRD pattern of the
grown LASS crystal and Mn2+ doped LASS crytals are shown in fig. 2 (a) and fig. 2 (b).
(140)
(120)
(131)

(043)
(04
3)
(251)
(142)
(110)

20 30 40 50 60 70 80

0
20 30 40 50 60 70 80

Fig. 2. (a): powder XRD pattern of pure LASS, (b): powder XRD pattern of Mn2+ doped LASS.

Ft-ir spectral analysis. The FT-IR spectrum of undoped and Mn2+doped L-alanine sodium sulphate
was recorded using FT-IR spectrometer in the region 4000-400cm-1.From the spectra,the Intensity of
bands have been altered and slightly shifted..It is due to the presence of Mn2+ ions in the lattice of
doped crystal. It is found that the N-H Streching vibration in the amine group is assigned wave number
of 3087cm-1. The transmission due to the O-H bond in the carboxylate group is observed in the region
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2730cm-1for LASS , whereas in the case of doped LASS, the peak is shifted to 2810 cm-1. The peaks
at 1359 cm-1 and 1360 cm-1 due to S=O stretching in sulphate groups of pure and doped LASS
repectively. Metal bondings are assigned the wave numbers 539 cm-1 and 540 cm-1 for pure and
doped LASS crystals[9-10].Thus all the molecular groups presents in the Mn2+ doped LASS crystals
could be identified. The FTIR spectra of pure and doped LASS crystals are shown in Fig.3(a) and fig.
3(b).

100.0
95

90
3981 100.0
95
774
90
85

80 772 85
80
1237
75

70 1960 6
75

70
1013 646
65 65

60

55
410.59 60

55
2108 1113 540
%T50

1235
50

45
2601 %T 45

40
1360
40
35
2605
35

30
647 30
25 2810
3081
25 20

20 2109 1010 15

15 539 10

1606
1603 1359
5

2730
10
0.0
5 4000.0
3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
0.0

4000.0 3600 3200 2800 2400 2000 1800 160


0
.97
1400 1200 1000 800 600 400
cm-1
cm-1

Fig. 3. (a) The FTIR spectra of pure LASS, (b) The FTIR spectra of Mn2+ doped LASS.

Optical Analysis
Non-linear optical analysis. The NLO property of the crystal is confirmed by the Kurtz and Perry
technique.The fundamental beam of 1064nm from Qswitched Nd:YAG laser is used to test the second
harmonic generation (SHG) property of the doped L-alanine sodium sulphate crystals. The output
power from the pure LASS and Mn2+ Doped LASS crystals were compared to that of KDP crystal
and the results are presented in table1.

Table 1. SHG efficiency of pure LASS and doped LASS crystal.


Sl. No. Name of the crystal Output Input Energy SHG efficiency
Energy (compared with KDP)
(joule)
(milli joule)
1 LASS 6.81 0.68 0.87
Mn2+ doped
2 10.01 0.68 1.28
LASS(0.01)

The result obtained for Mn2+ doped LASS shows that SHG efficiency is about 1.28 times that of KDP
crystal. When compared with LASS crystal, it is found that the SHG efficiency of Mn2+ doped LASS
crystal is high. This increase in the efficiency indicates that the crystals can be used for applications
in non-linear optical devices.
(ii) UV-VIS analysis. The UV - visible spectrum was recorded for the powdered sample of the
crystals. This study was carried out in the spectral range 190-800 nm for the grown LASS and MnSO4
doped LASS crystal. The recorded optical absorption spectrum of the grown single crystals are shown
in fig. 4(a), 4(b).

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Fig. 4. (a), (b) Recorded optical absorption spectrum.

It is observed from the spectrum that the lower cut-off wavelength is 204 nm for doped LASS and
the transmittance of 97%, which proves the good optical quality.Using the formula:

Eg = hc/ (1)

The optical band gap (Eg) was determined to be 6.05 eV for the grown manganese (II) sulphate doped
LASS crystal.The transmittance is decreased by adding dopant. The reduction of transmittance is
expected due to the incorporation of cations into the superficial crystal lattice and forming defects
centers.
Thermal Analysis. Thermogravimetry (TG) and differential thermogravimetric (DTA) analysis are
carried out for L-alanine sodium sulphate crystal using Perkin Elmer, Diamond TG/DTA instrument
between the temperatures 40C and 730C at a heat in rate of 20C/min under Nitrogenatmosphere.

Fig. 5. (a) Thermo gravimetric curve of pure LASS, (b) Thermo gravimetric curve of Mn2+ doped
LASS.

The figures 5 (a) and 5 (b) represents TGA trace of undoped and doped L-alanine sodium sulphate.
For pure LASS the decomposition point occurs at the temperature 294.5C.It indicates that the carbon
dioxide (CO2) sulpur dioxide (SO2), and NH2 gases are expected to be liberated from LASS sample.
In Mn2+ doped LASS,a tiny endothermic peak around 235 to 255 C might be attributed to
decomposition of metal ions Mn2+. The sharp endothermic peak around 255 to 340 C matches the
onset decomposition of LASS and it is stable up to 296C. The slight increment in temperature is
evident for the doped crystals suggesting that the substitution of dopant.

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Mechanical analysis
Vickers Micro hardness study. The mechanical property of grown crystals were studied by Vickers
hardness test. The applied loads were 25, 50 and 100 grams. The measurement was done at different
points on the crystal surface and the average value was taken as Hv for a given load.The Vickers
micro hardness was calculated using the relation,

Hv = 1.8544 P / d2 (2)

where P is the applied load;


d is the diagonal length of the indentation impression.
Fig. 6 (a) shows that the plots of the load p and Hv values.It is observed that the Vickers hardness
number increases with increasing load. Above 100g, cracks developed on the surface of the crystals
due to the to increase the hardness value. Fig. 6(b) shows that the plots of log d against log P for the
pure and Mn2+ doped LASS crystals. The work hardening exponents were calculated from the slopes
of the straight lines. The work hardening coefficients are found to be 4.4 and 3.07 respectively for
pure and Mn2+ doped LASS crystals. According to Onitsch, 1.0 n 1.6 for hard materials and n >
1.6 for soft materials .Since the value of n is greater than 1.6, the grown crystals belong to soft
material category [11-12].

120
1.75
100 1.7
80 1.65
1.6
60
1.55
HV
40 LASS 1.5
Mn2+ Doped LASS 1.45 LASS
Log d

20 Mn2+ Doped LASS


1.4
0 1.35
0 50 100 1.3979 1.4644 2

Load P Log P
Fig. 6. (a) Hardness behavior of pure and Mn2+ doped LASS, (b) plots of log d verses log P of
pure and Mn2+ doped LASS.

Summary. Good optical quantity of NLO transparent crystals of pure and doped L-Alanine sodium
sulphate are successfully grown by slow evaporation technique. Structural Characterization was
carried out by Powder X-ray diffraction. The FT-IR analysis shows the bands belonging to spectrum
of pure and Mn2+ doped L-Alanine sodium sulphate.All the functional groups are identified by this
analysis.From Optical absorption studies the value of bandgap is determined as 6.05eV for Mn2+
doped LASS. From SHG test, it is clear that the efficiency of the crystal is increased when Mn 2+ is
doped with pure crystal.The SHG efficiency of doped L-Alanine sodium sulphate was found to be
1.2 times greater than that of KDP crystal. The good second harmonic generation efficiency indicates
that the doped L-Alanine sodium sulphate crystals can be used for various applications in nonlinear
optical devices. The Mn2+ doped LASS crystal is thermally stable upto 296C and was confirmed by
TG-DTA studies.The slight increment in temperature is evident for the doped crystal suggesting that
the substitution of Mn2+.The Vickers hardness number of the grown crystals increases with load and
the work hardening coefficients are found to be 4.4 and 3.07 respectively for pure and Mn 2+ doped
LASS crystals. Since the value of n is greater than 1.6, the grown crystals belongs to soft material.
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References
[1] K. Seethalakshmi, S. Perumal. Recent Research in Science and Technology 2012, 4(6):13-16.
[2] K.K Hema Durga, P. Selvarajanj, D Shanthi, Int. J. Curr. Res. Rev., 2012, 4(14), 68-77.
[3]S.Gokul Raj, G. Ramesh Kumar, Adv. Mat. Lett. 2011, Vol. 2 (3), 176-182. DOI
10.5185/amlett.2011.1219
[4] K.D. Parikh, B.B. Parekh, D.J. Dave, M.J. Joshi, Journal of Crystallization Process and
Technology, 2013, 3, 92-96, DOI10.4236/jcpt.2013.33015
[5] T.G. Jayanalina, S. Rajarajan, S. Parthiban, C. Mojumdar, J Therm Anal Calorim. 2013. DOI
10.1007/s10973-013-3058-7
[6] D. Balaubrmanian, R. Jayavel, P. Murugakoothan, Journal of natural science, Vol. 1. No. 3, 216-
221, 2009. DOI:10.4236/ns.2009.13029.
[7] C. Ramachandra Raja, G. Gokila, A. Antony Joseph, Spectrochim. Acta A 72-753, 2009.
[8] M. Vimalan, T. Rajesh Kumar, S. Tamilselvan, P. Sagayaraj, C.K. Mahadevan, Physica B
Condensed Matter 405-65, 2010.
[9] P. Shanmugam, S. Pari, Journal of Chemical and Pharmaceutical Research, 7(5):44-53, 2015.
[10] Clothup N.B., Introduction to infrared and Raman spectroscopy, London: AcademicPress II ed.
1975.
[11] E.M. Onitsch, Mikroskopie 2, 1941, 135 p.
[12] G.Prabagaran, M.Victor Antony Raj, S. Arulmozhi, J. Madhavan,Der Pharma chemica,3(6): 43
650, 2011.

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Structural, Spectroscopic and Thermal Studies of Potassium Di-Hydrogen


Citrate Crystal20

N.D. Pandya1, J.H. Joshi1, H.O. Jethva1, M.J. Joshi1

1 Crystal Growth Laboratory, Department of Physics, Saurashtra University, Rajkot 360 005, India

DOI 10.2412/mmse.6.81.837provided by Seo4U.link

Keywords: potassium dihydrogen citrate, powder XRD, FT-IR, TGA.

ABSTRACT. Potassium dihydrogen citrate (KDC) finds wide applications in food products. Pure potassium dihydrogen
citrate crystal was grown by slow solvent evaporation technique at room temperature. Grown crystal exhibited needle like
morphology. The powder XRD shows triclinic structure symmetry with lattice parameters a=11.820 , b=14.970 ,
c=9.442 with angles = 91.60, = 93.35, = 110. The presence of various functional groups of grown crystal was
confirmed by using FT-IR spectroscopy. The thermogram indicates the thermal stability of the sample up to 100 oC and
then decomposes slowly into oxide stage through two stages. The results are discussed here.

Introduction. Potassium Dihydrogen Citrate (KDC) is a salt of tri-potassium citrate and citric acid.
It is widely found in citrus fruits, kiwi, strawberries and many other fruits [1]. KDC is known by its
various functions in food as an acidifying agent, as an emulsifier, as a flavor enhancer, to increase an
effect of preservatives, to inhibit bacterial action, as a buffer, as a sequestrant to protect food from
reaction with metals e.g. soft drinks, biscuit filings, jams, desert mixes and processed cheese [2]. It
regulates the blood balance and acid-base balance in the blood and tissues [3]. Along with food
application, KDC exhibits some applications in medical and pharmaceutical field also. The reduction
of urinary pH below recommended value forms uric acid which can further develop a uric acid stone
causing urolithiasis often known as neprolithiasis.The presence of potassium in KDC controls the
reduction of pH and maintains from 6.5 to 7 to dissolve existing uric acid kidney stone [4].
Carefully looking at the litrature, very scenty of work is reported in this material. The crystal structure
of citrate salt is studied by Love et al. [5] and of double citrate salt by Zacharias et al. [6] and solubility
study is explained by Van Auken [7]. Previously, Aygun performed structural study by AFM & SEM
of VO+2 doped KDC with different magnifications[8] and EPR study of Cu+2 and VO+2 doped KDC
[9]. Yarbasi et.al. done EPR and Optical study of vanadium doped KDC [10]. In the present context,
the authors investigated structral, spectroscopic and thermal properties of pure KDC crystals.
Experimental. The growth of Potassium dihydrogen citrate crystal was carried out by using slow
solvent evaporation technique at room temperature. The saturated solution was prepared in double
distilled water. The solution was stirred for about 5-6 hours to make it homogeneous. This solution
was kept at room temperature to evaporate solvent. The solution was sealed with porous lid and placed
in dust free atmosphere for solvent evapouration. Evaporation of solvent gives rise to crystallization
of needle shaped, transparent and colorless KDC crystal which was generally harvested in 20-25 days.
The photograph of grown KDC crystal is shown in the fig. 1.

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Fig. 1. Grown KDC Crystal.

Powder XRD. The Powder XRD was carried out using PANaytical Xpert pro set up using CuK
radiation within the range of 2 values from 10 to 50 and data analysed using Powder-X software.
FTIR was carried out on the THERMO NIKOLET 6700 within the frequency range 4000 cm-1 to 400
cm-1 in KBr media. TGA was carried out on the Linseis STA-PT-1600 from room temperature to
7000C at a heating rate 100C/min in an inert atmosphere.

Fig. 2. Powder XRD pattern of KDC crystals.

Fig. 2 shows powder XRD pattern of pure KDC crystals. The crystal structure of KDC showed
triclinic symmetry with lattice parameters a=11.820 , b=14.970 , c=9.442 with angles =
91.60, = 93.35 and = 110. Previously Love et al [5] reportd symmetry of the KDC revealed
triclinic symmetry with lattice parameters: a= 12.981 , b = 14.970 , c = 9.442 with angles =
91.60, =93.35 and = 110. This leads to the confirmation of above crystal structure.
The cell volume of KDC was found to be 1565.25 3. The crystallite size was determined by using
Debye-Scherrers formula

0.9
D =

where is FWHM;

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is the wavelength of incident radiation;


is the Braggs angle.
The crystallite size was found to be 8.795 .
FTIR Spectroscopy.

Fig. 3. FTIR spectrum of KDC crystals.

The FTIR spectrum of the KDC crystal is shown in the figure 3. The spectrum confirms the presence
of different functional groups. The CH2 out of phase and in-phase stretching vibrations are confirmed
by peaks at 2941.7 cm-1 and 2831 cm-1. This stretching leads to the vibrations (symmetric and anti-
symmetric) of O=C-OH carboxylate ion which is followed by oscillations of C-OH group for wave
numbers 1307.2 cm-1, 1249.9 cm-1, 1184.5 cm-1, 1127.5 cm-1, 1041.5 cm-1. These vibrations generate
stretching vibrations in C-C chains shown by a very small absorption endothermic peak for wave
number 963.9 cm-1. The observed vibrational frequencies and their assignments are listed in table 1.

Table 1. Assignments for different absorptions in FTIR spectra of KDC.


Wave Number (cm-1) Bond Assignment
5731, 3423.1 O-H Stretching
2941.7, 2831.3 CH2 out of phase & in phase stretching vibrations
1695 C=O stretching vibrations
1638.1, 1454.3 Symmetric & Antisymmetric oscillations O=C-OH (carboxylate) ion
1307.2,1249.9,1184.6,
Oscillations of C-OH group
1127.4,1041.5
963.9 C-C Stretching Vibrations

849.5, 825.0, 772.8 K-O (metal-oxygen ) Vibration

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Fig. 4 shows the thermo-gram of KDC crystals, which shows that the crystal is stable up to nearly
95oC. Then dehydration takes place through two stages at 100oC and 150oC, respectively, and
becomes dehydrated at 150oC after the loss of approximately 15% of its original weight. Then, the
anhydrous sample is converted into carbonate form at nearly 213 oC followed by the loss of
approximately 49% of its original weight. During the final stage of decomposition at 500 oC, the
sample is converted into oxide form after the loss of nearly 66% of its original weight. From the
analysis, it was found that two water molecules are associated with the crystals.
Thermal analysis.

Fig. 4. TGA curve of KDC crystal.

Table 2 gives details of the thermal decomposition of pure KDC with theoretically calculated and
experimentally obtained values of weight % of the sample at different stages.

Table 2. Theoretical and experimental weight % of KDC.

Theoretical mass Experimental mass


T(OC) Substance
loss (%) loss (%)
35 C6H7KO7.nH2O 100 100
(R.T.)
150 C6H7KO7 85.18 86.60

213 K2CO3 51.11 51.51


500 K2O 34.81 33.39

Summary. KDC crystals were grown by slow-solvent evaporation technique by giving rise to needle
shaped, transparent and colorless crystals. The triclinic symmetry of pure KDC was verified by
powder XRD. The existence of various functional groups was verified by FT-IR spectroscopy.
Thermal decomposition of KDC followed by various meta-stable stages was monitored by TGA
analysis. Two water molecules are found to be associated with the crystal.
References

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[1] Potassium dihydrogen citrate:IN 332(i), available at: www.foodnetindia.in/potassium-


dihydrogen-citratein-332i-3/
[2] Charles Sinclair, Dictionary of food, A & C Black Publishers Ltd, 1998.
[3] Elson M. Haas, Role of Potassium in Maintaining Health, available at:
www.hkpp.org/patients/potassium-health
[4] Treament with potassium citrate, Hypocitraturia, available at:
emedicine.medscape.com/article/444968-overview#a15
[5] Love W.E., A.L.Patterson. Acta cryst. Vol. 13 (1993), p. 426.
[6] Zacharias D.E. & J.P.Glusker, Structure of a citrate double salt: potassium dihydrogen citrate
lithium potassium hydrogen citrate monohydrate, Acta cryst. C49, (1993), pp. 1727-1730, DOI
10.1107/S0108270193002112
[7] Thomas V. Van Auken, Solubility and heat of solution of potassium dihydrogen citrate, J.Chem.
Eng. Data 36, (1991), pp. 255-257, DOI 10.1021/je00002a028
[8] Aygun Z., AFM and SEM Studies of VO2+ Doped Potassium Dihydrogen Citrate Single Crystal
Obtained by Slow Evaporation Method, J.Chem cryst. Vol. 43 (2013), pp. 103-107, DOI
10.1007/s10870-013-0391-4
[9] Aygun Z., Variable temperature EPR studies of Cu2+ and VO2+ doped potassium dihydrogen
citrate (C6H7KO7), Spectrochimica Acta. Vol. 104 (2013), pp. 130-133, DOI
10.1016/j.saa.2012.10.079
[10] Zeynep Yarbai, Abdulhalik Karabulut, Bnyamin Karabulut, EPR and optical studies of
vanadium doped potassium dihydrogen citrate (C6H7KO7) single crystal, Spectrochimica Acta. Vol.
79 (2011), pp. 1304-1307, DOI 10.1016/j.saa.2011.04.059

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Synthesis of Nd3+ Doped TiO2 Nanoparticles and Its Optical Behaviour21

Ezhil Arasi S.1,a, Victor Antony Raj M.1, Madhavan J.1

1 Department of Physics, Loyola College, Chennai-34, India


a jmadhavang@gmail.com

DOI 10.2412/mmse.21.46.481 provided by Seo4U.link

Keywords: sol-gel method, optical studies, energy transfer.

ABSTRACT. Pure and Rare earth ion doped TiO2 nanoparticles were synthesized by Sol-gel method. The synthesized
TiO2 nanoparticles were characterized by X-ray diffraction, Raman spectroscopy, UVVis spectroscopy and
photoluminescence emission spectra. From the UV-visible measurement, the absorption edge of Nd 3+-TiO2 was shifted
to a higher wavelength side with decreasing band gap. Photoluminescence emission studies reveal the energy transfer
mechanism of Nd3+ doped TiO2 nanoparticles explain.

Introduction. In the recent years, remarkable progress has been achieved in synthesis and
characterization of titanium dioxide (TiO2) nanostructures due to their unique physical and chemical
properties leading to extensive use as sensing materials, photo catalyst, H2 storage, and electrode
materials [1]. Compounds doped with rare earth ions have received considerable interest in both
fundamental and application studies due to their significant technological importance and are used as
high performance luminescent devices, solar cells, solid-state lasers, time-resolved fluorescence
labels for biological detection and other functional applications. As a host material, TiO2 is considered
as a promising semiconductor with outstanding optical properties [2]. Due to wide band gaps, TiO2
is an important applicant for UV light absorption, and is almost transparent for infrared (IR) and
visible light. It is a known fact that when dopants are added to a semiconductor they introduce band
gap states inside the band gap and these mid-states act as luminescent centers or nonradiative traps.
Because of the effective emission in the visible and near IR region, doping of TiO2 with rare earth
elements has attracted much attention [3].
Synthesis of TiO2 nanoparticles. Pure and doped TiO2 samples were synthesized by a sol-gel
method. 5ml of Titanium (IV) isopropoxide was added drop wise under vigorous stirring into 30ml
of isopropanol. This mixture was added drop wise into 30ml of distilled water under stirring. The
final pH was adjusted with an aqueous solution of ammonia. The mixture was left for 24 hours at
room temperature to complete the hydrolysis. The precipitate was dried at 100C for 1 hour and the
resultant white powder was milled. The obtained samples were centrifuged in distilled water and
ethanol three times in order to remove any impurities and further calcinated at 400C for 3hours.
The metal ion doped TiO2 nanoparticles were synthesized using the same technique as described
above. The Nd compound of Nd2O3 was used as a dopant source.
Result and Discussion:
X-Ray Diffraction Study. The synthesized TiO2 nanoparticles were characterized by a X-ray
Diffractometer with monochromatic CuK (=1.5406 ) and taken over the 2 range 20 70 by
step scanning with a step size of 0.05. The strongest peak for the anatase (101) phase of TiO2 was
used to determine the average size of the metal oxide nanocrystallites using Scherers equation,

21
2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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D=

where D - crystallite size:


K is the constant of 0.9:
is the wavelength of X-Ray:
is the full width at half- maximum (FWHM) of the selected peak and is the Braggs angle
of the diffraction of the peak.

Fig. 1. XRD patterns of pure and Nd3+ doped TiO2 nanoparticle.

Figure 1 shows XRD pattern of pure and Nd3+ doped TiO2 nano particles respectively. The diffraction
peaks corresponding to 2 values are identified as (1 0 1), (1 1 2), (2 0 0), (1 0 5), (1 2 1), (2 0 4) and
(1 1 6) and it matches well with the diffraction pattern of bulk anatase Titania peaks. XRD patterns
are matched with the standard XRD pattern of TiO2 (JCPDS file No: 21-1272).
The peaks at 2 correspond to the (1 0 1), (0 0 4), (2 0 0), (1 0 5), (2 1 3) and (2 1 3) planes of
TiO2:Nd3+ nanoparticles. The average crystalline sizes of pure and doped TiO2 nano particles were in
the range of 15 - 25 nm.
UV characterization. UV-Vis absorption Spectra was recorded by using Varian Cary 5E
spectrophotometer. The UV-Vis spectral analysis was carried out between 200 nm and 800 nm.

Fig. 2. UV-Vis absorption spectrum of pure and Nd3+: TiO2 nanoparticles.

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The plot between the absorption coefficient and wavelength is as shown in Figure 2 for pure and
doped TiO2 nanoparticles. The knee edge at 360 nm in the spectrum shows a shift compared to its
bulk counterpart which is nearly 50 nm, due to the weak quantum effect occurred during the growth
process.
The absorption spectra of Nd3+. TiO2 nanoparticle reveals sharp absorption edge observed at
395nm. The presence of Neodymium had shifted the absorption edge by 35nm from the undoped
TiO2.
FT-Raman analysis. Figure 3 shows the FT-Raman spectra of pure and doped TiO2 nanoparticles
synthesized via sol-gel method in the range of 100800 cm1. The FT-Raman spectrum was recorded
using BRUKER IFS66V spectrometer.

Fig. 3. FT-Raman spectrum of the pure and Nd3+: TiO2nanoparticles.

The Raman spectrum of the pure TiO2 shows peaks at 143.6 cm-1, 194.2 cm-1, 395.5 cm-1, 515.7 cm- 1
and 638.7 cm-1, which can be assigned to the anatase phase [4]. The spectra of Nd3+:TiO2 nanocrystals
are similar to that of anatase but being slightly shifted because of crystal structure modication via
doping. The Raman spectrum of Neodymium trivalent ion doped TiO2 (Figure 4.14) shows peaks at
144.76 cm-1, 147.76 cm-1, 398.68 cm-1, 517.93 cm-1 and 639.24 cm-1.Thus from the Raman studies
we can confirm that the anatase phase was not altered by the presence of trivalent lanthanide dopants.
Photoluminescence (PL). The photoluminescence spectrum of pure TiO2 nanoparticles was recorded
in the spectral range of 490-550nm. The peak positioned at 515 nm of the pure TiO2 is due to the
radiative annihilation of the exciton after excitation at 330 nm.
The PL spectra of 4F3/2 4
IJ belonging to f-f transition of the trivalent Nd ion in TiO2: Nd
nanoparticles are shown in figure. For the excitation wavelength of 350nm, Two main PL peaks were
found at 1095nm and 1366nm. In the prominent transitions are 4F3/2 4I11/2 and 4F3/2 4I13/2 lying at
1095 nm and 1366nm is due to the f-f transitions of Nd3+ [5, 6].

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Fig. 4. Photoluminescence spectrum of pure and Nd3+ TiO2 nanoparticles.

Summary. The successfully prepared TiO2, Nd3+ doped TiO2 samples were subjected to various
optical studies. From XRD results, it is clear that synthesized pure and doped Titania nanoparticles
exhibited the anatase structure. From the optical absorption spectrum, a significant spectral shift in
the wavelength is observed as compared to bulk TiO2 crystal. The broadening of absorption edge is
the result of absorption of nanocrystallites with distribution of anatase nanoparticles at different size
regime. The presence of trivalent lanthanide ions had resulted in shifting of the absorption edge
towards the visible region.
References
[1] Vijay K. Tomer, Suman Jangra, Ritu Malik, Surender Duhan, Effect of in-situ loading of nano
titania particles on structural ordering of mesoporous SBA-15 framework, Colloids and Surfaces A:
Physicochem. Eng. Aspects 466 (2015) 160165. DOI 10.1016/j.colsurfa.2014.11.025
[2] X. Qi et al. Controllable synthesis and luminescence properties of TiO2:Eu3+ nanorods,
nanoparticles and submicrospheres by hydrothermal method, Optical Materials 38 (2014) 193197.
DOI 10.1016/j.optmat.2014.10.026
[3] A.S. Bhatti et al, Tunability of morphological properties of Nd-doped TiO2 thin films, Mater. Res.
Express 3 (2016) 116410. DOI 10.1088/2053-1591/3/11/116410
[4] Mona Saif, Abdel Mottaleb M. S. A., Titanium dioxide nanomaterial doped with trivalent
lanthanide ions of Tb, Eu and Sm: Preparation, characterization and potential applications, Inorganica
Chimica Acta, 360 (2007) 2863 2874. DOI 10.1016/j.ica.2006.12.052
[5] Rajesh Pandiyan et al., Structural and near-infra red luminescence properties of Nd-doped TiO2
films deposited by RF sputtering, J. Mater. Chem., 2012, 22, 2242422432. DOI
10.1039/c2jm34708c
[6] S.Yildirim et al., Structural and luminescence properties of undoped, Nd3+ and Er3+ doped TiO2
nanoparticles synthesized by flame spray pyrolysis method, Ceramics International (2016), DOI
10.1016/j.ceramint.2016.03.131

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Electrochemical Determination of 4-Nitrophenol by Manganese (II) Schiff Base


Complex Modified GCE22

S. Praveen Kumar1, S. Munusamy1, S. Muthamizh1, A. Padmanaban1, T. Dhanasekaran1,


G. Gnanamoorthy1, V. Narayanan1,a

1 Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai, India


a vnnara@yahoo.co.in

DOI 10.2412/mmse.56.69.941 provided by Seo4U.link

Keywords: manganese (II) Schiff base complex, microwave irradiation, 4-nitrophenol, differential pulse voltammetry,
electrochemical polymerization.

ABSTRACT. A selective and sensitive electrochemical determination method was developed for the determination of 4-
nitrophenol by manganese (II) Schiff base complex modified glassy carbon electrode (GCE). The manganese (II) Schiff
base complex was synthesized by a simple green chemical route and it was characterized by FT-IR, Raman, UV-Visible
and fluorescence spectral techniques. The electrochemical redox behaviour of manganese (II) Schiff base complex was
examined in acetonitrile solution with the aid of cyclic voltammetry. The electrochemical behaviour of 4-nitophenol at
both electrodes were investigated thoroughly in acetate buffer solution at pH-5. The 4-nitrophenol yields an sharp
reduction as well as an oxidation peaks at manganese (II) Schiff base complex modified GCE. The well define redox
peaks at modified GCE has lower potential and higher peak current than bare GCE. Based on the electrocatalyitc redox
observations of 4-nitrophenol we can propose an electrocatalytic sensor for the 4-NP direct determination in real sample
analysis. In the electrochemical determination process various kinetic parameters were calculated, such as number of
electron and proton transfer, rate constant etc., differential pulse voltammetry technique was utilized for the determination
of 4-NP. Under the optimization conditions the peak current various linearly with the concentration of 4-nitrophenol in
the range of 8 M to 166 M. The detection limit of the proposed electrocatalytic sensing method is 0.457 M with the
sensitivity of 6.2354 A/M. Moreover, the fabricated electrocatalytic sensor has high selectivity and long-term stability.
This proposed electrocatalyitc sensor can be used for the determination of 4-NP in real water samples analysis.

Introduction. Phenolic derivatives are mostly used in many industrial synthetic processes and it was
released into environment. The phenolic compounds are of primary importance and utilized in the
synthesis of pesticides, dyes, pharmaceuticals, paints and petrochemical products. These phenolic
compounds were gives undesirable colour to water. They prevent the sunlight penetration and
retarding photosynthetic reactions in water. It affects the aquatic life and poses various detrimental
eects to living beings and plants. These compounds are considered as environmental hazards
material by USA Environmental Protection Agency, because of its toxicity to humans, animals and
plants. Among the phenolic compounds, 4-nitrophenol (4-NP) is the most hazardous substance, it
causes signicant effects to the environment. This 4-NP has been reported as a potential carcinogen,
mutagen and teratogen, and it also causes headaches, drowsiness, nausea and cyanosis. Hence, there
is a necessity for monitoring the 4-NP to avoid adverse eects on living beings. Therefore,
quantification of 4-NP and other phenolic compounds are getting urgent for environmental protection.
There are several methods were reported for the quantification of 4-NP, like ow-injection analysis,
spectrophotometry, HPLC, capillary electrophoresis, gas chromatography (GC), fluorescence and
electrochemical method. Among the reported methods, electrochemical method has great important,
because of its cost effect, faster response and simple procedure. Therefore, in the present work we
consider the electrochemical method has been utilized for the quantification of 4-NP. In this method,
the modified materials play a key role to improving the detection performances, based on this effect

22
2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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manganese(II) Schiff base complex was utilized as a modifier for the 4-NP quantification [1, 2]. The
manganese complexes with Schiff base ligands (N,O-donor ligand) getting more attention in the
research field, since its significant roles in various fields such as biological, chemical analysis and
industrial applications. The manganese complexes possess different types of magnetic behaviors, like
ferromagnetic, antiferromagnetic, metamagnetic, and spin flop have been observed. Hence the
manganese complexes can play a vital role in material chemistry. The highvalent manganese
complexes have been studied mostly in their physical and chemical properties; additionally these
complexes provided potential abilities in biological modeling application. The manganese complexes
were used as oxygen evolving complexes (OEC) in photosystem II (PS II), water splitting for
evolution of fuels. The manganese Schiff base complexes have suitable biometric properties, which
can mimic the structural features of the active site in metalloenzymes, redox and non-redox proteins.
In addition, manganese complexes were catalyze the disproportionation of hydrogen peroxide, it
produced a reactive oxygen species (ROS) in the body. These manganese complexes have different
oxidation states, which possess good electrochemical redox activity [3, 4]. By varying the substituent
groups in Schiff base ligand, chemists discovered potential manganese complexes for multiple
applications with the aid of novel synthetic process. In the present work manganses (II) Schiff base
complex was synthesized by microwave irradiation method and utilized for electroctalytic
determination of 4-nitrophenol.
Experimental procedure. Manganese (II) Schiff base complex was synthesized by microwave
irradiation method using following procedure. One mmol of o-phenylenediamine was added with the
2 mmol of salicylaldehyde under stirring in methanol medium. A yellow colour solution was obtained
it was subjected for microwave irradiation at 320 W for 2-3 min. After the irradiation it was kept in
normal atmosphere in room temperature for 24 hr. A yellow colour precipitate was obtained, it was
collected and recrystallized by hot ethanol. After that 1 moml of manganese (II) chloride was
gradually added with 1 mmol of Schiff base ligand under stirring condition in methanol medium. A
brown colour solution was obtained it was employed for microwave irradiation at 320 W for 5 min
and kept in room temperature for 24 hr. a brown solid was obtained it was collected and recrystallized
by hot ethanol (fig. 1).

Microwave
Irradiation N OH
NH2
MnCl2 .4H2O N O
2 + OH2
320 W, 2-3 min N OH Mn
NH2 OH
Microwave N O 2
O OH Irradiation
320 W, 5 min

Fig. 1. Synthesis of manganese(II) Schiff base complex.

Result and Discussion


FT-IR spectral analysis. The FT-IR spectrum of the manganese(II) Schiff base complex was
recorded in the range of 400-4000 cm-1 and shown Fig. 1a. In the IR spectra the imine group [ (C=N)]
absorption band was shifted towards lower frequencies due to the bond formation between the imine
nitrogen and manganese(II) metal ion. This peak was appeared at 1633 cm-1. The imine nitrogen
forms a bond with manganese(II) ion through its lone pair of electrons. This imine group normally
appeared in above 1650 cm-1 in free Schiff base ligand, the appearance of [ (C=N)] in lower
frequencies was confirms the complex formation between Schiff base ligand and manganese(II) metal
ion. In addition two other peaks due to metal nitrogen and metal oxygen also gives more clarity of
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complex formation in the range of 400-600 cm-1. The metal nitrogen peak [ (N-Mn)] was appeared
at 595 cm-1 and the metal oxygen [ (O-Mn)] peak was appeared at 540 cm-1. A peak was appeared
at 825 cm-1 was due to the presence of phenyl ring in the manganese(II) Schiff base complex. Other
characteristic peaks also observed in the IR spectrum, C-C single bond appeared at 2930 cm-1,
aromatic C=C double bond exhibits its vibrational peak at 1305 cm-1 and C-N peak was appeared at
1485 cm-1. These IR peaks were confirms the manganese (II) Schiff base complex formation.
UV-Visible spectral analysis. The UV-Visibl spectrum of manganese (II) Schiff base complex was
studied in methanol solution at normal ambient condition in the range of 200-800 nm, and it was
shown in Fig. 1b. The UV-Visible spectrum of the manganese(II) Schiff base complex shows an
absorbance peak at 275 nm is exhibit due to n* electronic transition in the organic moieties of
Schiff base ligands. In the electronic spectrum a band appeared at 220 nm is suggest that *
electronic transition in the aromatic ring. The d-d transition of manganese (II) metal ion is exhibit in
visible region 405 and 625 nm. The characteristic transitions suggest the geometry of the manganese
(II) Schiff base complexes is octahedral, and it has high spin the measured magnetic momentum is
3.76 BM, it highly matched with the theoretical magnetic momentum of manganese(II) complexes.
EPR spectral analysis. The EPR spectrum of manganese (II) Schiff base complex was studied in
methanol solvent at normal atmospheric condition. The EPR spectrum of the manganese complex
was shown Fig. 1c. The EPR spectrum of complex manganese (II) complex shows sextet splitting, it
clearly indicates that manganese present at +2 oxidation state, since I value is 5/2. The g factor value
of all splittings are closed to the free electron value of 2.156, it suggest the absence of spin orbit
coupling in the ground state. The g values indicate that the Mn (II) in these complexes are rhombically
distorted and the manganese hyper-ne splitting is not observed in the spectrum. In addition, they
have agreement with previous reported for similar structure of Mn (II) complex.
Electrochemical studies. The electrochemical redox behaviour of the manganese Schiff base
complex was investigated by cyclic voltammetry, in three electrode system. The glassy carbon
electrode was used as working electrode, silver and silver chloride (Ag/AgCl) was reference and
platinum wire used as counter electrodes. The Voltammetry measurement was carried out in 0.1 M
acetonitrile solution of manganese (II) Schiff base complex in presence of tetrabutylammonium
perchlorate (TBAP) supporting electrolyte. The obtained cyclic voltammogram shows the
electrochemical redox properties the manganese (II) metal ion and it was given in Fig. 2d. The
manganese Schiff base complex shows only an oxidation peak, which corresponds to the oxidation
of Mn (II) to Mn (III) oxidation state. In the anodic process number of electron transfer was calculated
using ip = nFQ/4RT equation, it confirms the one electron transfer in the electrochemical reaction.
The anodic peak was appeared at 0.439 V as a broad peak. From the cyclic voltammogram we
conclude that Mn (II) Schiff base complexes were electrochemically active and show response in the
potential range of 0 to 0.9 V vs Ag/AgCl. The redox potential of the Mn (III)/Mn (II) is dependent on
number of factors such as coordination number of the complex, bulkiness and hard/soft nature of the
ligand. The manganese (II) Schiff base complex shows good electrochemical redox properties due to
the electron transfer between two stable oxidation states Mn (II) to Mn (III).
Electrochemical polymerization. The electropolymeriztion was done in the potential range of 0 to
0.9 V at the scan rate of 50 mVs-1 and 20 cycles. The cyclic voltammogram for electropolymerization
of manganese(II) Schiff base complex was shown in the Fig. 2a. The poly-manganese Schiff base
complexes (poly-MnSBC) were deposited on the surface GC electrode. The modified electrode was
dried and stored at 10 0C when it was not used for the sensing process. The poly-MnSCB coverage
concentration was determined by the following equation, =Q/nFA. Where Q is the charge, n is the
number of electrons involved in the electropolymerization, F is the Faradays constant, A is the area
of the electrode (A = 0.0707 cm2). The calculated modified electrode surface coverage concentration
was 0.234610-11 mol cm-2. This modified electrode was used for the electrocatalytic sensing of 4-
NP. The Mn (II) Schiff base complex electrochemical polymerization follows the stacked
polymerization process [5].

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Fig. 2. (a) FT-IR spectrum, (b) UV-Visible spectrum, (c) EPR spectrum and (d) Cyclic
voltammogram in 0.1 M TBAP at the scan rate of 50 mVs-1 of manganese(II) complex.

Electrocatalytic sensing of 4-nitrophenol. The electrocatalytic sensing behavior of bare GCE and
manganese (II) Schiff base complex modified GCE towards 4-NP determination in 0.1 M phosphate
buer was estimated by cyclic voltammetry in the sweeping potential of 0.8 V to -0.8 V and it was
shown in Fig. 3b. The 4-NP was determine in the oxidation processes, which is monitoring after the
reduction of NO2 group to NH2, followed by oxidation of NH2 group. For bare GCE, the 4-NP
oxidation was appeared at 0.375 V with anodic peak current 2.67 A. IT is attributed to the
irreversible oxidation of the NH2 group. The modified GCE shows the same anodic process at 0.379
V with peak current of 5.25 A. The modified GCE exhibits a sharp anodic peak when compare with
bare GCE, Besides with it has more peak current double the amount of bare GCE. It explains that the
modified GCE has enhanced sensing activity for the 4-NP determination, it was attributed by the
polymerized manganese (II) Schiff base complex. The presence of Mn (II) ion in the active surface
will leads better electrochemical redox process of 4-NP, which gives better activity in the
quantification process [6, 7]. These results of 4-NP determination shows that manganese (II) Schiff
base complex incerase the activity and it can be a good electrocatalytic sensor. This manganese (II)
Schiff base complex can utilized for the determination of 4-NP in real samples.

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Fig. 3. (a) Cyclic voltammogram of Mn(II) Schiff base complex polymerization in 0.1 M TBAP, (b)
Cyclic voltammogram of Electrocatalytic sensing of 4-NP in PBS at the scan rate of 50 mVs-1.

Summary. Manganese (II) Schiff base complex was synthesized by microwave irradiation method
and it was characterized by FT-IR, UV-Vis and EPR spectral techniques. All the spectral techniques
were confirms the Mn (II) Schiff base complex formation. The electrochemical behaviour of Mn (II)
Schiff base complex was studied by cyclic voltammetry it shows an oxidation process of Mn(II) state
to Mn(III) and the manganese(II) Schiff base complex was subjected to electrochemical
polymerization. The polymerized Mn (II) Schiff base complex was deposited on the GCE surface and
the modified electrode was successfully studied for the detection of 4-NP. The modified electrode
shows a better result than bare GCE. Hence it can be used for quantification of 4-NP in real samples.
Acknowledgment
One of the authors (S.P.K) wishes to thank Department of Science and Technology (DST),
Government of India for the financial assistance in the form of INSPIRE fellowship (Inspire Fellow
no: 130032) under the AORC scheme.
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Anal. Methods, Vol. 7, 2015, 1794-1801, DOI 10.1039/c4ay02857k.
[7] J. Luo, J. Cong, J. Liu, Y. Gao, X. Liu, Anal. Chim. Acta, Vol. 864, 2015, DOI
10.1016/j.aca.2015.01.037.

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Synthesis of Vanadium (III) Schiff Base Complex and its Electrocatalytic


Sensing Application23

P. Supriya Prasad1, Praveen Kumar2, K. Bharathi1, V. Narayanan1,a

1 Department of Chemistry, DKM College for Women, Vellore, India


2 Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai, India
a vnnara@yahoo.co.in

DOI 10.2412/mmse.47.57.91 provided by Seo4U.link

Keywords: Vanadium (III) Schiff base complex, microwave irradiation, Vitamin-B6, differential pulse voltammetry,
electrochemical polymerization.

ABSTRACT. The coordination chemistry of vanadium complexes have been focused more than half a century because
of its interesting structural and chemical activities. The vanadium complexes are wide used in biological and industrial
fields. The vanadium Schiff base complex was synthesized by simple and green chemical microwave irradiation synthetic
process. The Schiff base ligand was synthesized by condensation reaction between 5-chlorosalicylaldehyde and N, N-
bis (3-aminopropyl)ethylenediamine, with this Schiff base ligand vanadium(III) chloride was added for the formation of
vanadium(III) Schiff base complex. The Schiff base ligand provide a tetradentate planar structure to vanadium (III) center
metal for the formation of stable complex. It was characterized by FT-IR, UV-Visible, Raman and fluorescence spectral
techniques. The electrochemical redox activity of vanadium (III) Schiff base complex was studied by cyclic voltammetry
with three electrode system. The synthesized vanadium complex was utilized for the electrocatalytic sensing of vitamin
B6. The vanadium (III) Schiff base complex was electrochemically polymerized, the polymer Schiff base vanadium
complex was deposited on the surface of GCE. The modified GCE was exhibits an anodic peak for vitamin B6 at 1.25 V
with peak current 8.89 A. The bare GCE shows the oxidation potential at 1.28 V with peak current is 7.77 A. From the
result we can conclude that the vanadium(III) Schiff base complex modified GCE has better electrocatalytic sensing
activity for the determination of vitamin B6 and it can be used for real sample analysis.

Introduction. Schiff base ligands have considerable attention, because of its facile synthesis and
wide range of applications in different fields. Schiff bases are privileged ligands due to their ligating
behavior towards metal ions. The Schiff bases are synthesized by a simple one-pot condensation
between a carbonyl group of ketone or aldehyde with amine, the carbonyl groups are replaced by an
imine group in an alcoholic solvent [1]. More than a century, the Schiff base metal complexes have
been rigorously studied and utilized in various elds, such as biological, chemical analysis, magnetic
materials, non-linear optics, electrocataytic sensors, catalyst in synthetic chemistry and photo
physical studies. The Schiff base metal complexes have high stability in different oxidation states,
hence these complexes have wide range of application. Among the various Schiff basemetal
complexes, the vanadium (III) have great interest in fast few decades due to its catalytic and
medicinal importance. Vanadium is an important trace bio-element, it plays a vital role in many
metabolic and mitogenic processes. To know the role of vanadium in biological process, it is necessity
to carry out the studies in model vanadium complexes. The interactions of amino acids and peptides
with vanadium complexes are better example for biological studies. The studies of vanadium (III)
complexes have been investigated less than the corresponding chemistry of vanadium (IV or V)
complexes. However, the vamadium (III) complexes can play important role in biochemical redox
processes and there are organisms, such as ascidians in which the principal oxidation state of
vanadium is +3. Even though the inorganic vanadium salts have less biological activities and toxicity,
the complexation with organic ligands of vanadium leads to minimize the adverse effects. The

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vanadium compounds have different physiological roles, such as insulin-mimetic action, anti-
hypertension, anti-hyperlipidemia, anti-obesity. The Henzes reported that certain ascidians sequester
have vanadium (III) complexes in their blood cells, it spurred the interest of chemists to investigated
vanadium (III) complexes [2]. However, the investigation of structures and activities of vanadium
(III) complexes in biological process may give some understanding the puzzling role of vanadium
(III) in ascidians. In addition, complexes of vanadium (III) with organic ligands like Schiff base can
explains, the efficiency of vanadium (III) complexes in catalytic process and other biological active
process. In the present work the vanadium (III) Schiff base complex was synthesized by microwave
irradiation method and it was characterized by several spectral techniques. The synthesized vanadium
complex was electrochemically polymerized and utilized for the sensing of vitamin B6. Vitamin B6
(pyridoxine) is an important vitamin for both mental and physical health process. Vitamin B6 (V-B6)
is much essential for the formation of red blood cells. It takes wide variety of functions in human
body for maintaining good health. The conversion of tryptophan amino acid to niacin vitamin needs
the V-B6. V-B6 is an important vitamin for the nervous and immune systems function. V-B6 is an
essential vitamin for the better healthy condition of human body. The deciency of V-B6 can causes
anemia that is similar to iron deciency anemia. Due to these health factors it is necessity to develop
a simple, selective and sensitive method for the analysis of V-B6. There are so many analytical
methods were available for the quantification of V-B6, but the electrochemical method gives better
results for the V-B6 determination. Hence, the electrocatalytic determination was used for the V-B6
quantification, it gives low detection limits, simple experimental procedure, cost effective and better
sensitivity. This vanadium complex has good electrocatalytic sensing ability for V-B6 determination.
Experimental Procedure. Vanadium (III) Schiff base complex was synthesized by the following
procedure. An absolute 2 mM [0.313 g] of methanolic solution of 5-chlorosalicyaldehyde was taken
in a 250 ml beaker to this aldehydic solution, 1 mM [0.174 g] of N,N-bis(3-
aminopropyl)ethylenediamine in methanol was added drop wise with the aid of burette under stirring
condition. A yellow colour solution was obtained. The yellow coloured reaction mixture was
employed for microwave irradiation at 320 W, 2-3 min. After that, the reaction mixture was cooled
to room temperature and kept for 12 hr. A yellow solid product was obtained it was collected and
recrystallized using 1:1 methanol in hot condition and dichloromethane. The synthesized Schiff base
ligand was used for the vanadium Schiff base complex synthesis. 1 mM of the Schiff base ligand was
taken and 1 mM of vanadium (III) chloride was added to Schiff base ligand under stirring using in
methanol medium. A brown colour solution was obtained and it was subjected to microwave
irradiation at 320 W, for 5 min. The reaction mixture was cooled to room temperature and kept in 24
hr. A brown vanadium (III) Schiff base complex was obtained. The vanadium (III) Schiff base
complex was collected and recrystallized by using hot ethanol solution.
Cl Cl +

Cl NH2 Microwave N OH N O
NH Irradiation OH2
NH NH
2 + VCl3 V OH
2
320 W, 2-3 min
NH NH2 NH N OH NH N O
Microwave
O OH Irradiation
320 W, 5 min

Cl Cl

Fig. 1. Synthesis of Vanadium(III) Schiff basecomplex.

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Result and discussion


FT-IR spectral analysis. The FT-IR spectrum of vanadium (III) Schiff base complex was shown
Fig. 1a. In the IR spectrum several peaks are observed for various bonds. The imine [ (C=N)] group
exhibits a band at 1625 cm-1, it appeared at lower frequency when compare to the free Schiff base
ligand C=N, due to the bond formation between the imine group nitrogen with the vanadium metal
ion. The free C=N in Schiff base ligand exhibits its vibrational frequency peak around 1650 cm -1. It
indicates that bond formation of the nitrogen atom with the vanadium metal ion. In addition the
complex formation was confirmed by two other characteristic peaks in the region of 400 600 cm-1,
these peak suggest the bond formation between the vanadium metal ion with the oxygen and nitrogen
atoms. The vanadium oxygen bond shows it vibrational frequency (V-O) at 496 cm-1 and the
nitrogen vanadium bond appeared at 595 cm-1, these three peaks confirms the complex formation.
Besides with few characteristic peaks were appeared, a peak at 3326 cm-1 shows the presence of
solvated water molecules in the metal complex, the C-C shows a peak at 2936 cm-1, a peak observed
at 1358 cm-1 due to aromatic C=C and the C-N bond exhibits a peak at 1455 cm-1 in the complex.
The phenyl ring shows its vibrational frequency at 820 cm-1. All these vibrational peaks are confirmed
the formation of vanadium (III) Schiff base complex.
Electronic spectral analysis. The electronic spectrum of vanadium (III) Schiff base complex was
recorded in the range of 200-800 nm, in the methanol solution and it was shown in Fig. 1b. In the
spectrum an absorbance peak at 220 nm appeared due to the * transition in the aromatic ring of
Schiff base ligand and another peak appeared at 300 nm, which is corresponds to the n* transition
in the azomethane group. The band at 410 nm is due to charge transfer (LMCT) transitions. The weak
band at about 650 nm corresponds to d-d transition of vanadium (III) ion, which can be assigned as
3
T2g 3T1g in octahedral geometry. The electronic transitions in the absorption study suggests that
the vanadium (III) Schiff base complex in octahedral geometry [3].
Raman spectral analysis. Raman spectrum of vanadium (III) Schiff base complex was given in
Fig. 1, c. In the Raman spectrum the imine group, metal nitrogen and metal oxygen bond vibrational
peaks was consider for confirms complex formation. The imine C=N group exhibits a sharp peak at
1525 cm-1, which is lower region when compare to that of free ligand imine group Raman spectral
analysis was carried out using laser Raman microscope in the range of 200 2500 cm-1 for vanadium
(III) Schiff base complex, which is shown in Fig. 1, c. We can observe the characteristic vibrational
bands of the complex in the expected region. In the Raman spectra the azomethine group -C=N-
vibrational frequency was observed in the range of 1525 cm-1. The C=N- peak appears at lower
frequency in V (III) Schiff base complex than the free ligand, it indicates that the nitrogen atom in
azomethane group has coordination with vanadium metal ion. In the spectrum a sharp peak appeared
around 810 cm-1 corresponds to vibrations frequency of phenyl ring in the V(III) Schiff base
complex. The metal nitrogen and metal oxygen bonds were exhibited around 551 and 480 cm-1 in
the Raman spectra which confirms the complex formation between Schiff base ligand and vanadium
(III) metal ion through metal nitrogen (V.N) and metal oxygen (VO) bonds. The complex
formation is confirmed by shift in a number of stretching frequency to lower than free Schiff base
ligand.
Electrochemical studies. The redox behaviour of vanadium(III) Schiff base complex was examined
by cyclic voltammetry, in three electrode system. The glassy carbon electrode utilized as working
electrode, silver and silver chloride (Ag/AgCl) as reference electrode and platinum wire was counter
electrode. Voltammetry measurement was carried in 0.1 M acetonitrile solution, in the presence of
tetrabutylammonium perchlorate (TBAP) as supporting electrolyte. The obtained cyclic
voltammogram explains the electrochemical redox properties of the vanadium metal ion, it was show
in Fig. 1d. The positive potential of metal ion shows that vanadium ion has lower oxidation state and
strongly binds with Schiff base ligand. The vanadium Schiff base complex shows an oxidation peak
and its corresponding reduction peak. The anodic peak appeared at 0.345 V due to the oxidation
process of V(III) to V(V). The cathodic peak exhibits at -0.282 V for the reduction process of V (V)
to V(III). The electrons were transferred between two stable oxidation states, when the potential was
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applied. The electrochemical studies show that vanadium (III) Schiff base complex has good
electrochemical redox behaviour [4].

Fig. 2. (a) FTIR spectrum, (b) UV-Visible spectrum, (c) Raman spectrum and (d) Cyclic
voltammogram in 0.1 M TBAP at the scan rate of 50 mVs-1 of vanadium(III) complex.

Electrochemical polymerization. The vanadium (III) Schiff base complex was electrochemically
polymerized and used for the sensing of vitamin B6. The glassy carbon electrode (GCE) was modified
by the electrochemical polymerization of 0.1 M vanadium (III) Schiff base complex in acetonitrile
solution, at -0.5 to 0.5 V working potential. The polymerized vanadium (III) complex was deposited
on the surface of GCE. The electrochemical polymerization was occurred due to the vanadium (III)
redox process i.e., {V (III) to V (V)} and {V (V) to V (III)}.
Electrocatalytic Sensing of vitamin B6. The electrocatalytic sensing of vitamin B6 (V-B6) using
vanadium (III) Schiff base complex modified GCE and bare GCE was investigated with the aid of
cyclic voltammetry in phosphate buffer as background electrolyte. Cyclic voltammograms of V-B6
at bare GCE and poly-V-SBC/GCE as working electrodes are shown in Fig. 2b. V-B6 exhibits an
anodic peak only for both the electrodes. The oxidation of V-B6 at bare GCE is 1.277 V, with the
peak current of 7.97 A. The poly-V-SBC/GCE shows the V- B6 anodic peak at 1.264 V, with peak
current is 8.95 A. The modified GCE shows lower anodic potential with higher peak current when
compare with bare GCE. These results clearly explains that the vanadium Schiff base complex
modified GCE has better electrocatalytic sensing ability for vitamin B6 determination. The enhanced
sensing activity was attributed by the vanadium (III) Schiff base complex [5, 6].

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Fig. 3. (a) electrochemical ploymerization of vanadium(III) Schiff base complex in 0.1 M TBAP, (b)
Sensing of vitamin B6 in PBS at the scan rate of 50 mVs-1.

Summary. Microwave irradiation method was utilized for synthesis of Vanadium (III) Schiff base
complex and characterized by FT-IR, UV-Vis. and Raman spectral techniques. The electrochemical
redox property of V (III) Schiff base complex was studied by cyclic voltammetry. The vanadium
Schiff base complex was electrochemically polymerized on the GCE surface and the modified
electrode was successfully used for the detection of vitamin B6. The modified electrode shows a
better result than bare GCE.
References
[1] Plass W. Chiral and Supramolecular Model Complexes for Vanadium Haloperoxidases:Host-
Guest Systems and Hydrogen Bonding Relays for Vanadate Species J. Coord Chem Rev, 2011, Vol.
255(19/20):2378-2387, DOI 10.1016/j.ccr.2011.04.014.
[2] Kanamori K. Structures and properties of multinuclear vanadium (III) complexes: seeking a clue
to understand the role of vanadium (III) in ascidians. Coord. Chem. Rev. 2003; 237:147161, DOI
10.1016/S0010-8545(02)00279-5.
[3] H. Podsiady, Z. Karwecka, Polyhedron Vol. 28, 2009, 15681572, DOI
10.1016/j.poly.2009.03.015.
[4] T.L. Riechel, L. J. D. Hayes, D. T. Sawyer, Inorg. Chem., Vol. 15, 1976, 1900-1904.
[5] B. Brunetti, E. Desimoni, J. Food Comp. Anal., Vol. 33, 2014, 155160. DOI
10.1016/j.jfca.2013.12.008.
[6] W. Qu, K. Wu, S. Hu, Voltammetric determination of pyridoxine (Vitamin B 6) by use of a
chemically-modified glassy carbon electrodeJ. Pharm. Biomed. Anal., Vol. 36, 2004, 631-635.

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II. Mechanical Engine ering & Physic s


M M S E J o u r n a l V o l . 1 0

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Negative Impacts on Railway Embankments Exposed to Wind-Blown Sand and


Optimizing the Economic Height24

Ahmed Abdelmoamen Khalil

1 Assistant Professor of Railway Engineering, Civil Engineering Department, Shoubra Faculty of Engineering, Benha
University, Postal Code: 11629 Egypt
a ahmed.khalil@feng.bu.edu.eg

DOI 10.2412/mmse.39.59.615 provided by Seo4U.link

Keywords: railway, embankment, track contamination, wind, sand, FLUENT.

ABSTRACT. Railway lines in deserts suffer from risks of migration of sand dunes, transport of sand by wind and its
accumulation over the tracks. This paper focuses on causes, types, and different characteristics of sand movement in
desert that affecting safety and performance of running trains. Risk and potential impact of accumulation of sand on
Bahariya railway line located in Western Desert of Egypt such as; several derailments and contamination of track
components are analysed. The purpose of this paper is to study the impact of embankment height on sand accumulation.
Thus, ANSYS FLUENT software is used to simulate the blown wind on the railway embankment to obtain the wind
velocity vectors and contours. Hence, embankment height that reduces deposition and accumulation of sand over the track
is obtained and recommended to 6 m. Cost analysis has been conducted to compare between the recent and the
recommended embankments. It is concluded that cost of the recommended embankment is about 63% of the overall cost
of the recent case.

Introduction. Wind is the main cause of sand movements, therefore; attention to the direction and
the velocity of the winds is also of importance. Needs for attention to this issue is especially important
when considering various preventive methods such as designing a wall [1]. In Egypt, sand deposits
and other aeolian forms cover about 27% of the whole country [2]. Morphologically these landforms
are subdivided into sand seas (ergs), isolated dunes and dune fields and sandy plains and sheets [2].
At several localities in Egypt, sand encroachment causes hazards to farmlands, highways, population
centers and other infrastructures. According to [3], sand encroachment over the inhabitable areas of
Egypt is classified into the following categories; (i) Severe dune migration ( > 15 m/year); it occurs
in South Al-Bardaweil (North Sinai) and Kharga-Baris and Dakhla in the South Western Desert, (ii)
Moderate dune migration (515 m/year); it prevails in Central Sinai, east of the Suez Canal, Siwa,
Abu Mongar, Farafra, Bahariya and El Rayan; (iii) Slight dune migration ( < 5 m/year); it occurs on
both sides of the Nile Delta, northern coast of the Nile Delta and along the Mediterranean Coastal
Zone. Source of the sand in the Sahara Desert is attributed to the fluvial processes which thereafter
reworked and deposited elsewhere by wind in later dryer ages [4].
Climate of western desert is too dry to have any rains. However the average value of rains is 3.6
mm/year. The average temperature is 29o C in the period from May to September in the north, but it
raises up to 32o C in the south. Maximum temperature reaches 50o C. January is the coldest month
in the year where the temperature reaches 13o C. However the minimum temperature lies between
0o C and 5o C. Wind blows from the north most of the year but it diverts to blow from the west in
winter. The wind speed reaches 20 m/s and it is usually high in the spring, hence sandstorms are
caused due to the high intensity of wind [5]. Railways had been established in the west desert of
Egypt in 1900 when the government offered the Company of the Oases of West Deserts a concession
to construct a railway line to connect the Oases with the Nile Valley. However, the company went

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bankrupt and the government seized the railway line in 1909. The line expanded from Mowasla
station to Kasr Elkharga station with a length of 210 km.
When the mining communities have been established in the west desert, especially with emergence
of iron and phosphorus ores, the railway transportation map has been changed where Egyptian State
has constructed Bahariya railway line. This line carried iron ore from Bahariya mines to the steel
factories in Helwan (South of Cairo). The line is also used to transport loamy clay from Oswan (South
of Egypt) to station (km 48), as well as ballast from a query at station (km 66) to different locations
in Egypt [6]. Nowadays, Bahariya railway line is a single track of length 346 km with 10 stations
including the start station in Bahariya mines and the end station at Helwan. During the wind blowing
period from November to end of April, sand which moves by the wind covers about 40% of the west
desert surface. So, land transportation including Bahariya railway line crashes in this period of the
year as shown in Fig. 1 [6]. This sand is transported by the wind which blows from the North-West
direction with an average speed of 15 m/s [6]. Bahariya railway line is about to be closed during that
period due to accumulation of sand over the tracks with average height of 0.10 m over the rail surface.
Thus, transportation of iron ore and other materials transferred to other transportation modes, e.g.
roadways, which have high cost. This transformation causes many losses to the Authority of Egyptian
National Railways (ENR) due to losing one of the most important sources of revenues.

Fig. 1. Bahariya railway track during the period of blowing sand.

It is also observed that accumulated sand affecting the track components with many negative impacts
such as; increasing the rail surface roughness which causes wear to the rails and train wheels, wear
and loosening of the rail fastening system. Because of those impacts, the train wheels are derailed
causing many derailment accidents. The derailment accidents result also in severe defects and
damages of the track sleepers and the whole stability of the track alignment. In addition to the
damages of track components and instability of the track system, ENR provided the line with two
sand sweepers and 7 loaders to remove the accumulated sand periodically. The annual deposited sand
on the track is about 250,000 m3 [7]. As the equipment removes sand and distribute it alongside the
railway line, the blown wind re-carries it causing re-covering the track. Investigation that carried by
[1] shows, by studding the direction and the intensity of the wind and identifying the removal and
sediment zones, one can design an optimize route through dunes with minimum dilemma. In [8]
studied the accumulation of fine sand in canals network in Toshka project which located in western
desert in Egypt. This researcher found that accumulation of fine sand is causing serious hydraulics
and biological problems such as rising of bed level which in turn change the hydraulic characteristics
of the canal (discharge, velocity, heads etc.). Also, the researcher recommended protecting means
was determined for the most regions exposed to active sand dunes movement as follow design of
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wind breaks, fixation the surface of one active sand dune by using stones on the sand dune surface
against the most common wind directions and construction of trenches on the bank of El Sheik Zayed
canal for trapping the moving sand.
This paper focuses on the negative impacts of wind- blown sand on the track of Bahariya railway line
and contributes in finding an optimized solution to reduce these impacts. Thus, the following
objectives are the core of this paper:
a) Investigating and detecting the railway track to assess and analyze the impact of sand accumulation,
b) Analyzing the wind simulation that has been carried out by the author using ANSYS FLUENT
software to find out the effect of the embankment height,
c) Determination of the optimized embankment height that reduces sand accumulation,
d) Recommend and check cross section for side ditches to minimize sand accumulation over the track.
The applied research methodology in this paper is based on collecting the different statistical data
from ENR reports, measurements and field observations of track deterioration and derailment
accidents that have been caused by the wind blown sand; hence the negative impact is determined.
The author conducted a simulation using basics of Computational Fluid Dynamics (CFD) through
ANSYS FLUENT software to analyze the impact of changing the embankment height and side slopes
on deposition of sand above the railway track. This simulation generates wind velocity vectors and
contours which indicate locations of sand deposition [9]. Also, a cost comparison between the recent
and the recommended embankments is carried out to determine the effectiveness of the optimized
embankment height.
Material and Methods
Characteristics of Bahariya Railway Line
Bahariya line is a single track of length 346 km with 10 stations including the start station in Bahariya
mines and the end station at Helwan. Other eight stations take their names from their kilometrages,
i.e. station 48, station 88, station 133, station 175, station 211, station 260, station 307, and station
328. Design speed of the line is 70 km/h and the operation speed is 50 km/h. Track is ballasted with
continuous welded rails of UIC 54 and wooden sleepers. Most of the longitudinal profile is filling;
hence the predominant depth of the embankment varies from 0.0 m to 2 m except three sections; from
kilometrage 37 to kilometrage 44, from kilometrage 277 to kilometrage 281and from kilometrage 336
to kilometrage 346 where the depth is about 6 m. A sample of the longitudinal profile in a section of
the predominant embankment and a typical cross section of the track are shown in Fig. 2 and Fig. 3
respectively (ENR, Design drawings of Bahariya railway line, unpublished).

Fig. 2. A Sample of Bahariya railway longitudinal profile.

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Fig. 3. Typical cross section of Bahariya railway track.

Field Statistics and Observations


Train derailments that occurred from 1/1/ 2011 to 2/9/2014 due to rebounding of train wheels and
sand accumulating above rails, their locations and costs in L.E are shown in Table 1 (ENR, Train`s
accident monthly records, unpublished reports). Although, ENR has distributed some equipment to
sweep sand; in addition to appointing special labors in some locations on the line, the efforts are not
sufficient to keep the line performs adequately. Distribution of equipment and the required labors on
the railway line is demonstrated in Table 2 (ENR, Bahariya railway line`s site technical records,
unpublished reports).

Table 1. Statistics of Derailments from 1/1 2011 to 2/9/2014 and Costs in L.E.

Year 2011 2012 2013 2014

No. of
10 6 12 8
derailments/ year

8.80-21.43 - 65.34-
9.56 -23.43- 8.00 -19.87-
23.90 -45.67- 104.13-106.14 -
67.45 -103.2- 21.00 -206.50 -
Locations of 65.32-69.90- 110.11-178.39 -
117.87-181.2- 211.32 - 219.06
derailments (km) 206.95- 182.00 -219.70 -
219.18-259.40 -
301.84 305.10-311.21- 258.46 -304.29
275.90-301.29
315.03
Delay cost 454125 272475 500272 310200
Derailments
420000 252000 470320 300015
removal cost
Track repair cost 47212 31015 52500 27122
Source: ENR, Train`s accident monthly records, unpublished reports

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Table 2. Distribution of equipment and the required labors on the railway line.
Station Km48 Km88 Km211 Km260 Km307 Km328 Km340
Sand sweeper 1 1 - - - - -
Loader 1 1 1 1 1 1 1
Labors 3 4 2 3 2 2 4
Source: ENR, Bahariya railway line`s site technical records, unpublished reports

Site visits have been done to detect and record the impact of sand accumulation on the track
components deterioration and on the track stability. It is observed that there is a reduction in the
thickness of rail seats especially in the location of heavy sand accumulation such as in km 36 and km
176. A loosening in the track fasteners (screw spikes) in those locations has been observed. A slight
surface roughness and vertical wear on the rail head have been recorded as 1mm to 2mm. Also, it has
been observed that track ballast contamination as a result of deposition of sand within the ballast, in
addition to track buckling, i.e. a lateral movement. Distances in meters of worn rails, fasteners and
contaminated ballast due to sand that have been changed according to ENR statistics are given in
Table 3 [10]. The time intervals of closing the line due to blown sand and its removal costs are shown
in Tables 4 and 5 respectively [10].

Table 3. Distances in Meters of Worn Rails, Fasteners and Contaminated Ballast.


Year 2011 2012 2013 2014
Rails 180 144 120 360
Ballast 540 810 650 900
Source: ENR, Maintenance Annual Statistical Reports, 2014

Table 4. Time Intervals of Closing the Line in Days.


Year 2011 2012 2013 2014
Time interval 60 93 80 70
Source: ENR, Maintenance Annual Statistical Reports, 2014

Table 5. Annual Cost of Sand Removal in L.E.


Year 2011 2012 2013 2014
Cost 3200000 3360000 3528000 3704000
Source: ENR, Maintenance Annual Statistical Reports, 2014

Simulation of Wind-Blown Sand on Embankment


The wind flow is commonly studied experimentally, theoretically or numerically. An alternative to
constructing a physical experiment is to perform a numerical analysis called (CFD) [9]. The govern
equations of the numerical process are very complicated and should be solved simultaneously to
provide solution. Therefore, the problem should be solved by making use of computers as a
computational tool [11] and [12]. This involves taking a meshed geometry, and using a CFD software

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package to create a simulation resembling the real world flow. The affected domain of the problem
is discretized into a finite set of cells, which is called mesh or grid. Plots for contours and vectors are
the output tools of examining the results of simulation [13]. Thus, a simulation has been constructed
by the author based on CFD in ANSYS FLUENT using the wind roses and velocity field
measurements that have been obtained and illustrated in Fig. 4 [5]. An average value of wind speed
(15 m/s) has been set up in a height of 10 m above the embankment upper level of Bahariya railway
line [5]. Properties of the wind- blown sand in the simulation process are described as follows: air
density = 1.225 kg/m3, air viscosity = 1.85 * 10-5 and particle density = 1760 kg/m3 [14]. The
boundary conditions and prepared mesh of the simulated model that have been used in processing the
calculation by the software are shown in Fig. 5 and Fig. 6 respectively. The simulation output of the
stream-wise velocity contours and vectors has been obtained for the predominant embankment cross
sections of 2 m and 4 m heights and shown in Figs 7, 8, 9 and 10 respectively.

Fig. 4. Wind roses affecting Bahariya railway line [5].

Fig. 5. Boundary Conditions of the simulated model.

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Fig. 6. Prepared mesh for the simulated model.

Fig. 7. Contours of X velocity for 2.0 m height embankment.

Fig. 8. Velocity vectors for 2.0 m height embankment.

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Fig. 9. Contours of X velocity for 4.0 m height embankment.

Fig. 10. Velocity vectors for 4.0 m height embankment.

Results and Discussion. Records of derailments and their locations which are shown in Table 1
indicate that derailments have been occurred in locations of 2 m height embankment as it is noticed
from the kilometrages where the accumulated sand is very heavy such that it covers the track
including the running rails and track components. It is, also, observed from records in Table 2 that
despite of the existence of the illustrated equipment and labor that have been appointed by ENR on
the line, the derailments were not eliminated. Regarding the magnitude of accumulated quantities of
sand, numbers of equipment and labor are not comparable.
Comparing the records of wear measurements of track components with the similar components on
other lines of ENR, it is noticed that vertical wear values of Bahariya rails is higher. The main reason
of that observation is the accumulation of sand over the track, which results in higher friction between
train wheels and rail surface. It is also observed that a loss of material at the rail seat has been
occurred. This effect has resulted in decreasing the fastening systems clamping force on the rail and
has led to track geometry problems such as gauge widening and loss of super-elevation.
Ballast contamination with sand that approaches the railway embankment due to deposition of sand
within the ballast has been noticed in most of the line. This contamination reduces the adhesion forces,
which are necessary to interlock the ballast grains. Thus, these types of track defects have increased
the derailment risk by altering the ratio of lateral to vertical forces and consequently reducing the
stability of the railway track. Because of problems associated with these defects and derailments, the
service life of many sleepers in service on Bahariya railway line has been reduced.
Estimation of Different Costs Due to Blown Sand
The financial impact of the blown sand can be categorized in 4 items:
a) Cost of derailments,

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b) Cost of track maintenance,


c) Cost of sand removal,
d) Cost of closing the line.
Total annual cost of derailments item (a) which is estimated from Table 1, and the average cost are
given in Table 6.

Table 6. Total Annual and Average Costs of Derailments in L.E.


Year 2011 2012 2013 2014
Cost of derailments 921,337 555,490 1,023,092 637,337
Average cost 784314

Cost of track maintenance (item b) includes changing the worn rails and contaminated ballast can
be estimated as follows:
Cost of changing one rail and its fasteners (18m) including the prices is 1200 L.E.
Total lengths of changed rails and related fasteners in 4 years = 180+144+120+360 = 804 m
Average annual cost of changed rails and related fasteners = 804 1200/4 = 241,200 L.E
Total lengths of changed ballast = 540+810+650+900 = 2900 m
Volume of one meter length of ballast = 1.05 m3
Total volume of ballast = 2900 1.05 = 3045 m3
Cost of changing 1m3 ballast = 150 L.E
Average annual cost of changed ballast = 3045 150/4 = 114,187.5 L.E
Thus, average annual cost of track maintenance = 241,200 +114,187.5 = 355,387.5 L.E
Average annual cost of sand removal (item c) which is estimated from table 5 = 3,448,000 L.E
Cost of closing the line (item d) is estimated according to closing time intervals which have been
given in table 4 as follows:
Cost of transporting 1 ton.km of iron ore = 0.25 L.E
Total closed time = 60+93+80+70 = 303 days
Total hauled distance = 345 km
Total cost of hauled loads = 2 trains/day 60 wagons 20 ton 345km 303 0.25= 62,721,000 L.E.
Average annual cost of closing the line = 62,721,000/4 = 15,680,250 L.E
Thus, the total average annual cost due to blown sand = 784,314 + 355,387.5 + 3,448,000 +
15,680,250 = 20,267,951.5 L.E.
Analysis of Simulation Results
The used CFD bases are upon that sand accumulates over the track in case of low friction velocities
whereas in case of high friction velocities, the crossing wind will transport sand from one side to the
other side without deposition over the track [11], [14], [15]. After the simulation was run; velocity
contours which give visualization for the wind directions; were compared among the various cross
section models. After comparing velocity contours, the velocity vectors which express the velocity
magnitudes have been analyzed. According to fluid dynamic concepts, the lower magnitude of
velocity causes larger quantities of sand deposition and vice versa. Analyzing the simulation results,
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it is observed for the case of embankment of 2 m height that low friction velocity that represented by
down contours and vectors (Fig. 7 and Fig. 8) is dominant and covered all the area including the
railway track. For the case of embankment of 4 m height as obtained in Fig. 9 and Fig. 10, the friction
velocity increases over the track; even though a low friction velocity exists over the area around the
embankment and over the side slopes.
According to the bases of sand deposition that have given by CFD, the low friction velocity in the
first case is due to very short height of the embankment which results in sever accumulation of sand
over the track; whereas in the second case, the magnitude of friction velocity raises over the track.
Thus, wind transports the sand from the blowing direction to the other direction of the embankment
with less accumulation of sand over the track. Result obtained in the second case assured that 4 m
height of the embankment is not enough to eliminate sand accumulation over the track and whole
embankment cross section. Therefore, other two suggested cases with 6 m height embankment
accompanied with right and left ditches of variable slopes have been simulated. The elements of mesh
which are processed by the software for this case are shown in Fig. 11. A side slope 3:2 for the ditches
is shown in Fig. 12, but the nearest side slope of ditches to the embankment is suggested to be 6:1 as
shown in Fig. 13. It is observed that raising height of embankment to 6 m and digging the ditches
with side slope 6:1 contributed in minimizing the accumulation of sand over the track than the case
of side slope 3:2, regardless the sand which has been accumulated in the ditches as shown in Figures
13 and 14.
To calculate the cost of raising the embankment to 6 m, it is assumed according to ENR prices in
2015 and referring to the cross section that is shown in Fig. 3:
Required volume of earthworks to raise the embankment from 2 m to 6 m = 29,420 m3, thus total
volume of 306 km = 9,002,520 m3, the price of 1 m3 = 67.98 L.E.
Total cost of 306 km = 9,002,520 67.98 = 612,000,000 L.E
Assuming that discount rates of initial cost equals the escalation rate of maintenance cost and life
time of embankment = 70 years, thus,
Average annual construction cost = 612,000,000/70= 8,742,857.14 L.E
It is, also, assumed that quantity of removed sand from side ditches is the same as in the actual case
without raising the embankment, so,
Average annual cost of sand removal from ditches = 3,448,000 L.E.

Fig. 11. Elements of mesh size for case of 6 m.

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Fig. 12. Contours of X velocity for 6.0 m height embankment with suggested ditches of slope 3:2.

Fig. 13. Contours of X velocity for 6.0 m height embankment with suggested ditches of slope 6:1.

Fig. 14. Velocity vectors for 6.0 m height embankment with suggested ditches of slope 6:1.

To calculate the cost of raising the embankment to 6 m, it is assumed according to ENR prices in
2015 and referring to the cross section that is shown in Fig. 3:
Required volume of earthworks to raise the embankment from 2 m to 6 m = 29,420 m3, thus total
volume of 306 km = 9,002,520 m3, the price of 1 m3 = 67.98 L.E.
Total cost of 306 km = 9,002,520 67.98 = 612,000,000 L.E

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Assuming that discount rates of initial cost equals the escalation rate of maintenance cost and life
time of embankment = 70 years, thus,
Average annual construction cost = 612,000,000/70= 8,742,857.14 L.E
It is, also, assumed that quantity of removed sand from side ditches is the same as in the actual case
without raising the embankment, so,
Average annual cost of sand removal from ditches = 3,448,000 L.E.
Cost Comparison
To compare the costs which resulted from blown sand and raising the embankment, it is assumed
that:
- Rate of train derailment in the case of raising the embankment is considered as in the other lines
which are not exposed to blown sand. This rate is found to be half the rate in the case of Bahariya
railway line.
- Cost of track maintenance in the case of raising the embankment is half the cost in the case of
Bahariya railway line. Therefore:
Average annual cost of derailments in the second case = 0.5 784314 = 392,157 L.E
Average annual cost of track maintenance = 0.5 355,387.5 = 177,693.75 L.E
Total annual cost in the case of raising the embankment = 8,742,857.14 + 3,448,000 +392,157+
177,693.75 = 12,760,707.89 L.E
Total annual cost in the case of raising the embankment / Total average annual cost due to blown sand
= (12,760,707.89/20,267,951.5) 100= 62.96 %.
Summary. The conducted simulation by ANSYS FLUENT in this paper concluded that:
1) The embankment height and side ditch slopes have a major effect on movement of wind and sand
accumulation above the railway track.
2) The major reason of sand accumulation on the track is the short height of the embankment and
those heights from 0 m to 4m are not adequate.
3) The optimized height of track embankment should be more than 4 m, thus the case of 6 m
embankment height which is accompanied with side ditches will be proper for new lines.
Also, the cost analysis concluded that:
1) Total average annual cost due to negative impacts of wind- blown sand on Bahariya railway track
is 20,267,951.5 L.E.
2) Total average annual cost of raising the height of embankment to 6 m is 12,760,707.89 L.E.
Thus, the cost of raising the embankment is about 63% of the cost of negative impacts of wind- blown
sand; therefore, raising the embankment to 6 m height is recommended to avoid consequences of
wind- blown sand such as train derailments and track deterioration.
Acknowledgements
I am grateful to engineer H. Fadel, the head of railway maintenance department in Cairo, as he
provided me with the necessary technical reports and facilitate my site visits to Bahariya railway line.
I would also like to appreciate M. Salah, the chief engineer of Bahariya railway line who accompanied
me in the site visits.
References
[1] Jabbar A. Zakeri and Mariam Forghani 2012. Railway root design in desert areas, American
Journal of Environmental Engineering, USA, doi: 10.5923/j.ajee.20120202.03

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[2] Gifford, A.W., Warner, D.M., and El-Baz, F. 1979. Orbital observations of sand distribution in
the Western Desert of Egypt. Apollo-Soyuz Test Project Summary Science Report, vol. II, p. 219-
236.
[3] Misak R.F. and El Ghazawy M.M. 1989. Desertification Processes in the Sinai Peninsula, Egypt,
International Meeting on Environmental Disasters and Desertification, Palermo, Italy.
[4] Ghoneim E. and El-Baz F. 2007. The application of radar topographic data to mapping of a mega-
paleodrainage in the Eastern Sahara, Journal of Arid Environments, Vol. 69, No. 4, pp. 658-675,
doi:10.1016/j.jaridenv.2006.11.018
[5] M. E. Hereher 2010. Sand movement patterns in the Western Desert of Egypt: an environment
concern, Environ Earth Sci. 59: 1119-1127. doi: 10.1007/s12665-009-0102-9
[6] H. Gad Elrab 2005.The Role of Railways in Economic Developing in Western Desert of Egypt:
Geographic study, Arabic edition, Kottob Arabia, Cairo.
[7] ENR. 2012. Annual financial budget of Egyptian National Railways Report, Cairo, Egypt.
[8] M. S. Abdelmoaty 2011. Protection of open channels from sand dunes movements. Case study -
Toshka Project, Fifteenth International Water Technology Conference, IWTC-15 2011, Alexandria,
Egypt.
[9] Kang Liqiang et al. 2008. Experimental investigation of particle velocity distributions in
windblown sand movement, Science in China Press, China, doi: 10.1007/s11433-008-0120-8.
[10] ENR . 2014. Maintenance Annual Statistical Reports, Cairo, Egypt.
[11] Anderson J. D.1995. Computational Fluid Dynamics: The Basics with Applications, McGrew
Hill Inc., London.
[12] J. Blazek 2001. Computational Fluid Dynamics: Principles and Applications, Elsevier, UK.
[13] ANSYS, Inc. Proprietary 2013. ANSYS Fluent Tutorial Guide. Available from internet:
http://148.204.81.206/Ansys/150/ANSYS%20Fluent%20Tutorial%20Guide.pdf.
[14] Jasper F. KOK et al. 2012. The Physics of Wind- Blown Sand and Dust, rep. Prog. Phys.,
doi:10.1088/0034-4885/75/10/106901.
[15] A. Watson 1985. The control of wind-blown sand and moving dunes: a review of the methods
of sand control in deserts, with observations from Saudi Arabia, Quarterly Journal of Engineering
Geology and Hydrogeology, London, Vol. 18, pp. 237-252, doi: 10.1144/GSL.QJEG.1985.018.04.19

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The Topology and Weight Optimization of a Truss Using Imperialist


Competitive Algorithm (ICA)

Arash Mohammadzadeh Gonabadi 1, a, Mohsen Mohebbi 1, b, Ali Sohan Ajini 1, c

1 Department of Mechanical Engineering, Islamic Azad University, Parand Branch, Tehran, Iran
a arash_mg@semnan.ac.ir
b Mohsen_mohebbi@ymail.com
c alisohanajini@gmail.com

DOI 10.2412/mmse.33.83.364 provided by Seo4U.link

Keywords: optimization, truss, imperialist competition, applying constraints, topology optimization, weight optimization

ABSTRACT. The main point of structure optimization, although being economical, is that none of the engineering
conditions and criteria must be neglected. Various methods such as Genetic Algorithm, Particle Swarm Algorithm,
Annealing Algorithm and so on, have been used for optimizing the structures up to now. In this research, a new method
called The Imperialist Competitive Method (ICA), which is inspired by a social-human phenomenon, is used in
topology, dimension and weight optimization of a structure and it is shown that is even useful for constraint problems as
well. Conclusions show that the resulting diameters for structure partial sections are better than other optimization
methods.

Introduction. From past decades, several optimization algorithms have been widely used in trusses.
Therefore, the design of truss structures is one of the active research branches in optimization.
Recently, some articles have used methods such as Genetic Algorithms [1], Particle Swarm Algorithm
[2], and other random search methods (which are inspired by nature) in truss optimization. In this
article, a new algorithm called 'The Imperialist Competitive Method (ICA)' is used. This algorithm
was used by Esmaeel Atashpaz and his partners for the first time [3, 4] and it is inspired by a social-
human phenomenon (not a natural one). Among the features of this algorithm we can point to the
novelty of basic idea of algorithm, the high potential of optimization compared with other algorithms
and appropriate convergence speed. The paper is organized in a way that ICA will be explained in
the next section. In the third part, we formulate and apply constraints and compare the results of ICA
with other optimization methods. The results show ICA is more convergent and functional than other
methods.
In this research, ICA is used in topology, dimension and weight optimization of a structure and it is
shown that's even useful for constraint problems as well. Conclusions show that the resulting
diameters for structure partial sections are better than other optimization methods.
Imperialist competitive algorithm method
Imperialist competitive algorithm starts with an initial population like other methods. In this
algorithm, each element of population is called a country. Countries are divided into two parts,
Colony and Imperialist, and each imperialist, has colonized some of the colonies and controls them,
depending on its power. Each imperialist country makes an empire with its colonies.
At first, we create an array using variables of the problem, which we are to be optimum. In this
algorithm, this array is called a country. In an optimization problem, the next of a country is a
1 array that is defined as follows:

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country = [p1 , p2 , p3 , , pNvar ] (1)

We are going to find the best country by solving an optimization problem using this method. In fact,
finding this country is equivalent to finding the best parameters for the problem which produce the
lowest cost function in variables. The cost of a country can be found by evaluating the f function in
(1 , 2 , 3 , ) variables. (Equation 2)

Cost i = f(countryi ) = [(p1 , p2 , p3 , pNvar ] (2)

To start algorithm, we create the initial country . Some of the best members of this population
(the lowest cost function countries) are chosen as imperialist countries out of .The remained
countries ( ) ; create colonies which belong to an empire. For distributing the first colonies among
empires, we give some of colonies to each empire depending on its power, thus the initial number of
colonies for each empire is: [4] and [7-15]


. = {| | . ( )} , i = 1,2, imp (3)
=1

In equation (3), . , is the initial colonies of an empire and is the total number of colonies
existing among initial countries. Then we create . number of initial colonies randomly and give
it to the -th empire. The total power of an empire is defined as the sum of total imperialist countries
plus a percentage of average power of colonies [4], as well. This is explained in equation (4).

. . = ( ) + %{( )} (4)

In the above equation, . . is the total power of -th empire and is a positive number which is
between 0 and 1 and is assumed near 1. Assuming the lowest amount for makes the total cost of an
empire nearly equal to the cost of its central government (colony). Assimilation and Imperialist
competition are two main pillars of this algorithm. Based on Assimilation, the imperialist countries
try to trans shape other countries by cultural and customs change. This policy makes the imperialist
tend to colonies. This phenomenon can be seen in figure 1 [3] and [7-15].

Fig. 1. The colony movement towards imperialist.


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In the colony movement towards imperialist and are random numbers with a uniform distribution
and is the distance between colony and imperialist (Equations 5 and 6) [3].

~(0, ) , > 1 (5)


~(, ) (6)

is bigger than 1 and approaches 2. = 2 can be an appropriate choice and is an optional number.
These show a limitation of which the colonies are moving near imperialist countries. If a colony
achieves a better success than an imperialist does, they will be replaced.
Based on imperialist competition, each empire that cannot improve its power and loses challenging
power will be eliminated. This takes place gradually meaning that the most powerful empire will
seize these colonies over time and improves its power. Finally, there will be a competition among all
empires to seize these colonies. To calculate the seize probability of the colony in the competition, at
first, we must define the normalized total cost based on total cost of empire (Equation 7).

. . . = {. . } . (7)

In this equation, . . is the total cost of -th empire and . . . is the normalized total cost of
that empire. By having normalized total cost, the probability of seizing the colony of competition by
every empire will be achieved.

...
= | | , = 1,2, (8)
=1 ..

We must consider that, mentioned colonies will be seized by the strongest empire; in fact, stronger
empires have more probability to seize.
By having the probability of seize for each empire, a mechanism like Rolette cycle will be needed to
give one of the empires the competition colony depending on the power of empires. In addition to the
possibility of using Rolette cycle, a new mechanism is used which lower calculation has cost than
Rolette cycle. This mechanism eliminates several operations for the calculation of the Cumulative
Distribution Function (CDF) in Rolette cycle and only needs Probability Density Function (PDF) [4].
Finally, the imperialist competition makes a condition of which only one empire survives. This
condition happens in ICA when it reaches an optimum point and algorithm stops. [4]
The steps of this algorithm are as follows:
1- Making the random nodes on selection function and make initial empires.
2- Moving colonies towards the empires. (Assimilation, Equation 5 and 6).
3- If there is a colony in an empire that reaches a better position than the imperialist, they will be
replaced.
4- Calculating the total power of an empire. (Equation 4)
5- Choosing a colony from the weakest empire and give it to the empire, which has the most
probability of, seize (Imperialist competition).

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6- If the pause condition is satisfied (only one empire is remained, maximum number of repeats, time
and so on), the algorithm will be stopped, otherwise we go back to step 2.
Applying constraints and formulation
To apply the constraints on target functions, two methods are suggested below:
The most general method that is usable for mentioned algorithm is the conversion of a constrained
problem to an unconstrained one, using penalty function. We change 'target function and applied
constraint method as follow [5] and [7-10]:

(, ) = () + () (9)
2
() =
=1{[0, ()]} (10)

In the above equation, (, ) is the target function with applied penalty, () target function,
a positive penalty parameter, the applied constraints on the problem and is the number of
constraints.
In the second method, we consider these conditions:
First Condition. We consider an imperialist as a country that, in addition to having more power,
satisfies the constraints applied to the problem.
Second Condition. If constraints are not applied due to movement deflection of colonies towards
imperialist, deflection must be prevented and movement must be done directly to imperialist.
Truss Optimization formulation
In this section, the mathematical formulation methods of an optimization problem are explained.
According to this, cross section vector [A] must be determined in a way that weight target function
reaches the minimum amount (Equation 11).

= () =
=1 (11

We usually consider these constraints for optimization:


[G1 ] = Basic Node
[G2 ] = Kinematic Stability
[G3 ] = all j 0 j = 1, , m
[G4 ] = max
k k 0 k = 1, , n
[G5 ] = Amin
i Ai Amax
i i = 1, , m

In the above equation is density, is the length of every linkage, is the cross section of
every link and is the member of a trust. In the following section, we analyze these constraints.
For the beginning, we can use a ground structure. In a perfect ground structure (perfect graph), if n is

the number of structure groups, we will have = ( ) links. It is not necessary for all m links to be

in ground structure because a perfect ground structure, which has several links, increases the local
optimization gain probability. Thus, we can choose a subset of m and start the process.

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So, from now on, we call m the numbers of structure links.


G1 constraint
In every truss structure, we have a series of important nodes that must be in every existing structure
for a reasonable design. These important nodes are called basic nodes.
These nodes are the ones that force is applied on or are on support.

Fig. 2. The basic nodes.

Number 1, 2 and 3 are the basic or ground nodes, must be in every design and we cannot eliminate
them at all. So, we must check whether this constraint is satisfied or not, in each step. If it is not
satisfied, this structure is not acceptable and cannot be chosen.
G2 constraint
This constraint checks the kinematic stability of structure. This means that the structure must not be
a mechanism. At first, we use Garbler criterion for this constraint. For this purpose, the static degree
of Indeterminacy of the structure is calculated using equation (12) before starting the structure
analysis operation. Here is an example for Grabler criterion:

Fig. 3. The analysis of kinematic stability constraint.

= + 2 (12)

where the number of members (links) in every step of algorithm processing;


the number of support reactions;

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the number of nodes in the truss.


If < 0 the structure will be a mechanism and it is unstable thus unacceptable. Therefore, we do not
do any more calculations for it.
This criterion is necessary but not enough for stability. Stiffness matrix of structure is used to analyze
internal instability in optimization process. This means when we process problem for structure
analysis, we achieve stiffness matrix (K) and it's positive definite will be examined.
From a kinematic approach, a steady structure is the one that has symmetric stiffness matrix and
positive definite matrix. If this condition does not satisfy, this structure is not acceptable and the
calculations must be redone with another structure.
G3 constraint
This constraint checks the amount of stress in all existing links meaning that after finite element
analysis and finding the amount of stress for each member, the amount of stress in every member
must be less than given allowable ( ) stress in problem description [16-22].
G4 constraint
After achieving the results of finite element analysis, the amount of achieved deflection in nodes must
be less than allowable deflection.
G5 constraint
In the second step of optimization (Dimension optimization) that we find the optimum cross section
for each link, the cross section of every link must be in [ , ] .
Overlapping Constraints
There must be no overlapping and duplication in a structure. For example, in figure 4, the link which
has connected node 1 to node 3 is extra between 1, 2, and 3 nodes and must be eliminated. Such links
must not be created in algorithm [16-22].

Fig. 4. The overlapping links


12
13
connectivity = 2 3 (13)
..
[ .. ]

The second row is extra, so it is removed.


Single linked constraint
If a node is used in topology matrix just once and is not a basic node, the link connected to that node
must be eliminated.
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Fig. 5. Single-link constraint.

12
13
connectivity = [ ] (14)
23
44

The link between node 3 and node 4 is single and this must happen in nowhere in the algorithm. In
this topology matrix, node 4 is only used once in this matrix thus the connected link to node 4 must
be eliminated.
The constraint of Duplicated link
The structure is examined to eliminate the duplicated link in topology matrix [7-15].

Fig. 6. Duplicated link.

12
23
connectivity = 3 4 (15)
14
[1 4]

The constraint of Empty link


The structure is examined to eliminate the empty link (which is only representing one node) in
topology matrix. For example:

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22
..
connectivity = . . (16)
..
[ .. ]

When all these initial constraints are checked, now we transfer the structure to finite element for
analysis to find the stress amount in links, nodes deflection and check whether the stress and
deflection constraints have contravention or not. When stress and deflection constraints are satisfied,
the ICA will be applied, a new topology will be achieved and the algorithm is repeated thus the target
function which is the weight of the structure will be achieved and the minimum weight of the structure
will be announced as the optimum structure.
Topology optimization process Steps
1. Selection of an initial topology
2. Analysis of initial constraints (If satisfied go to the next step, if not so, go back to the first
step)
3. Structure analysis and finding the amount of stress and deflection
4. Checking whether steadiness, stress and movement constraints are satisfied (if not so, go back
to the first step, if so, go to the nest step)
5. Applying ICA and achieving a new topology
6. Repeating this process until reaching stoppage condition
Size Optimization
As we have a two-step method, in the second step when the optimum topology is achieved, we begin
to process size optimization. In this step, it is perfectly clear whether a link exists or not and only
cross section of existing links in structure is optimum. The link cross sections are chosen continuously
[7-15]. Therefore, we use ICA which is naturally a continuous algorithm. The target function is the
weight of the structure, which is the result of this equation:

= () =
=1 (17)

Fig. 7. 10-linkage truss.

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There is a limitation for members' cross section meaning that all members' cross sections must be in
this limit:

(18)

Hence in size optimization, design parameters are members' cross sections which are chosen from
[ , ] continuously. We must consider components for each particle as long as design
parameters (number of members in second step). Meaning that a particle is a vector that has
components as long as design parameters [16-22].

= [1 , 2 , , ] (19)

where n the number of design parameters.


Numerical Example
It is shown in the below example that ICA has more functionality than Genetic and POS algorithm.
This algorithm is coded in Matlab [23, 25]. In this algorithm, in the first step of optimization
(Topology optimization), the number of population is 10 and the number of imperialist countries are
3 and in equation (5), is 2 and in equation (4) is 0.05 [16-22].

Fig. 8. Topology optimization.

After achieving optimum type, we go into the next step which is the optimization for structure weight
and diameters and in second step of optimization (size optimization), the number of population is 100
and the number of imperialist countries are 50 and in equation (5), is 2 and in equation (4) is 0.05

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Fig. 9. Convergence rate in topology optimization.

In this example, there is a 10-linkage structure with 6 nodes. The position of nodes and boundary
conditions are shown in figure and table (1) which is below.
Elasticity module: 107 Psi=68965.5 MPa, Density: 0.1 lb/in3=2768.096 kg/m3, Maximum applied
stress: 25000 Psi=172.41 Mpa, allowable displacement for every node in X and Y direction: 2 in=5.08
cm, Force (P)= 10000lb=444.8 KN , Linkage length (L) = 360 in=9.144 m , the maximum and
minimum cross section [Amin, Amax] [0.1,35] in2=[0.6452 225.806] [16-22].
After running the program, the structure is topologically optimum as you can see in figure 8 and its
structure is different and has found its optimum states based on constraints and properties. We can
see the convergence rate of the algorithm for this structure in figure 9.
In table 1 and table 2 we can see the results of optimization using ICA, Genetic algorithm and POS
and the weight convergence rate can be shown in figure 10.

Fig. 10. The convergence rate in topology optimization.

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Table 1. Achieved cross sections of optimization.


GA POS [6] ICA Link cross section
27.9012 in2 19.961 in2 19.1776 in2 Link cross section between node 1 & 5
20.4780 in2 25.0146 in2 22.1729 in2 Link cross section between node 1 & 6
16/6802 in2 22.7334 in2 20.8352 in2 Link cross section between node 3 & 5
24/5390 in2 15.0218 in2 1.8352 in2 Link cross section between node 3 & 6
30/8563 in2 27.9882 in2 32.8931 in2 Link cross section between node 4 & 5
6.6060 in2 5.947 in2 6.0080 in2 Link cross section between node 4 & 6

Table 2. Achieved weights of optimization.


GA POS [6] ICA Link cross section
10004.4432 718.596 690.3936 Link cross section between node 1 & 5
737.208 900.5256 798.2244 Link cross section between node 1 & 6
240.4872 818.4024 721.7568 Link cross section between node 3 & 5
883.404 240.7848 66.0672 Link cross section between node 3 & 6
1110.8268 1007.5752 1184.1516 Link cross section between node 4 & 5
237.816 214.092 216.288 Link cross section between node 4 & 6
4214.1852 lb 3899.976 lb 3677.4864 lb Total weights of the structure

Summary. The given optimization algorithm can be used as a simple, quick, and appropriate
optimization way for solving most optimization problems. This method will be converged to an
appropriate solution during a timeline. On the other hand, we can simply apply several kinds of
constraints in this optimization method.
In this article, ICA is used to optimize the truss. All results and figures are achieved due to the high
potential of this algorithm in quick convergence and finding optimum solution.
References
[1] Rahami, H., Kaveh, A. and Gholipour, Y., 2008. Sizing, geometry and topology optimization of
trusses via force method and genetic algorithm Engineering Structures, 30, pp. 23602369.
[2] Perez, R.E., Behdinan, K., 2007. Particle swarm approach for structural design
optimization.Computers and Structures, pp. 15791588.
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[7] A. Mohammadzadeh, A.Ghoddoosian. 2010. Balancing of Flexible Rotors with Optimization


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[11] Nader Mohammadi, Arash Mohammadzadeh, Optimizing the Collector Performance of a Solar
Domestic Hot Water System by the Use of Imperialist Competitive Algorithm with the Help of
Exergy Concept, International Journal of Engineering & Technology Sciences, Volume 3, Pages 65-
78, 2015
[12] Nader Mohammadi, Farahnaz Fallah Tafti, Ahmad Reza Arshi, Arash Mohammadzadeh,
Raghad Mimar, Extracting the Optimal Vibration Coefficients of Forefoot Offloading Shoes Using
Genetic Algorithms, International Journal of Engineering and Technology, Volume 2, Pages 487-
496, 2014
[13] Amir Mohammadzadeh, Nasrin Mahdipour, Arash Mohammadzadeh, Forecasting the Cost of
Water Using a Neural Network Method in the Municipality of Isfahan, Journal of Optimization in
Industrial Engineering, Volume 5, Pages 73-85, 2012
[14] Amir Mohammadzadeh, Nasrin Mahdipour, Arash Mohammadzadeh, Mohammad Ghadamyari,
Comparison of forecasting the cost of water using statistical and neural network methods: Case study
of Isfahan municipality, Volume 6, Pages 3001, 2012
[15] Arash Mohammadzadeh, N. Etemadee. 2011. " Optimized Positioning of Structure Supports
with PSO for Minimizing the Bending Moment." International Review of Mechanical Engineering -
(Vol. 5 N. 3) - Papers 5 (3): 422-425.
[16] Mohammad Nouri Damghani, Arash Mohammadzadeh Gonabadi (2016). Analytical and
Numerical Study of Foam-Filled Corrugated Core Sandwich Panels under Low Velocity Impact.
Mechanics, Materials Science & Engineering, Vol 7. doi:10.2412/mmse.6.55.34
[17] Mohammad Nouri Damghani, Arash Mohammadzadeh Gonabadi (2016). Investigation of
Energy Absorption in Aluminum Foam Sandwich Panels By Drop Hammer Test: Experimental
Results. Mechanics, Materials Science & Engineering, Vol 7. doi:10.2412/mmse.6.953.525
[18] M Nouri Damghani, A Mohammadzadeh Gonabadi (2017). Numerical study of energy
absorption in aluminum foam sandwich panel structures using drop hammer test. Journal of Sandwich
Structures & Materials. First published date: January-11-2017. doi:10.1177/1099636216685315
[19] M.Noori-Damghani, H.Rahmani, Arash Mohammadzadeh, S.Shokri-Pour. 2011. "Comparison
of Static and Dynamic Buckling Critical Force in the Homogeneous and Composite Columns
(Pillars)." International Review of Mechanical Engineering - (Vol. 5 N. 7) - Papers 5 (7): 1208-1212.
[20] Mohammad Nouri Damghani, Arash Mohammadzadeh Gonabadi (2017). Numerical and
Experimental Study of Energy Absorption in Aluminum Corrugated Core Sandwich Panels by Drop
Hammer Test. Mechanics, Materials Science & Engineering, Vol 8. doi:10.2412/mmse.85.747.458
[21] Arash Mohammadzadeh Gonabadi, Mohammad Nouri Damghani (2017). Multi-Objective
Optimization of Kinematic Characteristics of Geneva Mechanism Using High-Tech Optimization
Methods. Mechanics, Materials Science & Engineering, Vol 8. doi:10.2412/mmse.26.65.331

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[22] Nader Mohammadi, Arash Mohammadzadeh, Farahnaz Fallah Tafti. 2014. Design and
Optimization of Piezoresistive MEMS Pressure Sensors Using ABAQUS. International Journal of
Engineering & Technology Sciences - (Vol. 2 N. 6) - Papers 2 (6): 461-473.
[23] Arash Mohammadzadeh, N. Etemadee. 2012. Design of Heater for City Gate Station Assisted
by Solar Energy. International Review of Mechanical Engineering - (Vol. 6 N. 4) - Papers 6 (4):
730-735.
[24] M. Dehghan, M. Mirzaei, A. Mohammadzadeh, Numerical formulation and simulation of a
non-Newtonian magnetic fluid flow in the boundary layer of a stretching sheet, Journal of
Modeling in Engineering, 11 (34), 73-82 (2013).
[25] Mohammad Nouri Damghani, Arash Mohammadzadeh Gonabadi (2017). Experimental
Investigation of Energy Absorption in Aluminum Sandwich Panels by Drop Hammer
Test. Mechanics, Materials Science & Engineering, Vol 7. doi:
http://seo4u.link/10.2412/mmse.37.93.34

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Topology and Weight Optimization of a 3D Truss by Numerical Method

Arash Mohammadzadeh Gonabadi 1, a, Mohsen Mohebbi 1, b, Ali Sohan Ajini 1, c

1 Department of Mechanical Engineering, Islamic Azad University, Parand Branch, Tehran, Iran
a arash_mg@semnan.ac.ir
b Mohsen_mohebbi@ymail.com
c alisohanajini@gmail.com

DOI 10.2412/mmse.52.11.596 provided by Seo4U.link

Keywords: genetic algorithm, fitness function, 3D truss, topology, constraint, optimization.

ABSTRACT. One of the difficulties in designing a truss is finding the best condition for topology with the minimum
weight. Today, several techniques are presented for searching in computer science to find an approximate solution for
optimization and research problems that counts as a subset of artificial intelligence. Genetic algorithm is a special type of
evolution algorithms, which uses evolutionary biology techniques such as inheritance and mutation. In fact, genetic
algorithms use Darwin's natural selection principles to find optimum formula to forecast or fit the pattern. Genetic
algorithms are often good options for forecasting techniques based on accidents. Briefly, it is said that algorithmic is a
programming technique which uses genetic evolution as a solution pattern. Using this method along utilizing Matlab and
Ansys, we can design a 3D truss by having constraints, supports and applied forces on truss in the optimum condition
(geometry and weight) and by connecting these two software we can find FEM results, as well.

Introduction. With the development of science and technology and by relinquishing old methods,
which were in form of try and error and in addition to taking too much cost, they take too much time,
before conjugating too much money and time, by converting the problem into mathematical model
and doing some simple setting, we can find results close to reality
In the modern age, nobody is looking for old methods anymore and all majors are looking for different
software for speeding up the process of finding the results. Today, various optimization methods have
made it easy to find the best answers. Among optimization methods, we can point to genetic
algorithm, particle swarm algorithm and competitive colonization and so on. Today, genetic
algorithm has found its own place among other optimization methods for solving complex problems
and counts as an effective and efficient method for solving such problems in business, scientific and
engineering fields.
Working range of genetic algorithm is so wide and with daily increasing development of science and
technology the application of this method has been widely developed in optimization and problem
solving. Genetic algorithm is one of the subsets evolutionary calculations that has a direct relationship
with artificial intelligence and it is, in fact, one of the subsets of artificial intelligence. Genetic
algorithm can be a general searching method that imitates biologic evolution rules. Genetic algorithm
applies the survival of the best rule on a series of problem's answers to find better answers. In each
generation, using selection process suitable to answer values and reproduction, the selected answers
find better approximation for final answer using activisms imitated from natural genetic. This process
makes it possible for new generations to be more adaptive to problem conditions.
Now it is enough to model mentioned problem mathematically. By equating the parameters of the
problem with genetic algorithm parameters and applying constraints, which directs genetic algorithm
to create reasonable and correct answers, we can find the best and most optimum answer for the
intended problem. Genetic algorithm is emanated from Darwin's evolution process. According to

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Darwin's evolution process, only people with desirable genes can survive and reproduce new children,
thus people with shoddy genes will be eliminated.
Rechenberg mentioned the main idea of evolutionary algorithms for the first time [1]. In fact, genetic
algorithms that are subsets of these algorithms are computerized search methods based on
optimization algorithm, genes and chromosomes geometry that was mentioned by Prof.Holland in
Michigan University and was developed by a group of his students later [2].
For optimizing a truss using genetic algorithm there are four steps as follows:
1. Optimizing the section, which includes determining the optimum section for members [3, 4,
50].
2. Optimizing the shape or geometry of which the optimum constraint coordination for constant
topology (constant connectivity) of members are determined [6, 50].
3. Topology optimization, which contains determining the best layout of members in, assumed
space of constraint coordination [7, 8, 50].
4. Geometry optimization, which includes three previous steps together at the same time.
In this article, using genetic algorithm methods, a new method is represented for topology and cross
section optimization of truss constructions. Classic methods, for this purpose, require special
mathematics, but this end is easily accessible through genetic algorithm [9]. People like Grirson and
partners; Rajan [10, 11], Hajla and partners; Rajio and Chrishnamourti [13]; Ozaki [12]; Chai and
partners [15]; Vasques [14, 18, 17]; Kave and partners [16]; Sisok [20]; Tang and partners [19, 22];
Rahami and partners [21], D and partners [24]; Cheng and partners [23] and so on have proven this
matter using their suggested methods (GA) for topology, cross section, and truss constructions
optimization. Additionally, Arash M. Gonabadi [50] has optimized the topology and weight of a truss
using Imperialist Competitive Algorithm (ICA).
Now, by combining the modelling and one of optimization algorithms, we can reach a reasonable and
optimum answer.
Truss optimization formulation. The objective function is the one we want to optimize using genetic
algorithm. Genetic algorithm has approximately a general condition and is not only mentioned for a
specific problem but it has provided the possibility that by applying constraints, it will be specified
for mentioned problem [35-42, 50].
Constraint. Constraint literally means promise and covenant. In engineering applications, it means
that the mentioned system or action is supposed to be adhering to a series of rules and these rules are
called constraint. For example, assume a simple mechanism that consists of several joints and
supports, which create a regular and predictable movement. Hence, the mechanism has a series of
constraints (joints and supports) that is always depending on them while moving [45-51].
In optimization algorithms, due to different applications, we must define constraints depending on
the mentioned problem while using the algorithm. The defined constraints speed up the optimization
problem and sometimes prevent error creation while the program is operating. In mentioned
algorithm, we can apply constraints using these two methods such as: penalty function and using
constraint functions in algorithm geometry [50].
Penalty Function. In this method, we import the constraint in main function and involve it in the
answer. In optimization algorithms, some inputs are produced and then are used in fitness function
(the function that is to be optimized) then an output is created. Optimizing the output function is our
purpose. If the output of fitness function is not a single number, and consists of two or more numbers,
there is a function that is representing a cantilever beam that has a force applied on the other end [35-
40].

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Fig. 1. A cantilever beam.

This example can have several outputs: stress, strain, bending and so on. For this example, at the end
of fitness function, we sum up all the outputs that we want to optimize and model them as a number.
Then we set constraints in the fitness function with Penalty function. Knowing whether this constraint
is established or not, so the output of constraint is either 0 or 1 meaning that zero is correct and one
is incorrect. Thus, if the constraint is correct (meaning that the output of constraint is zero) when it is
multiplied in penalty magnitude, it will make the value of penalty zero. Now, if there are several
constraints, the penalty magnitude will be multiplied in every output of every constraint, and will
result in increasing the final value of fitness function [40-51].

() = () + () (1)

where () the output of fitness function with applied constraints;


() the output of fitness function;
penalty;
() equity or inequity answer;
Using constraint function in algorithm construction.
In genetic algorithm, we can define the constraints independently and the algorithm will select the
inputs for fitness function according to these constraints [35-42, 51].
G1 Constraint. In every truss construction, there is a series of important nodes, which must exist in
the construction for every reasonable design. These important nodes are called main points. These
nodes are the ones that a force is applied on or are on a support [35-42].

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Fig. 2. Main nodes of truss.

Nodes 1, 2 and 3 are main nodes.


G2 Constraint. The kinematic steadiness is analyzed in this constraint meaning the construction must
not be a mechanism.
According to degree of freedom (DOF) from Grobler criteria, we have:

= + 2 (2)

where number of links ( ) every step of algorithm;


Number of supporting reactions;
Number of truss constraints;
If 0 , the construction is not a mechanism and has a static state.
The overlap constraint: We must be careful to check that a link is not overlapping another one in a
construction, for example, in Fig. 3 there are two links between nodes 1, 2 and 3 and there is one link
between node 1 and 3 that must be eliminated.

Fig. 3. Overlapping links.

Single-linkage constraint: If a point is just used once in a topology matrix and is not a main point,
the link connected to that point will be eliminated.

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Fig. 4. The link between nodes 3 and 4 must be eliminated.

Duplicate linkage constraint: the construction is analyzed to eliminate the linkage that is repeated
in topology matrix.

Fig. 5. Repeated link.

Empty linkage constraint: the construction is analysed to eliminate the linkage that is empty
(representing only one point) in topology matrix.

2 2
. .
= . .
. .
[. .]
Fig. 6. Empty link.

After applying initial constraints, we are going to apply secondary constraints related to the outputs
of fitness function or mentioned answers which are as follows [35-45, 51]:
- The stress of every link must not exceed allowable stress amount
- The deflection magnitude of nodes must not exceed allowable amount
- The cross section of links must be in allowable limitation
Applying topology optimization steps:

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Choosing an initial topology.


Analyzing the initial constraints (In case of dissatisfaction go back to first step, in case of
satisfaction go to the next step).
Analyzing the construction to find stress and dislocation magnitudes
Are steadiness, stress and dislocation constraints satisfied? (In case of dissatisfaction go back
to first step, in case of satisfaction go to the next step).
Applying genetic algorithm method and gaining a new topology.
Repeating this process until stoppage point.
Size optimization
As this is a two-step method , after gaining the optimum topology in second step , we begin optimizing
the size. The existence or inexistence of a link is clear in this step and we only optimize the cross
sections of existing links in construction. The cross section of links are chosen continuously [40-45].
The objective function is the weight of construction and can be calculated from this relation:

= () =
=1 (3)

Assuming a limitation for the cross section of links which is:

(4)

Thus, in size optimization, the design variables are cross sections of links that are continuously chosen
from ( ). We must choose arrays for every particle as long as design parameters(the
existing links in second step) meaning that each particle must be considered as a vector of which the
arrays are as long as design parameters:

= [ , 1, , 2, , , ] (5)

The implementation plan


The goal of this section is creating the matrix model of the truss [40-50].
Defining the truss in writing code
To define these type of constructions , we must define the location of points that show the beginning
and end of links, at first. The number of columns shows the magnitudes of X, Y, and Z points and the
number of rows shows the number of points that create the construction. In other words, if the
construction has two columns it is a 2D construction and if it has three columns, it is a 3D one. In
Fig. 7 the points are near each other with a 1000-Inches length between each of them.

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0 0 0
0 1 0
1 0 0
1 1 0
2 0 0
2 1 0
Node_Coordinates = 1000 (6)
0 0 1
0 1 1
1 0 1
1 1 1
2 0 1
[2 1 1]

Fig. 7. Shows how to define truss coordinates.

How to define links between points


In this project we use this method of which a (n D) array is created and n represents the number
of links in constructions. On the other hand, every row contains information about every link.
In this method, the first column contains the number of point that a link starts and the second column
contains the end point of the link. Using this method to show the truss can keep a lot of information
in itself. For example, we can add a third column to matrix that can keep the cross section area of
every link in itself.

Fig. 8. The number of truss elements.

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Start Node End Node Cross Section


1 1 2 0.4 1 0.4 1
1 1 4 0.2 1 0.2 2
2 2 3 0.4 2 0.4 3 Number of nodes (7)
2 2 4 0.05 2 0.05 4
[3 ] [3 4 0.3 ] [3 0.3 ] {5

For this matrix, we can assume a standard of which in every row, the array of the first column must
be smaller than the array of the second one, and all the arrays of the first column must be arranged
from the most to the least. This will increase the search speed. Hence, we can rewrite the above matrix
like this:

1 2 0.4
1 4 0.2
2 3 0.4 (8)
2 4 0.05
[ 3 4 0.3 ]

Importing forces in coding


We import the forces in form of the matrix shown below which explains that the force is applied in
Y-direction in node 2 and node 3.

0 0
0 100
Connectivity table = 0 100 (9)
0 0
[0 0 ]

Importing supports in coding


We can define supports as it is explained in section (2-4), the difference is that if there is a support in
a node, we use 1 in the directions that the support is preventing movement.
Defining an object function for a truss
Fitness function is the one that is to be optimized. Our goal is to find a mathematical model for a 3D
truss that provides us the ability of analyzing the truss in Ansys software. This function must act in
such a way that by receiving inputs, the function will process all the topology creation of the truss
(truss geometry) including supports, forces and links. Then, we import the resulting truss in Ansys,
and the software will report the desired outputs of the problem (stress, strain and bending) as the
output.
Truss in Ansys
Among designing steps of a truss in Ansys we can point to: defining the types of elements, the
material of the truss, nodes, the elements between nodes, supports,forces and entering strength
modules. Among Ansys abilities, we can point to Session Editor [43-51] (see Fig. 9).

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Fig. 9. Session editor.

This command shows all the steps that are done in Ansys, on the other hand, it shows all the done
activities in design process. For example, a simple truss is designed in the Ansys )Fig. 10(.

Fig. 10. Designing a simple truss in Ansys.

Now we choose session editor command, see Fig. 11 and Fig. 12.

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Fig. 11. Session editor command.

Fig. 12. Session editor command.

Now if we run this text file in command section of Ansys, this will create the truss again. If we create
the lines of this file using Matlab software, we can create a different truss by entering intended inputs
(elements and cross sections) [37-54].
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The solved example of 3D Truss


Problem Description
There is a 3D truss with 12 nodes, 4 supports, and 2 forces. For optimizing the truss geometry and
cross sections using topology genetic algorithm we need material properties of links.
Elasticity module: 2 x 10e9 [pa]
Poissons ratio: 0.3

0 0
0 100
Connectivity table = 0 100 (10)
0 0
[0 0 ]
1 1 1
1 1 1
0 0 0
0 0 0
0 0 0
Support= 0 0 0 (11)
1 1 1
1 1 1
0 0 0
0 0 0
0 0 0
[0 0 0]
Solving
We should solve this problem by Ansys and Matlab [52, 53], see:

Fig. 13. Topology optimization.

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Fig. 14. Topology optimization.

Fig. 15. Penalty Function-Steps of Optimisation, topology optimization process, Matlab, history
report.

Fig. 16. Penalty Function-Steps of Optimisation, cross section optimization process, Matlab,
history report.

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Fig. 17. Optimization results, Matlab and Ansys, output report.

Discussion and conclusion


In this text, a new optimization algorithm based on mathematical modelling of genetic process for
truss optimization was presented. Different methods were explained for optimization. Some of these
methods repeatedly and based on gradient, find the optimum point of the cost function. These methods
have usually a high speed, but may be stuck in local optimum trap instead. In the opposite side, there
are methods that begin to search for absolute optimum point for the function. Genetic algorithm and
particle swarm optimization are examples for these methods.
The results of experiment show a suggested method on different cost functions that the mentioned
algorithm will be successful in finding optimum point for these functions. The different useful
problems solved using this algorithm show that the strategy of mentioned optimization can
successfully help us to solve useful and engineering problems alongside other mentioned optimization
methods such as genetic algorithm and particle swarm algorithm. The result comparison of mentioned
algorithm with current optimization methods shows us the relative excellence of mentioned
algorithm.
The mentioned optimization algorithm can be used as a simple, quick and proper optimization method
for solving most of the optimization methods. Given enough period of time, this method will be
converged to a suitable answer. On the other hand, in this optimization method we can simply apply
various constraints. In this project, genetic algorithm is used for truss optimization. All the results
and figures are created due to high ability of this algorithm in quick convergence and finding optimum
answer. Evolutionary methods, have digression of local minimum point ability. In the opposite side,
classic optimization methods have more convergence speed. To have both high convergence speed
and the ability of not being trapped in optimum local points, there is a common method which is the

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combination of evolutionary algorithms with classic optimization methods such as Newton method.
Hence, we can combine a mixture of mentioned algorithm with classic optimization methods.
Using this method, we hope to gain better results (in convergence). The presented optimization
algorithm can be used as a simple, quick and proper method for solving optimization problems. Given
enough period of time, this method will converge to an appropriate answer and we can apply different
constraints. The results show that this algorithm has a high ability to converge quickly and find
optimum answers.
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[36] A. Fereidoon, H. Hemmatian, A. Mohammad Zadeh, E. Elahe Asareh, Optimization of
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[38] Nader Mohammadi, Arash Mohammadzadeh, Optimizing the Collector Performance of a Solar
Domestic Hot Water System by the Use of Imperialist Competitive Algorithm with the Help of
Exergy Concept, International Journal of Engineering & Technology Sciences, Volume 3, Pages 65-
78, 2015
[39] Nader Mohammadi, Farahnaz Fallah Tafti, Ahmad Reza Arshi, Arash Mohammadzadeh,
Raghad Mimar, Extracting the Optimal Vibration Coefficients of Forefoot Offloading Shoes Using
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Numerical Study of Foam-Filled Corrugated Core Sandwich Panels under Low Velocity Impact.
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Energy Absorption in Aluminum Foam Sandwich Panels By Drop Hammer Test: Experimental
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of Static and Dynamic Buckling Critical Force in the Homogeneous and Composite Columns
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Experimental Study of Energy Absorption in Aluminum Corrugated Core Sandwich Panels by Drop
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Optimization of Kinematic Characteristics of Geneva Mechanism Using High-Tech Optimization
Methods. Mechanics, Materials Science & Engineering, Vol 8. doi:
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and Weight Optimization of a truss using Imperialist Competitive Algorithm (ICA). Mechanics,
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[51] Nader Mohammadi, Arash Mohammadzadeh, Farahnaz Fallah Tafti. 2014. Design and
Optimization of Piezoresistive MEMS Pressure Sensors Using ABAQUS. International Journal of
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[52] Arash Mohammadzadeh, N. Etemadee. 2012. Design of Heater for City Gate Station Assisted
by Solar Energy. International Review of Mechanical Engineering - (Vol. 6 N. 4) - Papers 6 (4):
730-735.
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non-Newtonian magnetic fluid flow in the boundary layer of a stretching sheet, Journal of
Modeling in Engineering, 11 (34), 73-82 (2013).
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Investigation of Energy Absorption in Aluminum Sandwich Panels by Drop Hammer
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Some Aspects of Model Equations Development for Viscous Materials25

Irina Viktorova1, a, Sofya Alekseeva1, b, Muhammed Kose2, c

1 Department of Mathematical Sciences, Clemson University, Clemson South Carolina


2 Department of Mechanical Engineering, Clemson University, Clemson South Carolina
a iviktor@clemson.edu
b salekse@clemson.edu
c muhammk@clemson.edu

DOI 10.2412/mmse.81.48.85 provided by Seo4U.link

Keywords: viscoelasticity, creep, stress, strain, relaxation, viscous, elastic.

ABSTRACT. Materials with viscous properties, polymers and composites with polymer matrix, have found increasingly
wider applications in modern industry. It is known that temperature and moisture are very important for correct estimation
of the environmental response of these materials. Therefore, the construction of the constitutive equations for the material
elements under real conditions of exploitation, takes on special significance in modern mechanical engineering.

Viscoelastic models. The term viscoelasticity is derived from two terms: elastic (spring) and viscous
(an oil-filled cylinder containing a piston). For an elastic element, Hookes law is valid where is
strain and is stress. is Youngs modulus

= ,

For a viscous element, Newtons law can be expressed as

= 3

If we combined springs and pistons in various combinations, we could construct many mechanical
models. Such compound models can describe, in some cases, the rheological behavior of materials.
Investigations such as this were alluded to during the middle of the 19th century in the works of
Maxwell, Voigt, Kelvin and many others. The elements can be connected in series or parallel. In the
series case, Maxwells model, the constitutive equation can be written in the form


= + 3 (1)

For the parallel case, the Voigt model is valid


= + 3 (2)

2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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Later on, it was shown that the simplest models constructed from the two elements could only be used
to describe either creep behavior through the Voigt model or relaxation processes through the
Maxwell model.
Of course, one can construct a complex system, which will contain more elements. This is a natural
way to develop the generalization of the models (1) and (2). In this way, one finds a relationship
between the derivatives of and with respect to time on both the left and right-hand sides


0 + 1 + + = 0 + 1 + + (3)

This differential relationship can be transformed into an integral equation. It was shown [1] that if
n = m, equation (3) is equivalent to the integral equation


= (t )()d()
0

Here

( ) = [ ( )]
=1

A =
=0

Parameters and are connected with coefficients of equation (3) as shown in [1-2]. Because of
the large number of parameters mentioned, the above equations are rather difficult.
Some empirical, or semi-empirical, approaches are popular for the description of creep and relaxation
processes. These theories are called the technical creep theories, they can be thought of as the
maximum limitation of a number of variables and stating some propositions on a functional
relationship between these variables. It is then necessary to connect them in an analytical relation, the
best of which will be a theory that demonstrates the best correlation with tests.
Creep theory must be able to describe the general material behavior, using the simplest tests, with
time dependent stress and strains, given the determination of a strain changing law using a stress
changing law and vice versa. In a particular case, the theory must allow one to construct the relaxation
curves using a series of creep curves, which is a cornerstone for any time-dependent theory.
Three basic creep theories to note:
1. Time-hardening theory

1 (, , ) = 0,
for example = 1 ()2 ()

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2. Flow theory

2 (, , ) = 0,

for example = 3 ()4 ()


3. Strain-hardening theory

3 (, , ) = 0,

for example = 5 ()6 ()


Power functions are the most popular choice for 1 (), , 6 (), though exponential or other
functions that demonstrate strong correlation with experiments can be chosen.
The approaches mentioned above were developed originally for the description of creep (or
relaxation) of metals at high temperatures. It should be emphasized that the value of is the
deformation without the elastic component. The application of such approaches is often limited
because, if the parameters of an equation for description of creep curves at constant stress can be
successfully estimated, then one can find only qualitative correlation for the description of relaxation
curves.
Other approaches were being developed when almost only metals were used as construction
materials. Creep in metals only becomes apparent at high temperatures and under certain loading
conditions.
The situation changed when polymers and composites with a polymer matrix found a wider
application in industry. Time-dependent properties of these materials are clearly evident at and below
room temperature. Therefore, it was necessary to conduct a complex investigation of the behavior of
these materials. Moreover, models must be established, which would use the same set of parameters
for creep, relaxation, loading with various regimes, cyclic loading, and unloading, etc.
Hereditary-type theories
The only approach from those currently known that answers all the above demands is an introduction
of the hereditary principle in mechanics of materials and a construction of the corresponding
constitutive equation. This approach aroused a revolution in the field of viscoelasticity, which began
with the work of the German scientist Boltzmann [3]. This work was published in 1878 and shows a
way by which the viscous behavior of materials can be explained using the conception of heredity.
Boltzmanns conception of the matter was as follows: Let us suppose that some physical or
mechanical process is defined by some function v(), < <t. A reaction response of a solid or
system of solids is determined by some function u(t). In general, the value of the function u(t) in the
present time t is affected not only by the value of an action at specific time t, but also by the whole
history of the function v changing. Therefore, the function u can be written as a function of v


= (v)

In the dependence of this type of function, one will find various types of constitutive equations. The
stress-strain state of a material can be considered: Let us consider that some stress () was applied
at the instant of time and was perpetuated for a time . The material retains a memory of the action
of the stress in the form of a small deformation , which is proportional to the stress () and the
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time and depends on the difference between the present time t and the instant , also known as
(time-lag) t. It gives = ( ). With the addition of an elastic term, the following integral
equation becomes the constitutive model


() = () + ( )() (4)

Here E is the elastic modulus and K( ) is the kernel of the integral equation, which describes the
hereditary properties, i.e. the properties of material memory.
Integral Volterras equations in biology
The Italian scientist Volterra chose the other approach for the construction of the hereditary equation
[4-5]. Works in the field of mathematical biology were the starting point of Volterras research.
The basic exponential model of population development belongs to Malthus [6]. The main
assumption was that the birth and death rates were equal. It was supposed that the rate of change for

the number of individuals , is proportional to the common number (N) of the individuals at that
time


= (5)

The solution of the above equation = 0 shows that if time rises in the arithmetic progression,
then the value N rises in the geometric progression. Malthus concluded that wars and other conscious
destructions of the population on Earth had to be considered since a population grows at a
considerable rate. In the 19th century, these works were analyzed and criticized. For example, it was
proposed that the coefficient was not a constant but a decreasing function of N connected with a
competition inside the species population


= ( ) (6)

where and are constants. Solving the equation gives


=
+

This shows that as , /, which is a constant value. The equations can be modified by
adding some other terms, such as periodic terms, which can appear because of a seasonal prevalence
of weather.
Volterra, however, was interested in the associations consisting of 2,3 or n kinds. Therefore, 2,3
or n differential equations must be written. The simplest example is the association consisting of two
kinds: predator and victim. For this case, we have

1
Victim: = (1 1 2 )1 (7)

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2
Predator: = (2 + 2 1 )2

Here, the coefficient of increase, 1, for victims has a positive value because, in the absence of
predators, the quantity of victims will increase. The coefficient, 2, is negative because the quantity
of predators will naturally decrease in the absence of victims. The terms, which are concerned with
competition, depend on the number of kinds meeting and are proportional to N1N2. The terms are
positive for predators and negative for victims.
Analysis of these equations led to interesting conclusions. For example, the periodicity of fluctuations
in the biological associations was proven. This property of periodicity was known previously, but
ecologists proposed that the phenomenon should be explained by other factors, for example by the
seasonal change of weather, or destruction from the human side.
The other interesting conclusion from equation (7) was stated by Volterra in his report About
Fishing, at the International Mathematical Congress in 1913. He stated that even destruction of both
kinds of fish (predators and victims) leads to a decrease in the number of predators and to an increase
in the number of victims. On the other hand, stopping fishing leads to an increase of predators. This
effect was confirmed via statistical analysis of fishing in the Adriatic Sea during WWI by biologist
DAncone.
Later on, Volterra developed a general theory for n of species and introduced the concepts of
conservative and dissipative associations. An association of the type seen in equation (5) is
conservative, but an association of the type described in equation (6) is dissipative. The equations (7)
also represent a conservative association. The equations for the dissipative association can be
obtained from (7) with account of inside competition

1
= (1 1 1 1 2 )1

2
= (2 2 2 + 2 1 )2

Now, the rates of change of N1 and N2 will be damped so their amplitudes will decrease over time
and have a tendency to occupy an equilibrium. Volterra showed that this property is universal for the
associations, which he named as dissipative. This caused him to think about an analogy with
mechanics. Conservative associations are ideal but do not exist in nature, while dissipative
associations are more common. The analogy with mechanics is seen in the fact that to the conservative
mechanical system with friction, the mechanical energy of the system will decrease if oscillations are
damped.
Having analyzed the differential equations, which describe the oscillations of mechanical systems
and biological fluctuations, Volterra proved the identity of the equations.
The similarity between biology and mechanics even more pronounced when considering the
phenomenon of after-effect, or delay. After-effect can be easily explained in biological content The
number of predators, N2(t), in the present depends not only on the quantity of victims in the present
time, t, but also on the quantity of victims in some previous instant, , and thus depends on the time
elapsed from the instant to the present time t, and thus on difference t-. From the equations (7), we
can now obtain the system with the equation that contains an after-effect integral

1
= [1 1 2 ()]1 ()

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2
= [2 + ( )d]2 (), 0

The above is the particular case of a more symmetric system, where the first equation also contains
an after-effect integral.
Pekar introduced the phenomenon of after-effect or delay, in physics in his studies of elasticity,
magnetism, electricity and other phenomena. The same principle can be seen in mechanics. Therefore,
in the inorganic world, a memory of the past exists. For example, to determine the stress-strain state
of some deformed structural element, it is necessary to know the previous stress states.
General principle of heredity
Influence of past on future is observed in areas other than biology, physics and mechanics. It clearly
exists in various fields of human activity such as economics, politics, psychology and the general
development of civilization. Therefore, after-effect is one of the basic laws of nature and human
development.
To take into account a continuous sequence of previous states, it is necessary to use the integral and
integro-differential equations, with the functions, which depend on some period of time that proceeds
the present. For mechanical systems, we assume that the past history acts as a force that can be
described by the functional


( )q()d

This additional force is a resultant of the elementary actions ( )q()d from the previous
intervals (, +d). Functions ( ) must be decreasing because of the assumption that the after-
effect is weaker with an increasing difference between the present time and the time of the force
application. If we know the displacement during a period of time equal to the after-effect duration
and the outside forces in the next interval of time, then it is possible to calculate the displacements,
which will develop in the next moment.
The phenomenon of after-effect, its mathematical formulation, analyses of dissipative processes and
fluctuations have been considered in detail in the works of Volterra.
Generally speaking, both the organic and inorganic natural worlds are subject to the same laws, which
are described by the same equations whose analysis allows one to demonstrate the general concept of
the laws of nature.
Kernels of the integral equation
Functions ( ), which are is introduced under the integral, are the kernel of the integral equation.
There arent any specific requirements except some mathematical restrictions that follow from the
analysis of the equation. Therefore, in mechanics, the first condition of kernel choice is strictly
correlated with the test results, with creep tests as the most popular for viscoelastic materials [1].

Boltzmann was the first to suggest the singular form of a kernel: ()
. It gives an infinitely large
rate of deformation at an initial moment, which is verified by experiments. However, not only the
rate of deformation becomes infinitely large but also the deformation, itself. Later, Duffing [7]

suggested to use the function () , where 0<<1, as a kernel. This kernel was named after Abel. Its
shortcoming is in the fact that at the limiting creep conditions the strain, as time, , which
contradicts with the experimental data. However, it was experimentally proven [8-9] that such type
of kernel might be used, especially for nonlinear viscoelasticity, because it allows to accurately

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describe the behavior of materials for the interval of at least seven-eight times orders. This result
means that if the kernel parameters are determined from the short-term creep tests, the behavior of
the material in construction at much longer exploitation periods can be predicted.
Many authors use a kernel in the form of the exponential function () , which is convenient for
calculations. However the drawback is for short periods of loading, the estimates do not correspond
to experimental results. Nonetheless extrapolation over large periods of time for some cases can be
sufficiently close to the tests. Attempts to combine the properties of exponents and weak singularity
kernels lead to the construction of many known types: Bronsky, Slonimsky, Rzhanitsyn, Koltunov,
etc. The analysis of some of them can be found in [10]. Their weakness is in the difficulty of finding
the resolvent solution, which restricts the application of the constitutive equations with such kernels.
The simplicity of mathematical solutions is the second crucial factor for the choice of an integral
equation kernel. Such a simple process as creep, when stress, is constant and the integral equation
transforms into a simple algebraic relationship is rare in practice. Instead more complex processes
and arbitrary types of loading, with given strains but not stresses, occur more often in engineering
practice. The difficulties can be eliminated, as shall be shown later, by using Abels or Rabotnovs
kernels.
Rabotnovs kernel
It must be emphasized that hereditary-type models have significant advantages in comparison with
differential-type models, which are often empirical in nature. The latter models are used for the
description of some specific type of loading, such as creep, relaxation, cyclic loading, etc. Therefore,
these models are restricted by narrow limits of application. It should be noted that the integral
equations for each of the above-mentioned types of loading can be transformed into the simple
algebraic equations via the integral operators and successfully used for the cases when the type of
loading changes during the loading process under consideration. Rabotnovs kernel is the most
universal and satisfies all the constraints that a kernel must satisfy. It was named an exponential kernel
of arbitrary order [1,11-12]



( )(1)
(, ) = ( )
[(n + 1)(1 )]
=0

The first term of the series is Abels kernel, but at the series becomes an exponential function.
The great input of Rabotnov consists in the construction of the class of the new resolvent functions
and algebraic operators. The advantage of these functions is in the procedure of finding the resolvent,
which is the same type of function but with some different parameters, which can be easily calculated.
This makes it possible to solve the problems in a simple way and preserve Volterras principle, with
which solutions to hereditary-elastic problems must be such that one must solve an ordinary elastic
problem by treating the operators as elastic constants. In the finite solution, these elastic constants
ought to be replaced by the operators, and the resulting solution must be interpreted through the
algebraic inverse operators.
Thus, the introduction of the new class of exponential functions with arbitrary order together
combined with Volterras principle provided a new approach to the solution of linear viscoelastic
solid mechanics based on classical theory of elasticity.
However the use of the linear theory is rather limited since the linear region cannot be found for some
materials such as polymers or composites with polymer matrix and gives good results only at
moderately high stresses.
Nonlinear equations

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The most general nonlinear equation was written by Volterra and represents an infinite series of the
multiple integrals

= + 1 ( )() +


1 ( )(1 )(2 )1 2 +


1 ( )(1 )(2 )(3 )1 2 3 +

If we choose a large number of terms in the above equation and hypothetically determine the
parameters of all the kernels , we can describe any process of deformation with any precision. That
was the approach taken in [13-15] and many others in construction of constitutive or governing
equation. Certain assumptions or restrictions in material behavior such as in compressibility, same
behavior in tension and compression and others can simplify the above infinite series and kernel
functions involved. But it is clear that use of the multiple integrals and determination of a large
number of hereditary kernels is a very difficult task. One of the practical applications of such an
approach through the quasi-linear Ilyushins theory ought to be noted [16], which shows the way to
simplify Volterras equation using some prepositions. The new equation contains three terms of the
series of ordinary integrals rather than multiple integrals.
Let us consider the nonlinear Rabotnovs equation, proposed in 1948


() = + 0 ( )() (8)

The left hand side of the equation, the nonlinear function strain () is called a curve of instantaneous
deformation. Rabotnovs equation found its practical application only after 20 years, in the late
sixties, when a large number of experiments were carried out on the short and long-term creep of
glass-reinforced plastics. It was shown that the equation with the exponential kernel of arbitrary order
allowed the prediction of long-term creep with the highest accuracy. In recent years Rabotnov's type
kernel had been successfully used in combination with optimization techniques for the creep
modeling of new type of viscous materials nanocomposites [17].
Application to dynamic problems
The constitutive equation (8) can be applied both: the quasistatic and dynamic processes of loading.
With an increase of strain rate, the strain diagrams are being shifted vertically and condensed, aspiring
in a limit to the curve of the instantaneous deformation ().
For dynamic problems, two basic approaches that have been subject to various modifications should
be mentioned. One of the approaches, the strongly simplified Rakhmatullins approach, is based on
the existence of two curves (static and dynamic) of deformation. The dynamic curve is located above
the static one and determined from any dynamic experiment. The other approach, Sokolovsky-
Malverns approach, which is more adopted agrees with experimental data, assumes the dependence
on stress-strain diagram on the rate of loading and is determined experimentally. This process is not
bounded from above. Using equation (8), with Rabotnovs kernel, we receive a fan of diagrams,
which is bounded by the two diagrams found at and 0. For example, in the works [18-
19], it is shown that this approach, based on the principle of heredity, allows one to describe processes
of creep and quasistatic loading with different rates and can also be used to find the solution to the

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waves propagation problems. It must be emphasized that the same parameters of a kernel and the
same curve of the instantaneous deformation can be chosen.
The equation (8) can be used both for the analysis of polymers, composite materials and metals [20].
Temperature and moisture effects
Environmental factors such as temperature (high and low) and moisture are known to affect the
viscous properties of polymers and composites thus leading to a numerous research efforts of
introduction temperature and moisture level functions into the constitutive equation. Many introduce
both temperature and moisture in a purely formal way with the parameters of the kernel and the
instantaneous deformation curve, the modulus of elasticity in the elastic case, are dependent on both
temperature and moisture in the most general way. Evidently, to determine the whole set of
parameters requires an extensive experimental program. The combined introduction of temperature
and moisture effects into the constitutive equations is quite rare.
The principle of the time-temperature analogy was introduced by Ferry [21]. It is based on the concept
that time, dependent on temperature, should be introduced in an equation


= [()]
0

Here aT is the factor of temperature shift and is determined from the formula:

1 ( 0 )
=
2 + ( 0 )

where C1 and C2 are empirical constants and T0 is the reduced temperature.


The type of the constitutive equation is unchanged, the value of time in the constitutive equation
depends on temperature. The solutions to problems remain the same as before but demand an
additional interpretation. Such an approach allows one to consider the thermo-rheological identical
processes, which is convenient for engineering practices since it is possible to carry out short-term
experiments at higher temperatures and to predict the behavior of a material at lower temperatures
and longer times of loading. The principle of the time-temperature analogy was thoroughly developed
by Latvian school of mechanics [22]. The principle of the time-moisture analogy was formulated as
well. It was based on the same concepts.
The analogy principles used in engineering allow to estimate the behavior of various materials.
However, there are considerable difficulties connected with the determination of the complete set of
parameters, the number of which is too large for nonlinear case and it leads to the lack of uniqueness
in the determination of the parameters. Moreover, considerable difficulties arise when solving some
specific nonlinear problems of mechanics.
The fundamental idea of a completely different approach [23] is based on assumption that the
instantaneous deformation curve, () is considered as a curve of absolute zero temperature. The
constitutive equation can be presented in the form


() = + ( )()()
0

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where () is bounding from above the deformation process. It has been shown that a function of
temperature influence can be chosen as a power function 1 () = , where T is the temperature in
Kelvin. For convenience of calculation, the function can be taken as
273+
1 () = ( ) (9)
273

The influence of moisture can be accounted for in a similar manner [24-25] and function f2(W) can
be introduced under the integral, where W is determined from the weight increase in percent at
moisture saturation level

0 +%
2 () = ( ) (10)
0

Here, W0 is some empirical constant of the percent weight decrease of an absolutely dry material
compared to the weight of the material under the room moisture conditions.
The constitutive equation becomes

273+ 0 +%
() = + 0 ( )1 ( ) 2 ( ) () (11)
273 0

Summary. Substantial experimental data verifies the validity of such an approach. With increasing
moisture-saturation, the effect of creep becomes increasingly more pronounced and the stress-strain
diagrams shift increasingly further down. On the other hand, viscous effects will become considerably
weaker as the material dries because the materials characteristics approach the lower bound of the
instantaneous deformation curve. This makes one think that the application of the moisture influence
function should be the same as the temperature function. However, the experiments on moisture
influence are labor-intensive and demand carefully taken measurements with special equipment, thus
very few have been recorded in literature.
The most important problem is the construction of a moisture-saturation scale with at least two basic
points. In terms of temperature in degrees of Celsius, the points are the melting temperature of ice,
0C, and the boiling temperature of water, 100C. In the SI temperature system, the points used are
at absolute zero, 0K (-273C), and at 273K (0C). With these basic points the temperature influence
function f1(T) can be built. But since there is no sufficiently reliable scale available to measure the
moisture saturation, it is a difficult task to build the moisture influence function f2(W). However, in
(10), the value W0 has a definite physical sense. If W% becomes equal to W0 during a drying process,
then f2(W)=0 and as shown in (11), the equation of the instantaneous deformation curve () can be
written in a form independent of any other loading conditions. The value W0 must be one of the basic
points on the scale of moisture saturation with the other point being the moisture content at room
conditions.
The validity of such approach had been confirmed in [26], where the influence of various effects,
including moisture, on the strength properties of polymethylmetacrilate was considered. It was shown
that at a low loading rate of 10-3 sec-1, the presence of moisture leads to a considerable decrease of
strength and increase of viscous effects. Another possible application of the approach in connection
with experimental data on polymers and composites is given in [27-28].
However, the combined influence of temperature and moisture on the behavior of materials can be
more complex than described above by equation (11). Some secondary effects might appear.

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References
[1] Rabotnov Yu.N. Creep Problems in Structural Members, North-Holland (1969).
[2] Bland D.R. The Theory of Linear Viscoelasticity, Oxford (1960).
[3] Bolzmann L. Zur Theorie der Elastischen Nachwirkungen. Ann.Phys. and Chemie, Bd.7 (1876).
[4] Volterra V. Lecons sur la Theorie Mathematique de la Vito pour la Vie, Paris (1931).
[5] Volterra V. Theory of Functionals and of integral and integro-differential Equations, Dover
Publication (1959).
[6] Malthus T.R. An Essay on the Principle of Population, J. Johnson, London (1798).
[7] Duffing G. Elastizitat und Reibung beim Riementrieb. Forsch.Geb. Ingenieurwes, Bd.2, 3
(1931).
[8] Suvorova J.V. The Influence of Time and Temperature on the Reinforced Plastics Strength. In:
Failure mechanics of Composites, North-Holland, V. 3, p. 177-214 (1985).
[9] Suvorova J.V., Vasiliev A.E., Mashinskaya G.P., Finogenov G.N. Investigation of the
Organotextolite Deformational Processes, Mechanics of composite materials, N 5, p.847-851 (1980)
(In Russian).
[10] Goldman A.Ya. Strength of the Structural Members Polymers, L., Engineering research, 320p.
(1979) (In Russian).
[11] Rabotnov Yu.N., Papernik L.Kh., Zvonov E.N. Tables of the Exponential Function of Arbitrary
Order and its Integral. M., Nauka, 132p. (1969) (In Russian).
[12] Rabotnov Yu.N. Hereditary Mechanics of Solids. M., Nauka, 383p. (1977) (In Russian).
[13] Christensen R.M. Theory of Viscoelasticity. An introduction, Academic press (1971).
[14] Green A.E., Rivlin R.S. The Mechanics of Non-Linear Materials with Memory. Part I. Archive
for Rational Mechanics and Analysis, v.1, 1 (1957).
[15] Green A.E., Rivlin R.S. The Mechanics of Non-Linear Materials with Memory, Part III. Archive
for Rational Mechanics and Analysis, v.4, 5 (1960).
[16] Iliushin A.A., Pobedria B.E. Basis of the Mathematical Theory of Thermo-viscoelasticity. M.,
Nauka, 280p. (1970).
[17] Viktorova I., Dandurand B., Alexeeva S., Fronya M. The Modeling of Creep for Polymer-Based
Nanocomposites Using an Alternative Nonlinear Optimization Approach. Mechanics of Composite
Materials, No.6, Vol.48, pp.1-14 (2012), doi 10.1007/s11029-013-9313-y
[18] Suvorova J.V. Condition of the Metal Plastic Deformation at Various Regimes of Loading.
Mechanics of solids, N 1, p. 73-79 (1974) (in Russian).
[19] Melshanov A.F., Suvorova J.V., Khazanov S.Yu. Experimental Verification of the Constitutive
Equation for Metals at Loading and Unloading. Mechanics of solids, N 6, p. 166-170 (1974) (in
Russian).
[20] Rabotnov Yu.N., Suvorova J.V. The Non-linear Hereditary-type Stress-strain Relation for
Metals. Int. J. Solids and Structures, 14, N 3, pp.173-185 (1978).
[21] Ferry J.D. Viscoelastic Properties of Polymers. New York London (1961).
[22] Urzchumtcev Yu.S., Maksimov R.D. Prediction of the Deformational Properties of Polymer
Materials. Riga, Zinatne, 416p. (1975).
[23] Suvorova J.V. Temperature Account in the Hereditary Theory of Elastic-plastic Media. Problems
of Strength, N 2, pp.43-48 (1977) (in Russian).

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[24] Machmutov I.M., Sorina T.G., Suvorova J.V., Surgucheva A.I. Failure of Composites Under
Temperature and Moisture Influence. Mechanics of composite materials, N 2, pp.245-250 (1983) (in
Russian).
[25] Suvorova J.V., Machmutov I.M., Sokolovsky S.V., Sorina T.G. Influence of Moisture and
Preloading on Strength of the Composites with Polymer Matrices at Unidirectional Tension.
Mashinovedenie, N 5, pp. 62-66 (1985) (in Russian).
[26] Tynnyi A.N., Kolevatov Yu.A., Soshko A.I., Kalinin N.G. About an Influence of the Rate of
Deformation on the Strength of Polymer Materials in the Liquid Media. Physico-chemistry mechanics
of materials, v.5, N 6, pp. 677-679 (1969) (in Russian).
[27] Nguen Din Dyk, Suvorova, Alexeeva S.I. Combined Account of Temperature and Moisture in
the Constitutive Equation of Hereditary Type. Zavodskaya laboratoria, N 12 (2000) (in Russian).
[28] Nguen Din Dyk, Suvorova J.V., Alexeeva S.I. Sorina T.G. Influence of Moisture Saturation on
Strength of Bazaltoplastics. Zavodskaya laboratoria, N 12 (2000) (in Russian).

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A Study on the COP of CO2 Air Conditioning System with Minichannel


Evaporator Using Subcooling Process26

Thanhtrung Dang1,a, Chihiep Le2,b, Tronghieu Nguyen1,c, Minhhung Doan1,d

1 Department of Thermal Engineering, HCMC University of Technology and Education, Vietnam


2 Department of Heat and Refrigeration Engineering, HCMC University of Technology, Vietnam
a trungdang@hcmute.edu.vn
b lechihiep@gmail.com
c hieunt@hcmute.edu.vn
d hungdm@hcmute.edu.vn

DOI 10.2412/mmse.46.29.103 provided by Seo4U.link

Keywords: air conditioning, CO2 refrigerant, subcooling, minichannel, evaporator, heat transfer.

ABSTRACT. Experimental studies on a CO2 air conditioning system with minichannel evaporator using subcooling
process are presented in this paper. Without subcooling process, the COP obtained for this case is nearly 1.59; it is lower
than that of conventional air conditioning systems. But, with subcooling process, the COP strongly increases as the gas
cooler outlet temperature is lower than 30C which confirms the need of subcooling CO2 used in air conditioners. In
subcooling process, the COP of 4.97 was achieved for the gas cooler pressure of 77bar and the evaporating temperature
of 15C, it is higher than those obtained by other published results. It is suggested that the CO2 air conditioning system
should be operated corresponding to the case where the gas cooler pressure ranges from 74-77bar and the evaporating
temperature ranges from 10-15C in transcritical mode for high effectiveness and safety.

Introduction. Scientists working in air conditioning engineering have been interested in problems
such as environmentally friendly refrigerants and high effectiveness heat exchangers. In these fields,
CO2 is considered as a good candidate in order to replace HCFCs and compact heat exchangers would
be used widely in the future. Regarding to CO2 and compact heat exchangers, an overview of the flow
boiling heat transfer characteristics and the special thermo-physical properties of CO2 in a horizontal
tube was investigated by Zhao and Bansal [1]. Due to the large surface tension, the boiling heat
transfer coefficient of CO2 was found to be much lower at low temperatures but it increased with
vapor quality (until dryout). However, this study was only reviewed for horizontal tube. Baheta el at.
[2] simulated performance of transcritical carbon dioxide refrigeration cycle by using EXCEL
program. In this study, the highest Coefficient of Performace (COP) was 3.24 at 10MPa gas cooler
pressure. The results indicated that COP increases as rising the evaporative temperature. Using
numerical simulation, Cheng and Thome [3] studied on cooling of microprocessors using flow boiling
of CO2 in a micro-evaporator. Based on the analysis and comparison, CO2 appeared to be a promising
coolant for microprocessors at low operating temperatures but also presented a great technological
challenge like other new cooling technologies. However, the investigations in [2, 3] did not
experimentally perform.
A comprehensive review of flow boiling heat transfer and two-phase flow of CO2 covers both macro-
channel tests and micro-channel investigations was presented Thome and Ribatski [4]. The results
showed that CO2 gives higher heat transfer coefficients than those of conventional refrigerants.
Ducoulombier et al. [5] studied carbon dioxide two-phase flow pressure drops in a single horizontal

2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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stainless-steel micro-tube having the inner diameter of 0.529 mm. The apparent viscosity of the two-
phase mixture was larger than the liquid viscosity at low vapor qualities, namely at the lowest
temperatures. Cheng et al. [6, 7] updated flow pattern map for CO2 evaporation inside tubes. The
updated map was applicable for a wider range of conditions: tube diameters from 0.6 to 10 mm, mass
velocities from 50 to 1500 kg/m2s, heat fluxes from 1.8 to 46 kW/m2, and saturation temperatures
from 28 to +25 oC. The new CO2 two-phase flow pressure drop model predicted the CO2 pressure
drop was better than the former methods. Boiling heat transfer of carbon dioxide inside a small-sized
microfin tube was investigated by Dang et al. [8]. The experimental results indicated that heat flux
has a significant effect on the heat transfer coefficient and the coefficient does not always increase
with mass flux. In addition, the experimental results also shown that using microfin tubes may
considerably increase the overall heat transfer performance.
Numerical analysis use the finite volume method on a microchannel evaporator for CO2 air-
conditioning systems was fulfilled by Yun et al. [9]. The performance of the microchannel evaporator
for CO2 systems can be improved by varying the refrigerant flow rate to each slab and changing fin
space to increase the two-phase region in the microchannel. Design optimisation of CO2 gas
cooler/condenser in a refrigeration system was done Ge et al. [10]. In this study, the design
optimisation of the heat exchanger dealed with different structure designs, controls and system
integration at different operating conditions in order to significantly enhance the performance in a
CO2 refrigeration system. As a result, the effect of heat exchanger sizes on system performance can
be enhanced with fan speed controls. Chen et al. [11] analyzed and optimized a hybrid 2
transcritical mechanical compression ejector cooling cycle. The hybrid cooling cycle is a
combination of a CO2 transcritical mechanical compression refrigeration machine (MCRM) powered
by electricity, and an ejector cooling machine (ECM) driven by heat rejected from the CO 2 cooling
cycle. Refrigerants R245ca, R601b (neopentane) and R717 (ammonia) are investigated as the
working fluids of ECM in the present study. In this study, using the ejector cooling cycle for
subcooling the CO2 gas after gas cooler allows increasing the efficiency of the CO2 transcritical
cooling cycle up to 25-30% depending on the refrigerant type of the ejector cooling cycle. However,
the investigations in [11] were done by theoretical methods only.
Kuang et al. [12] studied a semi-empirical correlation of gas cooling heat transfer of supercritical
carbon dioxide in microchannels. Based on the experimental data, a new semi-empirical correlation
was developed to predict the gas cooling heat transfer coefficient of supercritical CO 2 in
microchannels, within an error of 15% for most (91%) of the presented experimental data that were
obtained in an 11-port microchannel tube with an internal diameter of 0.79 mm and with a pressure
range of 8 to 10 MPa and mass flux range of 300 to 1200 kg/m2s. Haida et al. [13] studied numerical
investigation of an R744 liquid ejector. However, authors only mentioned mass entrainment ratio,
mixer length, diffuser angle, suction mass flow rate, and the motive mass; they did not mention COP
of air conditioning system.
A review by Dario et al. [14] summarized the two-phase flow distribution in parallel channels with
macro and micro hydraulic diameters. The investigation allowed us to identify the main geometrical
and operating conditions which influence the two-phase flow distribution in parallel channels. Dang
et al. [15], [16], [17] investigated the heat transfer and pressure drop phenomena of the microchannel
and minichannel heat exchangers, both numerically and experimentally. At the same average velocity
of water in the channels used in this study, the effectiveness obtained from the microchannel heat
exchanger was 1.2 to 1.53 times of that obtained from the minichannel heat exchanger. Moreover,
influences of gravity to heat transfer and pressure drop behaviors of the microchannel heat exchanger
were presented by variation of the physical inclinations of the microchannel heat exchanger system
used for experiments. However, in [15], [16], [17], the pure water was the working fluid; they did not
study CO2 in these studies.
Yu et al. [18] studied the two-phase flows in microchannels. The results showed that two phase flows
have many advantages in heat and mass transfer compared to single-phase flows in microchannels.
The heat transfer characteristics of R410A in microchannels were measured by Yun et al. [19]. In this
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study, the boiling heat transfer coefficients of R410A in microchannels were much higher than single
tubes at similar test conditions. Effect of inlet configuration on the refrigerant distribution in a parallel
flow minichannel heat exchanger was studied by Kim et al. [20]. However, this study dealt with the
refrigerant R134a, not CO2, as the working fluid. Hernando et al. [21] studied the pressure drop, heat
transfer rate, and overall heat transfer coefficient in a single-phase micro-heat exchanger, both
experimentally and analytically. A review of boiling heat transfer enhancement on
micro/nanostructured surfaces was made by Kim et al. [22]. In this paper, the state-of-art of several
researches on boiling enhancement surfaces was reviewed. However, experimental investigations on
CO2 air conditioning system with compact heat exchangers as well as subcooled process did not show
clearly.
From literature reviews above, there are no more experimental studies on CO2 air conditioning system
with compact heat exchangers. In addition, they did not indicate thermodynamic parameters of CO2
air conditioning cycle as well as subcooled process clearly. Therefore, it is essential to investigate
CO2 air conditioning system experimentally. In this study, an aluminum minichannel evaporator was
used to get thermodynamic parameters of the air conditioning cycle and compared with conventional
evaporator. In addition, the cycle will be discussed with transcritical mode.
Methodology
Experimental setup. The experimental test loop for CO2 air conditioning system is shown in Fig.1.
This cycle has four main components: a CO2 compressor, a cooler, a thermal expansion valve, and an
evaporator. CO2 playing the role of refrigerant enters the compressor in superheated vapor state and
then it is compressed to a state at pressure and temperature higher than those at critical point. The
superheated vapor is then routed through a cooler.

a. Without subcooling coil b. With subcooling coil


Fig. 1. Schematic of the test loop for CO2 air conditioning system.

With subcooling process, the cooler outlet refrigerant enters the cold room to continuously reject heat
(as shown in Fig. 1b). Then the cooled refrigerant continues to move to an expansion valve. The
pressure is dropped dramatically when the gas runs through an expansion valve. At the outlet of
expansion valve, as usual the refrigerant becomes wet saturated vapor at lower temperature. The wet
saturated vapor is then sent to the tubes of the evaporator where it refrigerates the enclosed space. A
fan blows the warm air in the enclosed space across the tubes, so the warm air (the room-temperature
air) is cooled. Meanwhile, the liquid part of the wet saturated vapor is also heated to evaporate by the
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warm air. To complete the refrigeration cycle, the refrigerant vapor from the evaporator with saturated
vapor state is superheated and is routed back into the compressor. The temperature sensors and
pressure gauges were installed to get thermodynamic parameters at main points of this system. A
photo for this test loop is shown in Fig. 2.
Aluminum minichannels were used to manufacture for the evaporator, as shown in Fig. 3. The
refrigerant runs in the channels with four passes (29 channels in the total). Each minichannel is
rectangular in shape, with the width of 1.6 mm and the depth of 1.2 mm. The total heat transfer area
and the outside volume of this evaporator are 2.5 m2 and 2.97 dm3, respectively. The desgin cooling
capacity for this minichannel evaporator is 2700 W. For the cooler, the copper tubes were used in the
study. The cooler and evaporator were tested with the hydraulic testing method. The former and the
latter did not tear or deform at the pressure of 150 bars and 90 bar, respectively. Accuracies and
ranges of testing apparatus are listed in Tab. 1 and equipments used for the experiments are listed as
follows:

Table 1. Accuracies and ranges of testing apparatuses.


Testing apparatus Accuracy Range
Thermocouples 0.1 C 0 100 C
Thermal camera 2% -20~250C
Infrared thermometer 1 C of reading - 32 400 C
Pressure gauge 1 FS 0100 kgf/cm2
Clamp meter 1.5 % rdg 0 200 A
Anemometer 3% 0 45 m/s

- Thermocouples, T-types
- Thermostat, EW 181 H, made by Ewelly
- Infrared thermometer, AT 430L2, made by APECH
- Infrared thermometer, Raynger@ST, made by Raytek
- Thermal camera, Fluke Ti9, made by Fluke, USA
- Pressure gauge, made by Pro Instrument
- Anemometer, AVM-03, made by Prova
- Clamp meter, Kyoritsu 2017, made by Kyoritsu

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Evaporator

Cold room

Cooler
Compressor

Fig. 2. A photo of the CO2 air conditioning system.

Fig. 3. Dimensions of the minichannel evaporator.

Governing equations. To analyze the thermodynamic properties of the tested CO2 air conditioning
system, the governing equations were given below:
The heat transfer rate for condensation was calculated as

(1)
Q 23 m c c p T2 T3

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The power input was determined using



W 12 m c h2 h1
(2)

The heat transfer rate for subcooling was calculated as

(3)
Q 33' m c c p T3 T3'

The isenthalpic process was presented by

h3' h4 (4)

The heat transfer rate for evaporation was calculated as

(5)
Q 4 1 mc h1 h4

Finally the COP of the cycle was quantified by

(6)
Q 4 1
COP
W 1 2


where m c is the mass flow rate of carbon dioxide.
Results and discussion
The air conditioning without subcooling.
The CO2 air conditioning system without subcooling was tested more than 200 times in order to
collect data for transcritical mode. The period for each time getting data is 30 minutes. The results
obtained from this experiment are very stable. Table 2 shows the thermodynamic parameters of the
cycle for five times under the ambient temperature of 31.5C. Due to pressure drop of the cooler and
evaporator, the pressures at the outlets of these heat exchangers are lower than those obtained from
the inlet ones. Therefore, isothermal and isobaric processes in this cycle are quasi with theory. The
data were drawn on the p-h diagram of CO2.

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Table 2. Thermodynamic parameters of the CO2 cycle without subcooling.


p1 t1 p2 t2 p3 t3 p4 t4
(bar) (C) (bar) (C) (bar) (C) (bar) (C)
36.0 20.2 87 85.8 86.5 39.2 37 5.1
36.0 20.1 87 86.0 86.5 38.8 37 5.2
36.5 20.2 87 85.7 86.5 39.3 37 5.0
36.0 20.0 87 86.1 86.0 39.4 37 4.9
36.0 20.2 87 85.9 86.5 39.1 37 5.0

The experimental points of the cycle on the p-h diagram are shown in Fig. 4. With this case, the mass
flow rate of refrigerant is 76.7 kg/h. Based on the equations from (1) to (6), the COP obtained for this
case is 1.59 with the cooling capacity of 2100 W. This COP value is lower than conventional air
conditioning systems. From Tab. 2 and Fig. 4, it is observed that the gas cooler outlet temperature
was high, the temperature difference between gas and air was also high, leading to the vapor quality
was high and the vaporization latent heat was small. Therefore, the actual cooling capacity was
smaller than the design cooling capacity of the cycle. As a result, this caused the high superheat for
the system. All reasons cased low COP for this system. However, the COP of this cycle is in good
agreement with the COP in [2] at the gas cooler pressure of 87 bar and the gas cooler outlet
temperature of 39 C.

Fig. 4. Experimental points of the cycle on p-h diagram without subcooling.

A conventional evaporator (using for an absorbed power of 750 W) was installed in this cycle. The
conventional evaporator was made from copper tubes, having the design cooling capacity of 2700 W
and the outside volume of 11.05 dm3. The conventional evaporator was tested hydraulic and it did
not tear or deform at the pressure of 90 bar. An experimental comparison between the minichannel
evaporator and conventional evaporator is listed in Table 3. At the same operating conditions, the
results obtained from the conventional evaporator are the same with those obtained from the

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minichannel evaporator. However, the outside volume of the minichannel evaporator is smaller than
the conventional evaporator (only equals 0.27 times). The results indicate that the minichannel
evaporator is suitable in the CO2 air conditioning system with high heat transfer rate and high
allowable pressure (as the same nominal thickness).

Table 3. Comparison between minichannel and conventional evaporators.


p1 t1 p2 t2 p3 t3 p4 t4
(bar) (C) (bar) (C) (bar) (C) (bar) (C)
Minichannel evaporator 36.5 20.2 87 85.7 86.5 39.3 37 5.0
Conventional 36.7 20.1 87 86.0 86.5 38.9 37 5.1
evaporator

The air conditioning with subcooling


With subcooling, the minichannel evaporator was also used in this test loop. The CO2 air conditioning
system was tested more than 100 times to collect data. The period for each time getting data was 30
minutes. The transcritical mode was also done in this study. The results obtained from this experiment
are also stable. The experimental results for thermodynamic parameters of the cycle with subcooling
are listed in Tab. 4. The data were drawn on the p-h diagram of CO2, as shown in Fig. 5. The
experimental results indicated that the pressure drop of the heat exchangers in this case is higher than
that obtained from the case of without subcooling. It may be some refrigerant lubricant or dirty enters
the two heat exchangers.

Fig. 5. Experimental points of the cycle on p-h diagram with subcooling.

Figure 5 shows the experimental points of the cycle on the p-h diagram for five times getting data.
The mass flow rate of refrigerant is 84.4 kg/h in this case. Based on the equations from (1) to (6), the
COP obtained for this case is 4.39, with the cooling capacity of 3890 W. The superheat in this case
is also 3 C, it is smaller than that obtained from the without subcooling case (15 C). A photo of
minichannel evaporator using thermal camera is shown in Fig. 6 for the evaporating temperature of
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9.2 C. The figure showed that the profile temperature of outside evaporator is the same (around 11
C). The results are in good agreement with evaporating theory.

Table 4. Thermodynamic parameters of the CO2 cycle with subcooling.


p1 t1 p2 t2 p3 t3 t3 p4 t4
(bar) (C) (bar) (C) (bar) (C) (C) (bar) (C)
45 9.2 77 55 77 32.2 29.4 47 13.5
45 9.4 77 55 77 32.1 29.2 47 13.5
45 9.3 77 55 77 32.1 28.9 47 13.3
45 8.9 77 55 77 32.4 29.1 47 13.5
45 9.2 77 55 77 32.2 29.2 47 13.2

Fig. 6. A picture of minichannel evaporator using thermal camera.

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6 4000 3.5

5 3
3000

Cooling capacity, W
2.5
4
2

COP
COP

3 2000
1.5
2
COP 1
1000
1 Cooling capacity
0.5

0 0 0
20 25 30 35 40 20 25 30 35 40 45
0 0
Gas cooler outlet temperature, C Gas cooler outlet temperature, C

Fig. 7. COP vs. gas cooler outlet temperature Fig. 8. COP vs. gas cooler outlet temperature
for the gas cooler pressure of 77 bar. for the gas cooler pressure of 87 bar.

Figure 7 shows correlations of COP, cooling capacity, and gas cooler outlet temperature. The results
obtained for the gas cooler pressure of 77 bar and evaporating temperature of 15 C. The parameters
obtained by adjusting the expansion device, the subcooling coil, the flow rate of gas and air, and the
compressor. It is observed that the COP strongly increases as the gas cooler outlet temperature is less
than 30 C. This is one of special properties of CO2 when it is used in air conditioning. This thing
also indicated an importance of subcooling for the CO2 air conditioner. The experimental results for
COP obtained from the present study are higher than those obtained from [2], [11]. In this study, the
COP of 4.97 was achieved for the gas cooler pressure of 77 bar, the evaporating temperature of 15
C, the super heat of 15 C, and the gas cooler outlet temperature of 25 C.
Figure 8 shows experimental correlation of the COP and the gas cooler outlet temperature for the gas
cooler pressure of 87 bar and evaporating temperature of 5 C. The COP of 3.14 was achieved for the
gas cooler pressure of 87 bar, the evaporating temperature of 5 C, the super heat of 15 C, and the
gas cooler outlet temperature of 25 C. From Figs. 7 and 8, it is suggested that the CO2 air conditioning
system should be operated for the gas cooler pressure of 74-77 bar and the evaporating temperature
of 10-15 C in transcritical mode for high effectiveness and safety. However, to get high COP, the
cycle has to add a subcooling coil. Compared with commercial catalogues, the COP of this cycle is
higher than the COP of air conditioners using HCFC refrigerant (about 3.1 3.5). From experimental
results above, they are needed and important for studying and developing the CO 2 air conditioning
systems.
Summary. Experimental studies on a CO2 air conditioning system with minichannel evaporator were
done. In these studies, the minichannel evaporator was also added in order to compare with
conventional one. The experimental results obtained from the two heat exchangers are nearly the
same when testing in the same conditions. However, the size of minichannel evaporator is lower than
that of conventional one.
Without subcooling process, the COP obtained for this case is 1.59 with the cooling capacity of 2100
W. This COP value is lower than the conventional air conditioning system.
With subcooling process, the COP strongly increases as the gas cooler outlet temperature is less than
30C. This important feature should be considered carefully when designing CO2 air conditioning
system working in transcritical region. In this case, the COP of 4.97 was achieved for the gas cooler

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pressure of 77 bar, the evaporating temperature of 15 C, the super heat of 15 C, and the gas cooler
outlet temperature of 25 C.
The experimental results for COP obtained from the present study are higher than those obtained from
several literature reviews. It is suggested that the CO2 air conditioning system should be operated for
the gas cooler pressure of 74-77 bar and the evaporating temperature of 10-15 C in transcritical mode
for high effectiveness and safety. However, to get high COP, the cycle has to add a subcooling coil.
Acknowledgment
The supports of this work by the project No. 35/2015/HD-SKHCN (sponsored by HCMC Department
of Science and Technology, Vietnam) are deeply appreciated.
Nomenclature

W power input

Q heat transfer rate

m c mass flow rate
h enthalpy
p pressure
t temperature
Subscripts.
c carbon dioxide
1 exit of evaporator
2 exit of compressor
3 exit of gas cooler
3 exit of subcooler
4 exit of throttling valve.
References
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[7] Cheng, L., et al., New flow boiling heat transfer model and flow pattern map for carbon dioxide
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VII. Environmental Safety


M M S E J o u r n a l V o l . 1 0

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Dark-Black Stains on Rooftops: Implications on the Quality of Water Harvested


from Rooftops in Uyo Metropolis-Nigeria27

Ihom A.P.1,a,b, Uko D.K. 1, Markson I.E. 1, Eleghasim O.C. 1

1 Department of Mechanical Engineering, University of Uyo, Uyo, PMB 1017 Uyo-Nigeria


a ihom@uniuyo.edu.ng
b paulihom@yahoo.co.uk

DOI 10.2412/mmse.100.67.317 provided by Seo4U.link

Keywords: rainwater, quality, harvest, WHO, dark-black stains, rooftops.

ABSTRACT. The study Dark-Black Stains on Rooftops: Implications on the Quality of Water Harvested from Rooftops
in Uyo Metropolis-Nigeria has been undertaken. The study took samples of harvested rainwater from the rooftops of
buildings in four different locations in Uyo Metropolis. The samples were taken for analysis at the Ministry of Science
and Technology Laboratory-Uyo. The parameters of the harvested rainwater investigated covered physical and chemical
properties, heavy metals, total organic carbon (TOC) and total coliform count (TCC). Gravimetric, titrimetric and
instrumental methods of analysis were used in determining the various parameters investigated. The result was analysed
by comparing it with WHO and Ministry of Environment standard specifications for drinking water. The result was
equally compared with the composition of the dark-black stains on the rooftops to establish whether the stains on the
rooftops were from the rainwater. Findings were astounding; the rainwater was acidic in all the four stations and could
not meet up with WHO standard for drinking water. Lead values of 0.75 mg/l and 0.22 mg/l in stations 2 and 3 respectively
exceeded WHO standard specification of 0.01mg/l for drinking water. The iron content in the water from stations 2, 3,
and 4 all exceeded WHO standard specification for drinking water of 0.30mg/l. All the four stations had cadmium content
in the rainwater, which was more than WHO specification for drinking water of 0.003mg/l. The water showed bacteria
contamination with total coliform count of 118MPN/100ml in station 4. Some of the parameters in the rainwater also
reported in the composition of the dark-black stains on the rooftops an indication that the rain contributed to the dark-
black stains on the rooftops in Uyo metropolis. The study concluded that harvested rainwater from the rooftops of
buildings in Uyo metropolis is polluted and is not suitable for drinking, bathing and even for use in fish farming. The
study therefore recommended that the health implication of this study be carried out by relevant agencies of government.

Introduction. Dark-black stains on rooftops are a common sight in Uyo metropolis. Nwokocha [1] in his work
has attributed oil and gas flaring as being responsible for the menace. He said this can be seen in most oil
producing states in Nigeria; particularly the Niger Delta region. Dara [2], agrees with Nwokocha [1], but goes
further to explain the mechanism of the formation for these stains. Gas flaring produces smoke and soot
including other particulates and gases. According to [1] these is discharged into the atmosphere, which already
have other particulates like Fe2O3, V2O3, CaO, PbCl2, PbBr2, fly ash, aerosols, etc. soot is a highly condensed
product of polycyclic aromatic hydrocarbons (PAH) compounds and can itself adsorb many PAH compounds
and toxic trace metals e.g., Be, Cd, V, Cr, Ni, and Mn, as well as carcinogenic organics such as benzo--
pyrenes. The air speed determines the settling of this mixture unto surfaces and rain also washes the mixture
from the air unto surfaces, and roofs are normally readily available surfaces for such deposits from the air.
This position is corroborated by several authors [3], [4], [5]. When water mixes with the mixture it forms the
dark-black stain that is seen on rooftops in oil and gas flaring areas [6], [7], [8], [9].
In an address presented by the governor of Akwa Ibom State, Mr Udom Emmanuel Gabriel at the environment
summit organized by the state government at Le Meridien Hotel and Golf Resort, Uyo. The governor lamented
the adverse effects of environmental pollution caused by oil flaring and fossil fuels combustion on humans and
the environment, he specifically mentioned darkening roof-tops in Uyo metropolis which has taken away the
aesthetics of many buildings in the state. According to the governor, the problem is so serious that many people
are now using dark and black coloured roofing sheets to conceal the black deposits on their roof-tops [10]. The

2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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nature of this black deposit is not understood, it is only assumed that it is from gas flaring and combustion of
fossil fuels from generators and automobiles. Olajire [11] and Nwokocha [1] also in their respective studies
have linked the dark black stains on the roofs to pollution from gas flaring and other industrial activities. Figs.
1-5 clearly captures the menace.

Fig. 1. Building in Uyo Metropolis: The Roof is Completely Covered with Dark-Black Deposit.

Fig. 2. Building Roof Completely Covered with Dark-Black Coating/Deposit.

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Fig. 3. Building Roof Completely Covered with Dark-Black Deposit.

Fig. 4. The Roof Top of the Building in the Front is covered with Dark-Black Deposit, the Storey Buildings
Behind are Roofed with Dark-colored Roofing Sheets to Conceal the Effect of the Dark-Black Deposit.

Fig. 5. Dark-Black Deposit on Colored Roofs in a Housing Estate in Uyo Town.

Dara [2] any human activity that impairs the use of water as a resource is called water pollution. With exploding
population and increasing industrialization and urbanization, water pollution by agricultural, municipal and

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industrial sources has become a major concern for the welfare of mankind. Water is essential for the survival
of any form of life. On an average, a human being consumes about 2 litres of water every day. Water accounts
for about 70% of the weight of a human body. About 80% of the earths surface (i.e 80% of the total 50000
million hectares in area) is covered by water. Out of the estimated 1,011 million km3 of the total water present
on earth, only 33,400m3 of water is available for drinking, agriculture, domestic and industrial consumption.
The rest of the water is locked up in oceans as salt water, polar ice-caps and glaciers and underground. Owing
to increasing industrialization on one hand and exploding population on the other, the demands of water supply
have been increasing tremendously. Moreover, considerable part of this limited quantity of water is polluted
by sewage, industrial wastes and a wide array of synthetic chemicals. The menace of water-borne diseases and
epidemics still threatens the well-being of population, particularly in underdeveloped and developing countries
like Nigeria. Thus, the quality as well as the quantity of clean water supply is of vital significance for the
welfare of mankind [12], [13], [14], [15], [16]. Uyo receives 2000-4000mm of rainfall annually. It is estimated
that 96% of this water is used for agriculture, 3% for domestic use and 1% for industrial activity [16]. The
various types of water pollution are broadly classified as organic, inorganic, suspended solids and sediments,
radioactive materials and heat pollutants.
Water harvesting is a common practice in different parts of the world including Uyo metropolis. Water
harvested from the rooftops of buildings is used for cooking, bathing, and washing, flushing of toilettes,
drinking, and agriculture. Fish farmers who have to be changing water for their fishes quite often, do find
raining season very convenient. Studies have shown that most of the rain water collected from rooftops is
polluted; to what extent? This may also depend on the area and the kind of natural and anthropogenic activities
going on in the area [1], [11], [17]. Definitely the pollution level in the oil and gas producing areas will be
more than that of serene and pristine areas where gas flaring, automobiles, and generating sets are lacking.
This present work seeks to answer the question to what extent is harvested water from the rooftops of dark-
black stained roofs polluted? is the content of the water similar to the composition of the dark black deposit
on the rooftops? Answering these questions is important because the health implications may be disastrous
and should be understood. There are reports of people who have complained of soapy-feelings and itching
skin after bathing with rain water from dark-black stained rooftops.
The objective of this work is to establish the quality of water harvested from dark-black stained rooftops of
buildings in Uyo metropolis.
MATERIALS AND METHOD
Materials. The materials used for this research work included, chemicals of various types like potassium
hydrogen phythalate buffer, sodium chloride, barium chloride, sodium sulphate, concentrated sulphuric acid
etc., which were used in the analyses of the samples, and rain water which was collected from different parts
of the metropolis from rooftops.
Equipment. The equipment used for the research work included sample collecting plastics buckets, specimen
bottles (McCartney), Scanning Electron Microscope (SEM), pH meter, electrical conductivity meter, turbidity
tube, conical flasks, test tubes, pipette, burette, spectrophotometer, steam bath, systronics flame photometer
128, coliform bottles, and as required by the various standard tests for the samples at the Ministry of Science
and Technology, Uyo Analytical Laboratory.
The Study Area. The study area of this research work is Uyo metropolis. Uyo is the Capital of Akwa Ibom
state. It is a major oil producing state in Nigeria, with a lot of gas flaring activities going on from the oil
exploiting companies. The population of Uyo according to the 2006 Nigerian census which comprises Uyo
and Itu is 436,606. The metropolitan area covers an estimated area of 168 km2 (65sq.mi). Uyo is a fast-growing
city and has witnessed some infrastructural growth in recent years. It is located on coordinates 502`N and
7056E.
The average annual rainfall in the study area is between 2000-4000mm with the period of fall usually between
April and October. The rainfall reaches its peak in the months of June and September, while the dry period
falls between November to March. The relative humidity of the area varies between 75% and 95% with mean
annual temperatures of about 26 to 36oC. Fig. 6 is the map of the study area. The samples for the work were
taken in different areas of the metropolis covering, Use Offot on Nwanniba road (station 2), University of Uyo,
main campus on Nwanniba road (station 1), Ikot-Okubo on Abak road (station3), and Mbaibong on Oron road
(station 4). The town is characterized by high usage of generators as a result of incessant power failure from
the national grid and high vehicular traffic typical of a growing metropolis.

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Fig. 6. The Map of Uyo Metropolis the Study Area.

Method. The rain water samples which were harvested from rooftops in four different areas of Uyo Metropolis
as indicated by the research study area above were sent to ministry of Science and Technology, Uyo for various
tests and analysis. Both wet and instrumental analysis were used for the testing of the test specimens. The
samples from the different locations were subjected to pH test using pH meter, which was calibrated earlier on
using standard buffer solutions. Standard procedures were adopted in carrying out the following tests on the
rain water samples collected from the rooftops of buildings in Uyo metropolis, electrical conductivity test,
turbidity test, temperature, total suspended solid, salinity, chloride, dissolved oxygen, biochemical oxygen
demand, chemical oxygen demand, total dissolved solid, hydrogen carbonate, hardness, calcium, magnesium,
lead, iron, copper, zinc, cadmium sodium, nitrogen, total organic carbon, nitrate, sulphate, phosphate, and total
coliform count which constituted the microbiological analysis of the water. The determination of the heavy
metals was done through digestion method using perchloric acid according to the standard methods proposed
by Association of Analytical Chemists. The Scanning Electron Microscope micrograph of the dark black
deposit on the rooftops was also carried out at Defence Industries Corporation of Nigeria (DICON).
RESULTS AND DISCUSSION
Results. The various results of the tests which were carried out on the rain water samples from various parts
of Uyo metropolis are here displayed in Tables1-4. Table 5 is the WHO and Ministry of Environment
specification for drinking water. Table 6 is the chemical composition of the dark-black deposit on rooftops.
Plates I-VI shows the plates of cultured rain water from the four stations with coliform growth. The SEM
micrograph of the rooftop coated dark black deposit is also shown in Plate VII.

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Table 1. Physical and Chemical Properties of Rain Water Collected from Four Different Locations from
Rooftops in Uyo Metropolis.
S/No Parameter SAMPLE IDENTIFICATION
Station 1 Station 2 Station 3 Station 4
1 pH 5.49 5.24 6.41 5.92
o
2 Temperature C 24.6 24.95 25.1 28.15
3 Electrical conductivity 35.12 50.41 82.6 50.6
(EC) (s/cm)
4 Total suspended solid < 0.01 0.01 <0.01 0.01
(TSS) (mg/l)
5 Salinity (mg/l) 15.41 23.4 35.1 23.4
6 Chloride (Cl) (mg/l) 10.65 14.2 21.3 14.2
7 Dissolved oxygen (DO) 7.17 8.3 6.37 8.22
(mg/l)
8 Biochemical oxygen 2.0 4.2 2.2 4.44
demand (mg/l)
9 Chemical oxygen 3.9 8.1 4.4 8.3
demand (COD) (mg/l)
10 Turbidity (NTU) (mg/l) 0.14 0.3 0.19 0.26
11 Total dissolved solid 17.55 25.3 41.4 25.3
(TDS) (mg/l)
12 Hydrogen Carbonate 18.3 18.3 12.2 24.4
(HCO3) (mg/l)
13 Hardness (CaCO3) 1.5 1.5 1.0 2.0
(mg/l)
14 Calcium (Ca) (mg/l) 23.47 1.87 1.07 2.93
15 Magnesium (Mg) 11.73 0.93 0.53 1.47
(mg/l)

Table 2. Heavy Metals and Metals in Rain Water collected from Four Different Locations from Rooftops in
Uyo Metropolis.
s/No Parameter Sample identification
Station 1 Station 2 Station 3 Station 4
1 Lead (Pb) (mg/l) <0.01 0.75 0.22 <0.01
2 Iron (Fe) (mg/l) 0.12 0.79 0.53 0.55
3 Copper (Cu) (mg/l) 0.11 0.21 0.2 0.19
4 Zinc (Zn) (mg/l) 0.33 0.91 0.91 1.16
5 Cadmium (Cd) (mg/l) <0.01 0.82 0.61 0.02
6 Sodium (Na) (mg/l) <0.01 1.79 1.86 1.65

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Table 3. Nitrogen and Salts in Rain Water Collected from Four Different Locations from Rooftops in Uyo
Metropolis.
s/No Parameter Sample identification
Station 1 Station 2 Station 3 Station 4
1 Nitrogen (N) (mg/l) <0.01 <0.01 <0.01 <0.01
2 Nitrate (NO3) (mg/l) <0.01 <0.01 0.01 <0.01
3 Sulphate (SO3) (mg/l) 0.01 0.01 <0.01 <0.01
4 Phosphate (PO4) (mg/l) 0.01 <0.01 <0.01 <0.01

Table 4. Total Organic Content (TOC) and Total Coliform (TCC) in Rain Water Collected from Four Different
Locations from Rooftops in Uyo Metropolis.
s/No Parameter Sample identification
Station 1 Station 2 Station 3 Station 4
1 Total Organic Content 50 75 75 66.67
(TOC) %
2 Total Coliform (TCC) 105 (18hrs) 61 (18hrs) 6 (18hrs) 118 (18hrs)
(MPN/100 ml)

Key: Station 1: University of Uyo, main campus on Nwanniba road, Station 2: Use Offot on Nwanniba road,
Station 3:Ikot-Okubo on Abak road Station 4: Mbaibong on Oron road.

Table 5. World Health Organization and Federal Ministry of Environment Drinking Water Standards.
s/No. Parameter WHO (2008) FMEnv (2007)
1 Appearance Clear Clear
2 Colour (HU) 15 15.00
3 Taste Inoffensive Inoffensive
4 Odour Inoffensive Inoffensive
5 Temperature (oC) 27-28 -
6 Ph 6.5-8.5 6.5-8.5
7 Turbidity (NTU) 5.00 5.00
8 Electrical conductivity (s/cm) 1000 1000
9 Total dissolved solids (mg/l) 500 500
10 Alkalinity as (CaCO3) (mg/l) 200 -
11 Hardness (mg/l) 100 150.00
12 Dissolved oxygen (mg/l) 6.00 7.50
13 BOD (mg/l) 6.00 10.00
14 Chloride (mg/l) 250.00 250.0
15 Nitrates (mg/l) 10.00 10.00
16 Nitrite (mg/l) 0.20 0.20

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17 Fluoride (mg/l) 1.00 1.50


18 Sulphate (mg/l) 250 200.00
19 Phosphate (mg/l) 3.50 <5.00
20 Residual chloride (mg/l) 0.2-0.4 0.2-0.4
21 Sodium (mg/l) 200.00 200.00
22 Calcium (mg/l) 75.00 200.00
23 Magnesium (mg/l) 150.00 150.00
24 Potassium (mg/l) 15.00 150.00
25 Nickel (mg/l) 0.07 -
26 Lead (mg/l) 0.01 0.01
27 Copper (mg/l) 0.05 1.00
28 Cadmium (mg/l) 0.003 0.003
29 Chromium (mg/l) 0.01 0.05
30 Zinc (mg/l) 0.10 5.00
31 Iron (mg/l) 0.30 0.30
32 Manganese (mg/l) 0.10 0.20
33 Cyanide (mg/l) 0.05 0.07
34 Mercury (mg/l) 0.001 0.006
35 Molybdenum (mg/l) 0.07 0.07
36 Selenium (mg/l) 0.01 0.01

Source: WHO (2008), FMEnv (2007)

Table 6. Chemical Composition of Dark-Black Material Scrapped from Roof-Tops (Analysed at NMDC Jos).
Parameters (in %)
S/No Sample Al2O3 SiO2 P2O5 SO3 K2O CaO TiO2 V2O5
1 Blackish 16.00 43.80 1.20 2.71 3.20 1.62 2.93 0.11
powder
from
roof-top

Cr2O3 MnO Fe2O3 NiO Co2O3 CuO ZnO Br Rb2O SrO


0.10 0.31 10.55 0.05 ND 0.09 0.22 0.07 0.03 0.05

ZrO2 Yb2O3 Re2O7 PbO Carbonaceous and volatile matter


0.20 0.001 0.06 0.11 16.59

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Plate I: coliform growth on sample rain water collected from rooftops at station 4 Mbiaobong Etoi Uyo, after
18hrs of culture.

Plate II: Coliform growth on sample rain water collected from rooftops at station 1 Uniuyo main campus after
18 hrs of culture.

Plate III: Coliform growth on sample rain water collected from rooftops in station 3 Ikot Ukuubo Uyo after
18hrs of culture

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Plate IV: Coliform growth on sample rain water collected from the rooftop at station 2 use offot after 18hrs of
culture.

Plate V: Coliform growth on sample rain water collected from rooftops at station 1 Uniuyo main campus after
18hrs of culture.

Plate VI: Coliform growth on sample rain water collected at station 4 Mbiaobong Etoi Uyo after 18 hrs of
culture

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Plate VII: Scanning Electron Microscope (SEM) Micrograph of Dark-Black Deposit on Aluminium-Base
Roofing Sheet. The light shining areas are where the deposit of the material is low and the dark areas are
where the deposit has covered the aluminium sheet completely.

Discussion. Previous works carried out by several researchers have established that the sources of dark black
deposits on rooftops are normally from rain, (which washes the air content of particles, soot, gases and aerosols
down unto the rooftops) dry air, and wet air. These three sources transport the deposits onto the rooftops [3],
[4], [5], [18], [19]. The discussion of the result of this present paper (which is part of a global research work
sponsored by TETFUND to investigate the root causes and possible remedies of quick corrosion and formation
of dark- black deposits on rooftops in Uyo metropolis) is going to be tailored in two directions. The result of
the harvested rain water from rooftops is going to be compared with WHO and Federal Ministry of
Environment quality standards for drinking water and on the second front, the composition of the water is
going to be compared to the chemical composition of the dark-black deposit on the rooftops which was
analysed in the earlier part of this ongoing research work.
Table 1 shows the Physical and Chemical Properties of Rain Water Collected from Four Different Locations
from Rooftops in Uyo Metropolis labelled station 1, station 2, station 3 and station 4. Looking at the result in
the Table and comparing it with WHO and Federal Ministry of Environment standards in Table 6 the only
parameters of concern are; pH, electrical conductivity, and chemical oxygen demand. The pH of rainwater is
normally 5.6, which is acidic, and this is because of the dissolution of carbon dioxide, sulphur dioxide and
other gases in rain water. Station 2 has the highest acidity of 5.24, which is even lower than normal rainwater
value of 5.6. Station 1 has pH value of 5.49 this is also lower than the normal rainwater value of 5.6. These
two stations have indicated pollution; the effect of these is that the water will affect the mucous membrane,
and give rise to increase leaching and corrosion of rooftops. If the water is passed through water supply system
it will corrode the system. The water has low electrical conductivity with station 1 having the lowest electrical
conductivity of 35.12 s/cm as compared to the WHO standard of 1000s/cm. The poor electrical conductivity
is as a result of the absences of plenty dissolved ion species in the rain water. Although in all the four stations
the chemical oxygen demand is less than the WHO standard of 10mg/l, the closeness of the values of stations
2 and station 4 to the standard value of 10mg/l is worrisome. They have the values of 8.1mg/l and 8.3mg/l
respectively. This is an indication of pollution but looking at the BOD values it cannot be of organic nature
but must be coming from the oxidisable inorganic components in the water [2], [6], [7], [8], [9], [19].
Table 2 Heavy Metals and Metals in Rain Water collected from Four Different Locations from Rooftops in
Uyo Metropolis and labeled station 1, station 2, station 3, and station 4. Looking at the result of Table 2, the
metals of concern are lead, iron, zinc, and cadmium. Lead content in stations 2 and 3 are worrisome this is
because the values are greater than WHO standard value of 0.01mg/l. Station 2 has the value of 0.75 mg/l and
station 3 has the value of 0.22 mg/l. Expected side effects is that this water is toxic. Lead causes an endemic
disease called lead colic. Lead is considered as a general protoplasmic poison which is cumulative, slow-
acting and subtle. The major biochemical effect of lead is its interference with heme synthesis; leading to
hematological damage. Lead inhibits several important enzymes involved in the overall process of heme
synthesis. It disrupts the synthesis of haemoglobin and other respiratory pigments such as cytochromes which
require heme. Iron content in stations 2, 3, and 4 are greater than WHO 0.3mg/l although the permissible range
is up to 1 mg/l. The value for station 2 is 0.79 mg/l, station 3 is 0.53 mg/l and station 4 is 0.55 mg/l, these
values are greater than the standard and therefore indicates pollution which will affect taste, appearance and
also have adverse effects on domestic uses and water supply structures, and promote iron bacteria. Zinc content

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in the rain water from stations 1-4 all exceed the WHO standard of 0.1mg/l but not higher than the permissible
range of 3 mg/l. Station 1 has the value of 0.33mg/l, station 2 value is 0.91mg/l, station 3 value is 0.91mg/l
and station 4 value is 1.16mg/l. These values all exceed WHO standard. This may lead to astringent taste and
an opalescence in water. Cadmium content in rain water from the four stations exceed WHO standard value of
0.003mg/l this is worrisome. Station 1 has the value of <0.01mg/l, station 2 has the value of 0.82mg/l, station
3 has the value of 0.61mg/l and station 4 has the value of 0.02mg/l. The water becomes toxic beyond the WHO
standard. Cadmium acts as inhibitor of sulphydryl enzymes. It has also got affinity for other ligands in cells,
such as hydroxyl, carboxyl, phosphatyl, cysteinyl, and histidyl sidechains of proteins, purines and porphyrin.
It can disrupt pathways of oxidative phosphorylation. Cadmium is highly toxic because of the absence of
homeostatic control for this metal in the human body. Cadmium in water at 10 ppm level can kill fishes in one
day while at 2 ppm level they will be killed in 10 days. This water therefore cannot be recommended for fish
farming [2], [12], [13], [14], [15], [16].
Table 3 shows Nitrogen and Salts in Rain Water Collected from Four Different Locations from Rooftops in
Uyo Metropolis and labeled as station 1, station 2, station 3 and station 4. Looking at the Table all the
parameters in the Table did not exceed or compromise WHO standards specifications and therefore did not
create any worrisome situation.
Table 4 shows Total Organic carbon Content (TOC) and Total Coliform (TCC) in Rain Water Collected from
Four Different Locations from Rooftops in Uyo Metropolis and labeled station 1, station 2, station 3 and station
4. Looking at the Table the values of total organic carbon and total coliform count are high in some of the
stations and therefore indicate some level of pollution of the rainwater collected from the rooftops. The total
organic carbon in station 1 is 50%, station 2 is 75%, station 3 is 75% and station 4 is 66.67%. This carbon
cannot be from natural source but from anthropogenic activities such as gas flaring, generating sets, burning
of fossil fuels and vehicular emissions. It is most likely that the black colour of the deposit on the rooftop is
from the carbon. Their connection to poly-aromatic hydrocarbons (PAHs) makes them poisonous. The total
coliform count in the four stations is as shown in Table 4. Station 4 has the highest total coliform count (TCC)
of 118 MPN/100ml followed by station 1 with 105 MPN/ 100 ml, the total coliform count shows the level of
contamination of the rainwater with coliform. This poses health hazard and pollution of the water harvested
from the rooftops; the availability of coliforms in any sample indicates the presence of the potential harmful
threats to man and environment. Coliforms are a broad class of bacteria that are readily available in our
environment. They can survive on roofs and walls of buildings [2], [20], [17].
Although, bacteria and fungi colonies have many characteristics and some can be rare, there are a few elements
that you can identify for all colonies. Most bacteria colonies appear white, cream or yellow in colour, and fairly
circular in shape. Yeast species such as candida, can grow as white patches with a glossy surface. We equally
have round, and pink yeast colonies, molds are actually fungi and they often appear whitish, with fuzzy edges.
They usually turn into a different colour from the centre outwards. Fungi are mostly green colonies, a white
cloud or a ring of spores [16], [19], [20], [21]. Plates I-VI shows cultures of rain water samples collected from
four different stations the micrographs show colonies of different organisms which grew during the culture
and incubation period of 18 hrs at 20oC for the total coliform count test.
Plate VII is the SEM micrograph of the dark black deposit on the rooftops. The dark black deposit was removed
and analysed using ED-XRF and the result is shown in Table 6. Comparing Tables 1-4 with Table 6 we can
see that the elements and some of the compounds in Tables 1-4 actually reported in the composition of the
dark black deposit on the rooftops confirming that rain is one of the sources of the dark black deposit on
rooftops. The composition of the rain water also show that it flushes microbial and chemical contaminants
from the rooftops. Several authors have agreed with the above discussions [2], [6], [7], [8], [9], [19]. Nwokocha
[1] worked on the effect of gas flaring on buildings rooftops in oil producing rural communities of River state
Nigeria and other authors have worked on the effect of vehicular emissions, generating set emissions, and
burning of fossil fuels. And all the authors have agreed that these sources release particulates, soot, and gases
of various chemical composition into the air which are washed-down to the rooftops the rain gets polluted even
before getting to the rooftops, the situation is only worsen by leaching of the roofing material by acidic rain
[2], [3], [4], [5], [12], [13], [14], [15], [16]. The rain also contributes in the dark black deposit on the rooftop
in addition to what has been deposited by both dry and wet air. The quantity of atmospheric deposition depends
on the amount and types of air pollutants emitted in the vicinity and upwind of the site [13].
Summary. The study titled Dark-black Stains on Rooftops: Implications on the quality of Water Harvested
from Rooftops in Uyo Metropolis-Nigeria was painstakingly investigated. The quality of rain water harvested

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from rooftops of dark-black stain coated roofs in different parts of Uyo metropolis was considered during the
research and the following conclusions were drawn
I. The study revealed that the water harvested from dark-black stained rooftops in Uyo metropolis is polluted.
It is worrisome the levels of metals, acidity and coliforms measured in the water.
II. Lead values of 0.75 mg/l and 0.22 mg/l in stations 2 and 3 respectively exceeded WHO standard
specification of 0.01mg/l for drinking water.
III. The iron content in the water from stations 2, 3, and 4 all exceeded WHO standard specification for
drinking water of 0.30mg/l
IV. All the four stations had cadmium content in the rain water which was more than WHO specification for
drinking water of 0.003mg/l
V. All the four stations had pH that did not meet WHO standard specification for drinking water. The water
will affect the mucous membrane and increase the leaching of the roofing material if in direct contact.
VI. The study has shown that the water has contributed to the dark-black deposit of the rooftops of buildings
in Uyo metropolis. The total organic carbon must have been responsible for the dark-black colour and its
source is from the soot of fossil fuels combustion from gas flaring, vehicular emissions, and generating sets
used everywhere in the metropolis.
VII. The result of this work calls for serious action from government to further investigate the health
implications of this findings on the masses.
Acknowledgements. The authors of this work wish to acknowledge the contributions of Engr. Nicholas Agbo
of the Defence Industries Corporation of Nigeria, Kaduna and Mr Musa Chaga of the National Metallurgical
Development Center Jos which led to the successful completion of this work. The authors equally extend their
unfathomable thanks to Mr. Monday Inyang of the state Ministry of Science and Technology Uyo, Akwa Ibom
State for his contribution in sampling and analyzing the test specimens.
Sponsorship. This research work is sponsored by TETFUND under the Institutional Based Research Grant
for University of Uyo-Nigeria.
References
[1] Nwokocha, C.O. (2010) Environmental Impacts of Oil and Gas Production in Nigeria, Journal of Energy
and Power Engineering 6, 70-75
[2] Dara, S.S. (2007) A Textbook of Environmental Chemistry and Pollution Control, New Delhi: S. Chand
and Company Ltd pp1-70
[3] Wark, K., Warner, C.F. and Davies, W.T. (1998) Air Pollution: its Origin and Control Boston, USA:
Addison Wesley Publishers
[4] Ryemshak, .S.A., Ihom, A.P. (2015) The Effects of Flue-Gas Emission and Carbon-Soot from Combustion
of Fossil Fuel Leading to the Phase-out Campaign of Coal- A Review, International Journal of Modern Trends
in Engineering and Research, 149-161
[5] Ihom, A.P., Agwu, O.E., John, A.J. (2016) The Impact of Vehicular Emissions on Air Quality in Uyo,
Nigeria, MMSE Journal, DOI 10.13140/RG.2.1813.7845,
[6] Chang, M. and Crowley, C.M.(1993) Preliminary Observations on water quality of storm runoff from four
selected residential roofs Water Resources Bulletin. 29:pp777-783
[7] Ayenimo, J.G., Adekunle, A.S., Makinde, W.O. and Ogunlusi, G.O.(2006) Heavy Metal Fractionation in
Roof runoff in ile-Ife,Nigeria, International Journal of Environmental Science and Technology 3(3): pp221-
227
[8] Bielmyer, G.W., Arnold, W.R., Tomasso, J.R. Isely, J.J. and Klaine, S.J.(2011) Effects of Roof and Rain
Water Characteristics on Copper Concentrations in Roof runoff. Environmental Monitoring and Assessment,
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[9] Brandenbanger, C.P. Julius, M. and Remteke, S.G. (2011). Chemical and Biometric Analysis of Puget
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[10] Udom, G.E. (2016) Address of the Governor of Akwa Ibom State-Nigeria at conference on climate
change, held at Le Meridien hotel and Golf Resort Uyo.
[11] Olajire, A.A., Ayodele, E.T., Onyedirdan, G.O., Olugbemi, E.A. (2003) Levels and Specification of
Heavy Metals in Soils of Industrial Southern Nigeria Environmental Monitoring Assessment, 82(2): 135-155,
DOI 10.1023/A:1023613418727
[12] Thomas, S.K., Greene, M.T. (1993) Effect of Seasonality on rainwater quality in California, Journal of
Applied Biotech, 1(2): pp18-23
[13] Foster, J. (1996) Patterns of Roof runoff contamination and their Potential Implications on Practice and
Regulation of Treatment and local infiltration, Water Science and Technology. 33 (6):pp39-48
[14] Mendez, C.B., Afshar, B.R., Kinney, K., Barret, M.E. and Kirisits, M.J. (2000). Effect Roof Materials on
water quality for Rain Water Harvesting System. Teas Water Development Board, Austin, TX
[15] Premlata, V. (2009) Multi-variant Analysis of Drinking Water Quality Parameters of Lake Pichkola in
Udaipur, India, International Journal of Environmental Science 1(2):97-102
[16] Okon, V.E.(2016) Investigation of Factors Responsible for Dark Stains on Emulsion Paint Finished
Buildings in Uyo, M.Eng Dissertation in the Department of Mechanical Engineering University of Uyo-
Nigeria.
[17] Samuel, E. (2012) Health Security, Safety and Environment (HSSE) A training Manual of the Millenium
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[18] Alsup, S.E., Ebbs, S.D., Battagalia, L.L. and Ratzlaff, W.A. (2011) Heavy Metals in Leachate from
simulated Green Roof Systems Ecological Engineering, p37:1707-1717
[19] Asanusung, K.E. (2014) Investigation of the possible causes of Aluminium Roofing Sheet Discoloration
and its Remedy: A case study of the University of Uyo Male Hostel Roof, Permanent site. PGD Project in the
Department of Mechanical Engineering, University of Uyo-Nigeria.
[20] Hoek, V. Mann, D.G., and Jahn, H.M. (1995) Algae: An Introduction to Psychology, Cambridge,
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Study of the Efficiency of Dust Filters in Terms of Coal Mines28

S.. Cheberiachko1, a, Yu.. Cheberiachko 1, b, .A. Yavorska1, c, D.. Radchuk1,d

1 State Higher Educational Institution National Mining University, Dnipro, Ukraine


a sihc@yandex.ru
b cheberiachkoyi@ukr.net
c lenayavorskay@mail.ru
d ruis@i.ua

DOI 10.2412/mmse.81.48.85 provided by Seo4U.link

Keywords: Dust respirator, pressure drop, breathing resistance, dust content, particle size distribution.

ABSTRACT. The objective of the research is to determine protective properties of the filters of dust respirators being
used in coal mines; the properties to be studied are obtained under laboratory conditions. It has been determined that
penetration coefficient of dust-loaded filters gets worse along with the moisture increase in terms of volume filtration
phase; however, the coefficient gets better in terms of the phase of surface accumulation of dust deposit at the expense of
filter surface porosity reduction. It has been proved that the increase of dust concentration in the air of a working zone in
terms of air moisture and high filtration rate within the initial phase helps improve protective properties; the effect is
stipulated by the nonavailability of volume filtration phase. It is shown that a prefilter (made of special-purpose
hydrophilic material with low fabric weight) being placed on a filter box prolongs the life of a main filter at the expense
of the reduction of surface potential flowing off and as well as decrease in dust load.

Introduction. Working conditions in terms of coal enterprises are determined mostly by dust factor,
i.e. they depend upon dust content in the air of a working zone, its generation type, and dust deposition
near dust sources. In this context dust properties stipulates selection of the corresponding measures
to deal with this problem.
Current regulatory documents on labor safety based on sanitary-hygienic standards or levels of
permissible dust loads if the standards are impossible to meet. Moreover, miners are provided with
respiratory protective devices. Their selection is regulated by several standards [1, 2]. It is considered
that if filtering respirator is selected correctly, it can protect a worker against pneumoconiosis and
dust bronchitis. Despite the fact that the use of respiratory protective devices is obligatory, the number
of people with dust etiology diseases increases year by year. Thus, study of the efficiency of dust
filtering respirators use under production conditions is of high importance and topicality.
Outlining of the unsolved problem. Polypropylene materials have become very popular to make
filtering respiratory protective devices as the materials are characterized by slight initial breathing
resistance, ease in their manufacturing and use, and high mechanical hardness. However, their
protective properties depend greatly upon the available electrostatic charge. The research shows that
in terms of linear filtration rates up to 0.006 m/s the efficiency of electrostatic mechanisms of aerosol
particle catching reaches 80% of total action of all the mechanisms [3]. However, it is unstable and
its behaviour can be unpredictable especially under the effect of high temperature and air moisture
[4, 5]. Taking into account the fact that mine workings of coal mines are characterized by unfavorable
climatic conditions, especially by high air moisture, there is the topical problem to research its effect

2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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upon protective efficiency of filters made of polypropylene materials to determine its respiratory-
protection period.
Analysis of studies and publications. Publications concerning the estimation of the influence of air
moisture upon the efficiency of aerosol catching by means of electret filters differ considerably. Some
papers study deterioration of protective properties connected with the decrease of value of particle
charges and fibers entering such conditions [4]. On the contrary, other papers do not admit such
conclusion. For example, some authors [5] note that air moister has almost no effect on the penetration
coefficient of aerosol particle being up to 100 nm in diameter. Experiments were carried out in terms
of relative humidity from 40 % up to 90 %. However, there are studies demonstrating that catching
of large particles improves if humidity increases; this effect is explained by the increase of capillary
forces which increase their sticking to the material fibers [6]. There is a conclusion that the filters
with the brought charge within the field of corona charge demonstrate worse protective features as in
this case electrons on the fiber surface can be easily removed by means of water molecules. Electret
filters are another case as they are obtained by means of electrospinning (when special-purpose more
water-resistant coating is generated) [7]. Authors of the papers [8, 9] tried to find solution of the
problem of electret life extending at the expense of introducing various composite additives into the
structure of a filter. However, the studies have no clear answer concerning the ability of electrets
filters to offer enough protection during one working shift under conditions of high humidity.
Formulation of the research objective. Study of the interrelation between penetration coefficient of
polypropylene material filters and value of electrostatic charge on their fibers under conditions of
high air humidity to determine the period of respiratory protection life.
Materials and research methods. The research involved three different types of filters for
nondisposable respirators complying with the second class of protection according to DSTU EN
143:2002 (confirmed by quality certificates). They were made of polypropylene filtering material
with 2.5 micron mean fiber diameter, 4 mm filtering layer thickness and following fabric weight: first
filter 55 g/m2 (type ); second filter 45 g/m2 (type B); third filter 40 g/m2 (type C).To reduce
testing error of respirator protective efficiency and filters air flow resistance was determined first to
select the ones with similar parameters to use during experiments.
Following parameters were determined under laboratory conditions:
- penetration coefficient of filters that is the ratio of test aerosol concentration before and after
respirator during clogging using the formula [4]

1
K 100 , % (1)
2

where 1 and 2 are aerosol concentration within undermask area of respirator and in a test chamber,
mg/m3, respectively; value of surface charge on filter surface using the formula [10]

= 2V/S, Kl/m2 (2)

where is dielectric air penetration,


2 is dielectric penetration of electret material;
V is potential of electret surface, V;
S is the area of measuring electrode, m2; pressure drop on filters in terms of 30 dm3/min air
flow using the formula [10]
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R (ni n0 ) K1 , (3)

where ni is indication of filters resistance using micromanometer, Pa;


n0 is the initial resistance of the measuring system, Pa;
K1 is the adjustment coefficient for temperature and atmospheric pressure.
Tests were carried out to determine the effect of relative humidity and dustiness of the air on the
penetration coefficient and pressure drop of filters in terms of laboratory conditions. Levels of relative
humidity were from 60% to 80% and dust concentration in the chamber was 250 300 mg/m3. Each
test was being carried out until pressure drop on a filter was 100 Pa. While dusting coefficient of
penetration in terms of sodium chloride test-aerosol (with size-consist being from 0.2 micron up to 2
micron) was being determined at regular intervals. Paper [10] described in detail its method of
determination. Filter was weighed before and after the tests to determine total weight of water and
amount of dust on it. When the tests were completed the filter was left to dry at room temperature
within 24 hours. After drying it was weighed again to obtain the mass of the deposited dust.
Special-purpose stand was used for dusting (Fig. 1) that allowed simulating real working process with
the dust available in the air of a working zone. Dusty air was blown through the filter with 30 dm3/min
air flow.

Fig. 1. General view of a testing stand: 1, 9 compressed air supply; 2 prefilter to purify
compressed air; 3 ejector; 4 diffuser; 5 cyclonic collector; 6 flowrate meter; 7 exhauster
fan; 8 outlet fitting; 10 dust generator; 11 dust distributor; 12 damping plate; 13 testing
chamber.

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The stand operates as follows. Ejector is used to deliver dust into a testing chamber from a generator.
Diffuser available in the structure of a testing chamber allows equal dust and airflow distribution
within a chamber providing its laminarity.
Filter is mounted on a proper adaptor in a testing chamber. Dust concentration is measured using
sampling instrument with AFA filter being placed near test specimen. Dust concentration is
determined according to the formula:

2 1
= ,

where m1 is the mass of AFA filter, mg;


m2 is the mass of AFA filter with dust after sample collection, mg;
Q is the air flow, dm3/min.;
t is the time of air sample collection, min.
Potential on filter surfaces were determined experimentally to calculate the value of electrostatic
charge. The plant consists of two blocks (measuring and indicating) (Fig.2). It allows measuring
effective voltage on electret surface up to 1000 V. Principle of its operation is based on the use of as
electron-beam wobbulator as a null-indicating instrument with the displaying of compensation
voltage on a digital voltmeter. Before the test started, the filter was unfolded; then a measuring
electrode was placed on its internal surface. For the purpose of experiment repeatability areas of
electrode placing were marked (Fig. 3). Further, filter was folded with the help of matrix (Fig. 4) and
after the dusting it was unfolded again to determine surface potential within the same areas.

Fig. 2. Scheme of the stand to measure electrostatic potential on the surface of filtering material.

Production research of the filters was carried out in terms of Western Donbas mines. Miners of the
following professions participated in the experiment: machine operator, assistant of machine
operator, and mineworker. They were given respirators of RPA type with filters tested previously
under laboratory conditions. It should be noted that half masks were selected according to facial
parameters. There were no additional trainings for workers participating in the research concerning
the proper use of respiratory protective equipment except for the ones envisaged by the initial-training
program. Experiments lasted for 4 hours. While measuring, air humidity and temperature within each
working place were controlled by means of -4 aspirator; dust concentration was also determined
by means of IZSA dust counter. After the experiment, filters were placed into individual packets for

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the following measuring of their dust-loaded weight and determining surface electrostatic charge and
penetration coefficient under laboratory conditions.

Fig. 3. Points of electrode placing to Fig. 4. Matrices to form pleated filters of cone-
measure electrostatic charge on the surface like blank part for a respirator.
of filtering material.

The results. Table 1 demonstrates results of penetration coefficient, surface potential, mass and
pressure drop of filters measuring before the tests as for their dustiness in terms of their compliance
with DSTU EN 143 requirements.

Table 1. Average values of penetration coefficient of filters under laboratory conditions.


Filter Mark Filter weight, g Breathing Value of the Coefficient of
resistance, Pa in surface potential, penetration in
terms of 30 V terms of sodium
dm3/min air flow chloride, %
Type 6.45 27 455 0.226
Type B 6.25 23 415 0.511
Type C 6.55 17 376 0.806

Tables 2 and 3 show the results of experimental research to study the dependence of pressure drop
and penetration coefficient of the filters carried out in the laboratory under various testing conditions
simulating mine working air (marked 1 to 5 on Fig. 5a).
The analysis of the obtained data has shown that under certain conditions high air humidity along
with coal dust can deteriorate considerably the quality of the filters. We can see that just in 30 min
their operational properties weaken significantly. Similar results have been obtained in the research.
However, it cannot be said definitely that the tested filters will protect the workers properly under
production conditions. More research is required; first of all it is necessary to explain why air
humidity along with dust effect filtering properties.

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Table 2. Average values of penetration coefficient and pressure drop of filters in terms of various
testing conditions in 30 min.
Filter mark Testing conditions characterized by the temperature in a testing chamber, t, 0C,
humidity, %, available dustiness, 2, mg/m3
23 0, 60 % 23 0, 60 %, 28 0, 95 % 28 0, 95 % 37 0, 95 %
200 mg/m3 200 mg/m3 200 mg/m3
Type 0.25/27 1.2/55 4.3/29 6.2/55 8.6/61
Type B 0.5/23 3.8/45 5.5/25 9.1/46 13.2/52
Type C 0.8/17 5.2/37 7.1/22 12.3/39 15.3/44
Note: numerator indicates coefficient of penetration, denominator indicates pressure drop

If the obtained results are studied thoroughly, it will be clear that if there are changes only in climatic
conditions then breathing resistance shows almost no growth (testing conditions 1 and 3); in this
context coefficient of penetration has grown almost tenfold. Such deterioration of filtering properties
at constant filtration rate and similar particle size distribution can be explained by the weakening of
the action of electrostatic mechanism of particle catching due to charge flowing-off. Fig.6 shows the
dependence of penetration coefficient of filters upon the value of electrostatic charge. It is seen that
the filters with charge being less than 2.5 nC /cm2 will not correspond to DSTU EN 143:2002
requirements. Increase in air temperature and humidity as well as deposition of charged dust particles
are also the factors deteriorating coefficient of penetration. The research shows that filtering
polypropylene material with fabric weight not less than 45 g/m2 at the available charging system is
not efficient in filter production so only filters of A type are used in the further research.
The results of experimental research to determine the effect of air humidity upon the value of electric
potential of filters confirm the aforementioned statement. On average, process of flowing-off may
last from several days up to several months. The research shows that under standard conditions charge
decrease on filters made of polypropylene material takes one-two months; after that it stays the same
for a considerable period of time. At the same time if air humidity increases up to 95%, then the
process of charge flowing-off is accelerated (Fig.7). It is considered that when water molecules fill in
certain part of electret surface, electroconductive channel evolves which reduces sharply the value of
surface potential.

Fig. 6. Curves of the dependence of penetration coefficient of polypropylene filters with various
fabric weight of fibers upon the value of surface electrostatic charge.

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Fig. 7. Curves of electrostatic charge flowing-off at 95 % air humidity and 26 0 temperature (1)
and 60 % and 23 0 respectively (2) on polypropylene filters.

Fig. 8. Curves characterizing change of filters coefficient penetration in terms of sodium chloride
test aerosol within certain period of time.

However, due to different reasons the process can take too much time; thus, within the certain
intervals of filter operation it is possible to have stable result in terms of high air humidity as well
(Fig. 8). In particular, in terms of low filtration rates the initial stage shows improvement of protective
properties owing to the precipitation of aerosol water particles on fibers and porosity reduction.
Accumulation of coal dust on fibers will result almost in the same effect. It is confirmed by the change
of the penetration coefficient of filter in terms of its dusting (Fig. 9). It should be also noted that in
time protective efficiency of filters will improve. Accumulation of aerosol and moisture which reduce
porosity of filtering material also helps improve the protective properties.

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Fig. 9. Curves characterizing change of filters coefficient penetration in terms of sodium chloride
test aerosol within certain period of time.

Fig. 10. Dependence of changes in filters coefficient penetration in terms of sodium chloride test
aerosol upon dust content.

If we compare dependence of filters coefficient penetration in terms of sodium chloride test aerosol
upon the amount of the accumulated dust with the curves of changes in pressure drop in term of dust
deposition, then we can say that the improvement of protective properties will be possible only when
the volume phase of dust deposition is over (Fig. 10, 11). It is characterized by nonlinearity explained
by the deposition of dust particles within a filtering layer. In this context increase in air humidity
reduces the duration of this phase (Fig. 11).
Value of respirators coefficient penetration within the initial operation phase can be decreased at the
expense of placing prefilter made of special-purpose hydrophilic material with low fabric weight, e.g.
SMMS, in front of a filter box (Fig. 12). Tests have shown that most moisture amount and coarse
fraction of dust deposit right on it; it is confirmed by sharp growth of its mass relative to main filter
(Table 4). It allows not only making respirator service life longer but reducing flowing-off of
electrostatic charge on filters to improve protective properties of half masks in general (Fig.13). It
means that the use of such additional prefilters will make it possible to prolong service life of
respirators.

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Fig.11. Curves of dependence of pressure drop upon dust content in terms of different air humidity
obtained at 30 dm3/min filtering rate.

Fig. 12. Prefilter being mounted on a respirator filter box.

Table 4. Average values of filter coefficient of penetration with the mounted prefilter.
Parameters Test conditions characterized by the temperature in a testing
chamber, t, 0C, humidity, %, and available dustiness, 2,
g/m3
23 0, 60 %, 200 28 0, 95 %, 200 37 0, 95 %, 200
mg/m3 mg/m3 mg/m3
Initial mass of a main filter, g 6.33 6.27 6.24
Initial mass of a prefilter, g 1.51 1.43 1.62
General coefficient of 0.35 1.12 3.63
penetration, %
Mass of a main filter with 6.58 6.48 6.49
dust and moisture, g
Mass of a prefilter with dust 1.86 2.01 2.04
and moisture, g

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Fig. 13. Curves characterizing change in filters coefficient penetration in terms of sodium chloride
test aerosol within a certain period of clogging time.

Tests of filters under production conditions within one shift have shown that it is the increase of dust
concentration in the air of a working zone in combination with high humidity and pressure drop that
results in the increase of protective properties of a filter (Table 1).
The analysis of the obtained data has demonstrated that the increase of filters test aerosol penetration
coefficient is not crucial. Even in the worst case they will provide sufficient protective level.
Summary. Because of the research the following facts have been determined. Respirators with
polypropylene filters give sufficient protection for the workers operating during a shift (with not more
than 6.0% coefficient of penetration and up to 70 Pa pressure difference). However, protective
properties of polypropylene filters are not constant value as they depend on the operating conditions;
thus under conditions of high humidity and temperature their parameters worsened in time at the
expense of decrease of the value of surface electrostatic charge.

Table 5. Values of filters parameters after their testing under production conditions.
Parameters of Dust Mass of the dust Pressure drop, Coefficient of
filter groups concentration, deposited on a after clogging, penetration, ,
worn by the mg/m3 filter, g Pa %
miners
Cutter-loader 3206.4 0.920.24 651.6 0.780.05
operator
Assistant 175 5.1 0.520.31 521.3 3.85 0.11
operator
Mineworker 53 3.4 0.090.16 451.4 5.70.31

It has been determined that penetration coefficient of dusty filters deteriorates along with the increase
of humidity within the phase of volume filtration while when there is the phase of surface
accumulation of dust deposit this coefficient improves at the expense of reduction of filter surface
porosity. It has been proved that on the contrary the increase of dust concentration in the air of a
working zone in terms of the available air humidity and high filtration rate at the initial phase favours
the improvement of protective parameters; such effect is stipulated by the nonavailability of the phase
of volume filtration. It has been shown that the prefilter (made of special-purpose hydrophilic material

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with low fabric weight) being placed on a filter box increases the working life of a main filter at the
expense of the decrease of surface potential flowing-off and dust load.
The research being carried out requires further specification of the dependence of penetration
coefficient upon surface electrostatic charge.
References
[1] SRARP 0.00-1.04-07 Rues to select and use respiratory protective devices issued by State
Committee of Ukraine on Industrial Safety, Labour Protection and Mines Inspectorate under order
No. 331 of 28.12.2007.
[2] DSTU EN 529:2006 Respiratory protective devices. Recommendations on the selection, use, and
maintenance. Instruction (EN 529:2005, IDT).
[3] P.I. Basmanov, S.L. Kaminskiy, .V. Korobeinikov, .Ye. Trubitsyna, Respiratory protective
devices: Instruction manual, S.Pb.: GIPP Isskusstvo Rossiyi, 2002.
[4] J Kuzmin, Yu.I., Pshchelko, N.S., Sokolova, I.M., Zakrzhevskiy, V.I. The percolation behaviour
of electret at presence of water condensation. In: Proc. of the 8th Int. Symp. on Electrets, Ed. by J.
Lewiner, D. Morisseau, C. Alquie, ESPCI, IEEE. 1994, Paris, France. P. 124-129.
[5] Romay, F.J. Experimental study of electrostatic capture mechanisms in commercial electret filters,
Aerosol Science and Technology, Vol. 28 (1998) Nr 3, pp. 224-234. DOI
10.1080/02786829808965523
[6] Ackley, M.W., Degradation of electrostatic filters at elevated temperature and humidity, Filtration
and Separation, Vol. 22 (1992) Nr 4, pp. 239-242.
[7] Moyer, E. S. & Stevens, G. A., Worst Case aerosol testing parameters: II. Efficiency dependence
of commercial respirator filters on humidity pretreatment. American Industrial Hygiene Association
Journal, Vol. 50 (1989), pp. 265-270.
[8] Chen C.C., M. Lehtimaki and K. Willeke: Aerosol penetration through filtering facepieces and
cartridges. Am. Ind. Hyg. Assoc. J. 53: 566574 (1992). DOI 10.1080/15298669291360166
[9] Schmidt, F.; Breidenbach, A.; Duber, E.; Ergebnisse der RLT-Filterprfung nach EN 779 im
Vergleich zu Messungen an Filtern aus dem Betrieb; Chem. Ing. Techn.; 84, No. 6, 808-812 (2012).
[10] V.I. Golinko, S.I. Cheberiachko, V.Ye. Kolesnik, .S. Ishchenko (2004), Analysis and
estimation of the protective efficiency of filtering respirators, Scientific Herald of Naional mining
University, No. 12., pp. 33 36.
[11] S.I. Cheberyachko, D.I. Radchuk, Y.I. Cheberyachko, M.O. Ziborova (2016). On Development
of a New Filtering Half-Mask. Mechanics, Materials Science & Engineering, Vol 4. doi:
10.13140/RG.2.1.3389.4802

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IX. Philosophy of Research and Education


M M S E J o u r n a l V o l . 1 0

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Model of Professionally Important Qualities of Bachelor Degree Students of


Higher Technical Educational Institution for the Admission to Masters Course29

O. Artemenko1, a, D. Artemenko2, N. Cherednychenko1

1 Flight Academy National Aviation University, Kropivnitskiy, Ukraine


2 Central Ukrainian National Technical University, Kropivnitskiy, Ukraine
a o_artemenko@list.ru

DOI 10.2412/mmse.40.52.685 provided by Seo4U.link

Keywords: automatic admission, a graphical model of professionally important qualities, the chart in the polar coordinate
system.

ABSTRACT. The analysis of professional training activity of Bachelor degree student was performed and the main
factors affecting the PIQ of future magistracy graduates were defined. The minimum PIQ level of future masters was
experimentally investigated and substantiated. A graphic model of the PIQ in the polar coordinate system was offered to
assess the suitability of the Bachelor degree student for the admission to the magistracy.

Introduction. The modern system of higher technical education in higher education institutions
(HEIs) of Ukraine is aimed at creating appropriate conditions for training of competent professionals
focused on continuous professional development, self-improvement, which will provide further high
level of competitiveness, professional mobility, performance of professional activities and as a result,
career growth and self-realization [1]. In addition to successful mastering the necessary knowledge
base and skills, according to the specifics of the chosen specialty (Bachelor degree), is also important
to possess professionally required qualities and skills that are a prerequisite for the effective exercise
of professional functions at any stage of professional development of the individual [2].
Formulation of the problem. In this regard, there is an urgent need for expanding the systematic
study of the integrity of the future expert at maturity (Bachelor student) while his individual, personal
and subjective and active properties are considered in the unity of all relationships. The
abovementioned qualities of future specialist in a technical college are formed while getting the
master's degree in the fields of the chosen specialization. Therefore, the selection of students
according to their bachelor professionally important qualities (PIQ) when entering the magistracy is
important and timely.
In addition, nowadays the automation of knowledge control is a global trend. Computer support for
learning and knowledge control has more than 30-year history. Today there is a large number of
knowledge control systems developed as separate software, and embedded in the educational system.
Therefore, design model of PIQ master in the future will automate the process of selection of Bachelor
students.
Analysis of recent research. Professional activities, their structure and selection of professionally
important qualities for future technicians in various fields of training were discussed in theoretical
and practical pedagogies.
Works of V.F Bessarab [3], E.F Zeyer [4], V.G Kuntysh [5] and others are devoted to issues of
development of professional skills of future engineers-teachers.

2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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V.A Yadov devoted his research to creation of social and psychological portrait of future design
engineer [6].
Determination of the features in formation of professionally significant qualities of future engineers-
navigators are the main area of studies of A.F Shiyan [7], V.O. Yakunin [8] and others.
The development and construction of model of professionally important qualities of future graduates
of Magistracy as professionals towards technical training in universities are neglected.
The latest research on the necessary qualities of Bachelor and Master degree students are presented
in papers [19, 20].
The purpose of the work: the development and justification of professionally important qualities of
a Bachelor degree student at a technical college for the selection to the Magistracy.
To achieve the goal, we solved the following problems:
1. To analyze the professional activity and training of Bachelor degree student at a technical college,
literature, regulations and to formulate PIQ required for admission to the Magistracy.
2. To analyze and select methods for determining the quality of each formation and expert PIQ
complex.
3. To evaluate Bachelor degree students suitability using PIQ model to enter the magistracy.
Presentation of basic material. Each kind of professional activity sets its demands to the prospective
specialist. Any Bachelor student of technical college should: know the status and prospects of
engineering and technology in the industry and in the related industries; master modern methods of
job evaluation, modern design; have a clear idea of the subject of scientific methodology, the problem
of the industry, forecasting methods and development of technology; be familiar with the basics of
production, labor and management, with the economy sector; be able to understand the issues of
health and safety, proved control of measuring and office equipment [9].
According to Professor S.E. Yachyn, the mainstream of technical education in the XXI century is not
typical of natural scientific laws, but to economic, environmental, cultural and political realities. [10].
Nowadays, the operation of technical devices and human operations with them are considered in
interrelationship, which caused to be formed the concept of "human - machine" cooperation (HMC)
[11, 12].
Based on system approach, V.D Shadrykov [13] clarifies that system is a structure which is
considered in its relation to certain functions and that specialists professional activities should be
performed in unity of its three aspects: subject-effective, physiological and psychological. He
considers "human - machine" to be a system where the operation of machines and human activity are
related to a single loop control. However, the main attention should be paid to the specifics of the
mechanisms of human reflection of reality and the regulation of its activities.
As for Bachelor students PIQ, they are formed during the training and educational process by
external conditions that can speed up this process and make it more successful. Regardless of
specialization and the nature of future professional activity, any junior specialist should have a
fundamental knowledge and professional skills. The creative experience and research will allow the
future Masters determine his position on a particular issue or problem professionally.
Based on expert survey (questionnaire survey of experts in the field of technical education and
employers in technical field) and processing of regulatory documents [2], we have marked the most
significant PIQ for the Bachelor student of a university, as a future professional (Figure 1).
Analyzing the results and conducting their ranking, we have found that Bachelor student who wants
to get the Masters degree should have the following professionally important qualities (according to
experts in %): mathematical ability - 95%; good spatial imagination - 91%; creativity - 84%; creative
approach to solving technical problems - 79%; dedication - 73%; desire for constant new knowledge
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- 68%; responsibility for the results of work - 65%; organizational skills, required for management of
staff - 60%.

Fig. 1. Diagram of the most significant PIQ of Bachelor degree student.

As the model is a formal description of the real system, it can be set analytically, graphically (block
diagrams, graphs) and in charts. Having analyze their suitability and usability to display Bachelor
students PIQ for enrollment to Magistracy graphic representation was elected, namely a graphical
diagram system of polar coordinates as a visual way of representing objects and processes in the form
of graphics [14, 15]. It represents the value of each category along a separate axis that starts in the
center of the diagram and ends on the outer ring. Each category of charts in polar coordinates system
has its own axis of coordinates and a description. The order of the values can not be changed on this
bar chart.
Thus, the diagram in polar coordinates system acts in this case as visualization of the results of expert
survey (reflects the basic level of PIQ) the results of testing bachelor student at Technical Universities
(reflecting the level of students PIQ).
Polar coordinates system chart enables us:
- to show clearly and comprehensively the basic (the minimum required) level of students PIQ
development degree and level of PIQ required for admission to the magistracy;
- to compare visually and identify the Bachelor students PIQ that are poorly developed;
- according to the basic results, make adjustments to vocational training of students in undergraduate
Bachelor;
- provide individual approach to the educational process.
In order to develop the basic model of Bachelor students PIQ of a technical college for enrollment
to the Magistracy we have conducted experimental research that made it possible to clarify and
determine the importance of each quality for future expert.
During the research, we have conducted two expert surveys:
- survey on the V.N. Mashkovs methodology aimed to identify expert opinion regarding the
definition of the qualities that should be included in a set of future Masters PIQ [16];
- the method of expert assessments to determine basic level (the minimum required level) of each
PIQ.
Teachers of technical departments who have over 10-year-teaching experience (including experience
of preparing Masters) took part in the survey.

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When asked whether they had the Masters who had low level PIQ, 100% of respondents answered
positively. For example, undergraduates are not often responsible (are late for consultations, do not
always perform tasks in time, etc.), not all of them are ingenious and organized.
It is hard for the head to work with these postgraduates and the results of their work do not always
meet expectations.
In order to conduct a survey all PIQ were systematized and described:
1. Mathematical ability - is the human ability to capture the order of items required for mathematical
proof. The presence of this kind of intuition is the main element of mathematical creativity, and it
relies not only on knowledge and experience, but spatial imagination as the main condition for
mathematical thinking is of paramount importance for the future scientist. Model of Masters
mathematical skills is defined as a system of thinking qualities that shows progress in the development
of higher mathematics necessary for future research activities
2. Spatial imagination - is the ability of person to create mental images of objects in his mind based
on their drawings or descriptions. It is essential for the future Master to be able to create and read
drownings and schematic symbols.
3. Resourcefulness is a human property to find a way out in difficult situations. As for Master, it is
the ability to respond to questions quickly, find the correct answers and use this knowledge in practice.
4. A creative approach to problem solving (creativity). The creativity of an individual is a synthesis
of features and traits that characterize the degree of compliance with certain type of educational and
creative activities that define to the level of effectiveness of this activity. Future scientists need to be
inclined to organizational creativity in order to organize successful research in their field. Human is
able to create peculiar and independent theory.
5. Commitment is a person's ability to subordinate their actions to the objectives to be achieved, a
mobilization of forces to identify correctly the ways, methods and techniques of its activities is the
aim of the decisions and their implementation, persistence in achieving the desired result.
6. The pursuit of new knowledge is a quality which can lead to the best results, the desire to get new
information will broaden students' outlook and make him a more valuable employee in the future.
7. Responsibility is a person's ability to anticipate events or actions when they are committed or when
they are implemented. It is also the ability to respond not only for themselves but also for other people,
by nature of their relationship with them. Future Masters should have such traits as diligence,
perseverance and persistence.
8. Organizational skills is the ability to organize their own activities and the activities of subordinates,
create a team as a collective tool for solving current problems and personal development, the future
Masters ability to manage a team.
In order to organize expert survey, the questionnaires were worked out by means of which necessary
information was collected. A clear and meaningful question wording and description of PIQ were
especially important. The questionnaire also used the open-ended questions where the expert
expressed his opinion on any of them.
The reliability of examination also depends on the number of experts in the group and their individual
competence. The number of experts in the expert group depends on many factors and conditions. As
a result, the expert group included 10 people, according to the regulation that the defining number of
experts should be not less than the number of objects ranging (in this case we have 8 PIQ).
The list of PIQ and their description were offered to experts according V.N. Mashkovs expert survey
methodology and each expert had to put a number 2 - if this PIQ is necessary for the future Master;
1 - if it is desired; 0 - if it does not matter.

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Processing of the results is based on a calculating points that are put for each criterion, i.e. the idea
of the expert group is expressed as an arithmetic mean. The calculation is as follows:

AN 0 BN 1 CN 2
Z, (1)
K

where A, B, C the point appropriate to each response options (0; 1; 2);


N 0 , N1 , N 2 the number of experts who chose this answer;
K the total number of respondents who answered the questionnaire, and answered the
questions (K=10).
This condition is verified:

1,6 Z 2 (2)

If the average expert assessments lie within these limits, then we can talk about the need for selected
professional important qualities.
The results of processing expert opinions are presented in Table 1.

Table 1. Experts on the Evaluation of selected PIQ


PIQ Number of respondents Grade
point
0 1 point 2 points
average
1. Mathematical ability - 1 9 1,9
2. Spatial imagination - 1 9 1,9
3. Resourcefulness - 3 7 1,7
4. A creative approach to problem solving - 4 6 1,6
(creativity)
5. Commitment - 2 8 1,8
6. The pursuit of new knowledge - 2 8 1,8
7. Responsibility - 1 9 1,9
8. Organizational skills - 3 7 1,7

Since the average expert assessments are provided within a given method, then we talk about PIQ
selected. Thus, after analyzing and processing the results of the expert survey, final set of PIQ future
Masters was approved.
The second survey (expert survey) was conducted to determine the basic level (the minimum
required) of PIQ, which a future Master should have. Experts had to assign the minimum required
score to each PIQ, which a future master should have on a scale of 1 to 5 (5-point scale chosen as the
most convenient and familiar, and it can be changed in the future).

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Based on the results of the expert survey matrix of experts group benefits was formed (Table 2).

Table 2. Matrix of experts group benefits.


PIQ Experts
e1 e2 e3 e4 e5 e6 e7 e8 e9 e10
1 4 4 3 4 4 4 3 4 4 5
2 4 3 3 4 4 3 4 4 4 4
3 3 4 3 3 2 3 3 3 2 3
4 4 5 5 4 4 4 4 4 4 4
5 4 4 5 5 4 4 3 4 4 4
6 4 4 5 4 4 3 5 4 4 4
7 5 5 5 4 5 5 5 5 4 5
8 4 4 4 4 5 4 4 5 4 4

A mathematical processing of the results have been performed, to determine the consistency of
experts opinions [17, 18]. First, the average of experts views Rav was calculated according to the
formula:

R 1
Rav i 1
(3)
m

For each value Rav is determined. The consistency of expert opinion is determined by the method of
expert evaluations. The variance for each PIQ is determined by the formula:

R av Ri 2
Di i 1
(4)
m 1

The standard deviation for each PIQ is determined by the formula:

i Di
(5)

Then determine the coefficient of variation for each PIQ by the formula:

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i
i 100% (6)
Ravi

All calculations were performed in the MS Excel application package.


Thus, mathematical processing of opinions was made, which allowed to judge the consistency of the
panel. Since the coefficient of variation is less than 33% of all PIQ, it means that the distribution
corresponds to a normal appropriate law, i.e. most thoughts are grouped around the avarage, and
polars constitute an absolute minority. All results of the expert survey processing are shown in Table
3.

Table 3. The results of mathematical processing of expert opinions


PIQ Rav Rgr Di vi,%
1 3,9 4 0,322222 0,567646 14,55503
2 3,7 4 0,233333 0,483046 13,05529
3 2,9 3 0,322222 0,567646 19,57401
4 4,2 4 0,177778 0,421637 10,03898
5 4,1 4 0,322222 0,567646 13,84503
6 4,1 4 0,322222 0,567646 13,84503
7 4,8 5 0,177778 0,421637 8,784105
8 4,2 4 0,177778 0,421637 10,03898

Based on these results, the basic (minimum required) PIQ level of a future Master has been identified.
PIQ reference model for candidates for Magistracy is shown in Figure 2-1.
Figure 2 is an example of a comparison reference model for PIQ student with options when: student
PIQ meet reference model (Figure 2-2); student PIQ does not meet the reference model (Figure 2-3).

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Fig. 2. PIQ reference model personality of the future Master. 1 PIQ reference model; 2 PIQ
student meet the reference model; 3 PIQ student does not meet the reference model.

Thus, the model can be further used as the basis for an automated system of selection of Bachelor
degree students to graduate Master that will make the process more transparent, effective and
objective.
Summary. Today the selection of bachelor students according to their professionally important
qualities (PIQ) at the stage of entry into the Magistracy is an important and urgent task.
1. Based on the analysis and synthesis of the literature, and the requirements for future masters PIQ
complex was formed which is necessary for the admission the Magistracy.
2. In order to display information in a system of polar coordinates, the convenient method was
proposed to build a model of future development of Masters PIQ.
3. PIQ Complex was reasonable and basic (minimum required) level of PIQ for future Masters was
defined. Based on expert survey, was reference PIQ model was constructed. It allowed:
- to consider all PIQ necessary for modern Master according to Ukrainian and world trends of higher
education;
- to increase the objectivity of the evaluation in the selection of students (excludes subjective factors);
- to provide a detailed picture of PIQ of the students entering the Magistracy (comparing the students
PIQ model and reference model).
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[3] Bessarab, V.F., Ushakova, V.V. 2003. Vocational Training Methodology: Lectures (in Russian).
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[4] Zeyer, E.F. 2006. Professional Development Psychology (in Russian). - Moscow: Academy, 240
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[16] Mashkov, V.N. 2003. "Expert technique to identify professionally important qualities".
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Mikhailov, V.A., 380 P.
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The Zenith Passage of the Sun and the Architectures of the Tropical Zone
30

Amelia Carolina Sparavigna1, a

1 Department of Applied Science and Technology, Politecnico di Torino, Torino, Italy


a amelia.sparavigna@polito.it

DOI 10.2412/mmse.20.89.933 provided by Seo4U.link

Keywords: architecture planning, history of architecture and engineering, satellite images, solar energy software.

ABSTRACT. In ancient cultures all over the world, summer and winter solstices and equinoxes had a great importance.
These astronomical events had been widely considered in the planning of monuments and other architectures. But in the
zone of the Earth delimited by the Tropics of Cancer and Capricorn, we can see another relevant event, the zenith passage
of the sun. In this paper we will show that several examples are existing too, of the role of this astronomic event in the
architectures of tropical zone. To evidence this role, we will use a software developed for the best solar energy
management, which is showing azimuth and altitude of the sun on satellite maps.

Introduction. Zenith is the point of the celestial sphere which is vertically above an observer. Only
in the area of the Earth, which is delimited by the Tropic of Cancer and the Tropic of Capricorn, we
can see the sun passing through the zenith. Anywhere outside the tropics, this is impossible.
Therefore, in the tropical zone the sun has, besides the astronomical events of solstices and equinoxes,
also two zenith passages. On the Tropical lines, only one passage is observed, coincident to one of
the solstices. On the Tropic of Cancer for instance, it happens on the summer solstice. At the equator,
the zenith passage is on the equinoxes.
The zenith passage of the sun, being the moment when it passes through the top point of the sky, is
easily observed using a gnomon, that is, by a straight vertical pole, because at that moment it casts no
shadow on the ground. Or, if we have a deep water well, we can see the sun reflected at noon by the
water at its bottom. Both these facts were well known to ancient people living in the tropical zone.
And in fact, Eratosthenes (c.276 BC c.195/194 BC) used them to calculate the circumference of the
Earth [1]. Eratosthenes knew that at local noon on the summer solstice in Syene (the modern Aswan),
the sun was reflected by the water of a deep well. By the shadow of a gnomon in Alexandria, he
measured the angle of sun elevation at the noon on the same day and found it being 1/50th of a circle.
Assuming that the Earth was a sphere and that Alexandria was due north of Syene, he concluded that
the meridian arc distance from Alexandria to Syene was 1/50th of the Earth's circumference. From
this distance, he evaluated the circumference of the Earth.
Peoples all over the world recognized in the past as very important astronomical events the summer
and winter solstices and the equinoxes and celebrated them consequently. It is not surprising then that
these astronomical events had been also considered in planning of monuments and other architectures,
which are consequently displaying alignments with the direction of sunrise or sunset on these days.
As evidenced by several examples [2-11], the planning of the architectonic structure becomes a
symbolic local horizon, a microcosm representing the apparent motion of the macrocosm that,
thorough the year, is revolving about its axis mundi, that is, the axis of the world.

2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

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In this paper we will discuss that several examples of the role of the zenith passage of the sun are also
existing, displayed by some architectures of the tropical zone. To evidence the role of the zenith
passage in the proposed examples, we will use a software developed for the best solar energy
management, which is showing azimuth and altitude of the sun on satellite maps.
The Zenithal Sun in America. As previously told, in the tropical zone, to solstices and equinoxes
we have also to add, as relevant astronomic events, the zenith passage of the sun. And in fact, we can
find that pillars and wells exist, used by people to observe what happens to light and shadows at the
zenith passage of the sun.
The people of pre-Columbian Mexico had a specific astronomical instrument" to observe this
passage: a vertical zenith sighting tube inserted in the vault of an underground structure. One of these
instruments is at the observatory of Xochicalco, in the Mexican state of Morelos. The image in the
Figure 1 (left) illustrates how it looks like the shaft of light passing through the ceiling of the artificial
cave of Xochicalco. A vertical opening produces in a dark chamber a perfectly perpendicular beam
of light, when the sun is passing through the local zenith. Besides the cave, at Xochicalco there is a
white stone pillar in the ceremonial area that could had been used to observe the shadow disappearing
when the sun reaches an altitude of 90 degrees (Figure 1, right).

Fig. 1. On the left: the image illustrates how it looks the shaft of light in a cave passing through a
tube in its ceiling, when the sun has its zenith passage in the sky. On the right: a pyramid and the
ceremonial pillar at Xochicalco, Mexico. Courtesy Maxtreiber, Wikipedia.

For Meso- and South America, several researchers have recognized and evidenced the importance of
the zenithal sun [12-18]. In [19,20], it is stressed that among the ancient civilizations that recognized
the zenith passage, we have also those of the Andean people of Peru, that incorporated it into their
cosmology. The Andean people used pillars, such as the Chankillo Towers [18,21], for solar
observations and for their calendars.
Let us add to the pillar shown in the Figure 1, another monument that we can easily imagine the
ancient architects had built to observe the zenithal sun and for related ceremonial purposes too: it is
the Gate of the Sun at Tiwanaku (Figure 2). Being under the linter of this gate, an observer could see
the shadow of it coincident to the base [22].
Tiwanaku is a Pre-Columbian archaeological site in western Bolivia. The site was first described by
the Spanish conquistador Pedro Cieza de Len. He came to the ruins of Tiwanaku in 1549, while
searching for the Inca capital Qullasuyu [23]. During the time period between 300 BC and AD 300,
Tiwanaku is thought to have been a ceremonial center for the Tiwanaku Empire to which people made
pilgrimages.

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Fig. 2. The Gate of the Sun at Tiwanaku.

The Zenithal Sun in Sri Lanka. The zenith passage was important also for people of Asia. And in
fact, in [24], we have shown that the archaeological complex of Sigiriya, the Lion Rock, in Sri Lanka
has its axis oriented to the sunset of day of a zenith passage of the sun.
Sigiriya is a huge palace built by King Kassapa I (477495 CE) on the top of a granite rock, the Lion
Rock [25,26]. This site is in the heart of Sri Lanka, dominating the neighboring plateau, inhabited
since the 3rd century BC, and hosting some shelters for Buddhist monks. A series of galleries and
staircases, having their origin from the mouth of a gigantic lion made of bricks and plaster, provide
access to the ruins on the rock. From the satellite images, it is possible to see the site surrounded by
a wall and the rock inside. At the summit of the rock, there is the fortified palace with its ruined
buildings, cisterns and rock sculptures. At the foot of the rock we find the lower city surrounded by
walls. The eastern part of it has not yet been totally excavated.

Fig. 3. The Sigiriya archaeological site in Sri Lanka. On the right, the Lion Rock. (Courtesy: Google
Earth).

The Gardens of Sigiriya are an important characteristic of the site. They are divided into three distinct
forms: the water gardens, the cave and boulder gardens, and the terraced gardens. The water gardens
are in the central section of the western precinct. They were built according to an ancient garden form,
of which they are the oldest surviving examples.

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The design of these gardens is symmetrical, however the axis is not oriented along the cardinal east-
west line: the site is inclined of 9 degrees, as we can easily measure from satellite maps (Figures 3
and 4). Since this angle is not negligible, it can correspond to a specific azimuth of the sunset, different
from the direction it has on equinoxes.

Fig. 4. The direction of the sun on April 9, given by SunCalc.net, at Sigiriya. This site provides a
diagram, overlaying a satellite map, showing the sunrise (yellow line) and sunset (red line) of the sun
for any day of the year. As explained in SunCalc.net, the thin orange curve is the sun trajectory, and
the yellow area describes the variation of sun trajectories during the year. The closer a point is to
the center, the higher is the sun above the horizon. Courtesy: SuncCalc.net and Google Earth.

Let us remember that the azimuth angle is formed by the vector from the observer to the sun rising or
setting on the horizontal plane and a reference vector on this plane. There are several web sites that
allow to know the azimuth and the noon altitude of the sun and moon at a specific location on a given
day of the year. One is the site Sollumis.com. Using it, we can obtain at Sigiriya, the data for the noon
altitude and sunset azimuths. We find that we have the zenithal sun on April 9 and on the First of
September, and that the sunset azimuth on these day is coincident with the axis of the western gardens.
In [24], we have shown this coincidence, also giving the satellite maps and the polar diagrams of the
solar azimuths from Sollumis.com. Here we show in the Figure 4 the same by using SunCalc.net
software.
On the Tropic of Cancer. Let us consider the very important Buddhist religious center of Sanchi,
India, because it has interesting astronomical orientations as discussed by N. Kameswara Rao [27];
the site possesses a particular alignment of stupas with the sunset direction on the summer solstice.
Since Sanchi latitude is very close to the Tropic of Cancer, we have also that, on this day, the noon
altitude of the sun is about 90 degrees. Therefore, the alignment of stupas is also giving the sunset
direction of the day of the zenithal sun [28]. In the Figures 5 and 6, we see the Sanchi religious
complex and the directions of sunrise and sunset on solstice.
The first written mention of the passage through the zenith of the sun in Indian literature comes from
Varahamihira in the 6th century [29,30], who noted that in the kingdom of Avanti the day of summer
solstice and zenith passage were the same (the Avanti Kingdom of ancient India was described in the
Mahabharata epic). He further discussed that north of Avanti, no zenith passage occurs. Varahamihira
wrote these observations when he was in the ancient city of Ujjain, located at latitude of 23 10 12
N [29]. In fact, as observed in [29], the ancient India had a prime meridian and a north-south zero
line of latitude crossing at Ujjain and running straight down to the island of Lanka.

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Fig. 5. N. Kameswara Rao had investigated the orientation of Sanchi stupas [27], showing that they
could had been planned to be oriented towards the moonrise and the sunset on the day of Buddha
purnima (purnima means "full moon"), the birthday of Siddhartha Gautama. (Courtesy: Google
Earth).

Fig. 6. The image shows the direction of the sunset on summer solstice as given by SunCalc.net. We
find the alignment of two stupas along the sunset. Courtesy: SuncCalc.net and Google Earth.

Angkor Wat. A very interesting paper is discussing the importance of the zenith passage of the sun
in the architecture of the temples at Angkor Wat, Cambodia (Figure 7). The authors of this paper [29],
Edwin Barnhart and Christopher Powell, University of Texas, Austin, in August of 2010 and 2011
investigated the importance of the zenith passage of the sun for the ancient Khmer culture. They
concluded the research with a positive answer. "From architectural features and orientations to art
panels and monuments, the evidence that zenith passage was recognized permeates the entire city"
[29]. According to the authors, their idea "to search for evidence of zenith passage at Angkor was
inspired by prior research in Mesoamerica. In [29], besides discussing the discoveries at Angkor, the
authors are proposing that the Hindu culture was also including some references to the zenith passage
of the sun.

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Fig. 7. On the left, aerial view of the central structure. Courtesy Shyam tnj, Wikipedia. On the right,
the Angkor Wat surrounded by a moat used for helping stabilize the temples foundation [31].
Courtesy: Google Earth.

Fig. 8. Alignments on day of the summer solstice (upper panel) and on the day of one of the zenith
passage of the sun (25 April). Courtesy: SuncCalc.net and Google Earth. The azimuth of the sunrise
on the day of the zenithal sun is about 76.2 degrees.

Barnhart and Powell have discovered that Angkor temples had vertical zenith sighting tubes too.
Though it is not apparent from the outside, each one of the beehive shaped temples of Angkor are
hollow on the inside. Walking in and looking straight up, the roof is open all the way up to the top
and that top has a hole where the sun shines in. We were told by the temple attendants that the holes
on top of the roofs were there because the capstones had all been knocked off by erosion or more
commonly by looters searching for jewels. Finding these fallen capstones among the rubble around
the temples was our first surprising clue. Most capstones were beautifully carved as lotus flowers and
all had a hollow tube running down their axes. Each had a very straight, long tube that would have
let only true zenith passage sun light down into the temples. Whether or not this was their intention,
functionally this makes every single temple of this kind at Angkor a zenith tube [29]. Besides the
temples which are beautiful artificial caves for the zenithal sun, the authors have observed that this

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architectural possesses also alignments to mark the zenith passage at Angkor Wat. In the Figure 8,
we can see two possible alignments. In the upper panel, it is given an alignment according to the
sunrise on the solstice, the lower panel is according to the sunrise on a day of zenithal sun.
The temples of Java. The temples we are considering for our discussion about the connection of the
zenith passage of the sun and architecture are those Sewu, Prambanan and Borobudur temples in Java.
The Sewu temple, an eighth century Buddhist temple complex, is predating the nearby Rara
Jonggrang, simply known as Prambanan, by over 70 years and the Borobudur by about 37 years. Prior
to the construction of these temples, probably the Sewu temple served as the main temple of the
kingdom [32]. Since Candi Sewu was built before the other two temples, we can suppose that it was
a model for them, in particular for what concerns the number of ancillary temples and stupas (in Java,
candi means temple).

Fig. 9. The zenith passage of the sun on 12 October 2016 at the Sewu temple complex. Courtesy
SunCalc and Google Earth.

Fig. 10. The solstice and the other zenith passage on 28 February (or first of March, the
Photographers Ephemeris software is giving for these days the same altitude of the sun) at the Sewu
temple complex. Courtesy SunCalc.net and Google Earth.

The Sewu temple complex occupies a large rectangular area with the sides oriented along the cardinal
directions (Figures 9 and 10). The complex has an entrance at each of the four cardinal points. The
main entrance is located on the east side. The temple is composed of 249 buildings, arranged in a
Mandala around the main central temple. Along the cardinal north-south and east-west axes of the
complex, between the second and third rows of smaller buildings, we find the apit (flank) temples.
The complex had a couple of apit for each cardinal direction; only the eastern couple is visible today.
In the Sewu temple complex, the alignment marking the passage through the zenith of the sun is given
by the central temple and one of the eastern apit temples [33]. The passage happens on 12 October

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2016, and it is displayed by the SunCalc.net software as in the Figure 9. After the zenith passage of
October, the sun reaches the solstice of December and then it has the other zenith passage at the end
of February (or the first of March), as we can see in the Figure 10.
Counting the days between 12 October 2016 and 21 December 2016, inclusive of both these dates,
we have 71 days. From December 21 to the first of March 2017, we have a total of 71 days again.
From the first of March to June 21, 2017, inclusive of these days, we have 113 days.
Let us try to connect these numbers to the number of the temples in the complex. Actually, the first
and the second rows of the Sewu temple, those inside the couples of the apit temples, are composed
by 72 small ancillary temples (Perwara) (see Figure 11). It seems therefore that a connection of the
even number of Perwara to the number of the days from the zenith passage of October to the solstice
of December is possible.

Fig. 11. The central part of the temple contains the main temple and 72 ancillary temples.

Probably, the people who built the temple determined the zenith passage of the sun according to the
observation of the stars. For instance, one can see that a particular star would always rise at a certain
point a few days before such or such a zenithal sun, hence it would be possible to know beforehand
the exact date of any given sun. [34,35] It means that 71 days are 72 nights (inclusive counting), and
this legitimates the use of the corresponding even number, equal to the number of Perwara.

Fig. 12. The Prambanan temple as given by Google Earth.

A link between the number of ancillary temples and the number of the days from the zenith passage
of the sun to the June solstice had been proposed for the Prambanan temple [36] (see the temple
complex in the Figure 12). In [36], it is told that the temple complex of Prambanan had 224 ancillary
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temples, connected to the number of 112 days after or before the June solstice. In the case of the Sewu
temple, it is the December solstice which is involved.
It is not simple to determine the number of ancillary temples of Prambanan from the satellite images,
because many of the smaller temples have been not yet restored. Let us follow the reconstruction
suggested by the symmetry that the temple probably had and by the image we find in [37]. We have
the Figure 13, in which we can see the 224 ancillary temples.

Fig. 13. Simulation of a satellite view of the reconstruction of the Prambanan temple, as proposed in
[37].

Fig. 14. Borobudur in Google Earth.

It seems therefore that the Sewu temple and the Prambanan are linked to astronomy; the Sewu temple
is connected to the sun moving about the December solstice, whereas the Prambanan is linked to the
sun moving between the zenith passages about the June solstice.
Let us consider the Borobudur temple too (Figure 14). Borobudur is one of the greatest Buddhist
monuments in the world. The temple consists of nine stacked platforms, six square and three circular,
topped by a central dome. The temple is decorated with 2,672 relief panels and 504 Buddha statues.
The central dome is surrounded by 72 Buddha statues, each seated inside a perforated stupa [38].
Again, we have the number 72; as we have previously told, it is equal to the even number of the days
passing from the zenith passage of October to the December solstice, and also from the December
solstice to the zenith passage on the end of February or the first of March.
It seems therefore that, for the people who built the temples, the astronomical year was based on
periods of even numbers of days with an inclusive counting: 72 days from the zenith passage of the
sun to the December solstice, and from this solstice to the zenith passage of the first of March. Then,
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there was another set of 112 days, from the zenith passage to the June solstice, and the same from this
solstice to the zenith passage of October. Adding these periods we have a total of 368 days. However,
the counting was inclusive, and then we have to remove some days. For instance, if we start the count
from the zenith passage of the first of March, we have to remove one day for the other zenith passage
and two days for the two solstices. We obtain 365 days.
However, let us note that a religious interpretation of the seventy-two temples of the Sewu central
structure exists, as for those of Borobudur. Within the Buddhist Abhidharma philosophical schools,
the Sarvstivdins identified three unconditioned Dharmas whose nature is free from the laws of
causation (asaskta) as well as 72 conditioned Dharmas (see Wayman 1997:269) which are subject
to the laws of causation (saskta). So one might conjecture that these 72 auxiliary shrines had
pertained to what Vilsavajra had called the second circle of Mahvairocana containing the divinities
belonging to the perfectly pure Dharmadhtu of Vairocana [39].
Let us just add a comment: it is possible that people observed a coincidence between religion and
astronomy, and that the conditioned Dharmas were the days conditioned by the zenithal sun.
Summary. The examples discussed above, provide evidence of the importance of the zenith passage
of the sun. Many other sites had been discussed in literature and on web sites [40-50]. However, many
others require further investigations for what concerns the astronomical alignment.
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