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Materials Today: Proceedings XX (2017) XXX–XXX www.materialstoday.com/proceedings

ICMMM - 2017

Optimization of Electroless Copper coating parameters on graphite

particles using Taguchi and Grey Relational Analysis
Y P Deepthia*,M Krishnab
a
Department ofMechanical Engineering,Amrita School of Engineering,Bengaluru,Amrita Vishwa Vidyapeetham,Amrita University,India
b
Department of Mechanical Engineering,RV College of Engineering,Bangalore,India

Abstract

Electroless process is employed to get uniform coating of copper on graphite particles. Electroless coating process was performed
based on Taguchi L16 orthogonal array. Optimal coating parameters were determined by Taguchi method using Grey Relational
Analysis. ANOVA technique was further employed to know the optimal parameters from grey relational grade. The present study
is to maximize thermal conductivity and coating thickness characteristics of electroless copper coated graphite, by optimizing the
four coating parameters viz. composition of zinc, copper sulphate, graphite and sensitization time. Microstructural aspects were
studied through SEM analysis.

© 2017 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of International Conference on Materials Manufacturing and Modelling (ICMMM - 2017).

Keywords: Electroless process;Taguchi method; Grey relational Analysis; ANOVA

1. Introduction

Sliding bearings should be able to withstand high temperature during running condition. PTFE is widely used in
sliding applications because of their low coefficient of friction [1-2]. PTFE bearing widely used in petrochemical
plants, pipelines, buildings and bridge girders where they can accommodate expansion, contraction and other
reciprocating motions of the structure[3]. The thermal properties of PTFE can be enhanced by adding conductive

* Corresponding author. Tel.: 9535473064 ; fax: +0-000-000-0000 .

E-mail address: deepthi.prajna@gmail.com

2214-7853 © 2017 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of International Conference on Materials Manufacturing and Modelling (ICMMM - 2017).
2 Author name / Materials Today: Proceedings XX (2017) XXX–XXX

fillers like graphite, ceramic or metal particles [4]. With outstanding thermal stability, coefficient of thermal
expansion (CTE), good chemical resistance and low friction coefficient, graphite has been used widely as
reinforcement for polymer metal matrix [5-8]. Graphite has some deficiencies like brittleness, low strength and
relatively poor conduction [9].

To overcome the problems many researchers developed metal coating techniques to coat graphite with metals such
as copper[10], silver[11] and nickel[12] which helps in preventing interfacial reaction and improves wettability of
the particles[13-14]. Rajkumar et al.[15] reported in his study that copper and its alloy are extensively used in the
applications that requires thermal conductivity, corrosion resistance and wear resistance properties. Moustafa et al.
[16] concluded in their studies that copper coated graphite composites showed high thermal conductivity and
excellent lubrication properties for sliding contacts. W Lu et al.[17] reported in his work that Copper coating acts as
a protective layer to minimize the exfoliation of the graphite in polymers.
The density difference between graphite and copper is high, because of that uniform powder mixture cannot be
obtained. So sintering cannot be done. Instead of mixing copper with graphite, when graphite particle coated with
copper better particle distribution expected to achieve and develops continuous copper network [18].

There are many coating methods available. Some of the methods are Electroless chemical and Electrochemical
method, physical vapour deposition, chemical vapour deposition, spraying, roll to roll coating process. For coating
on micro or nano particles only electroless process is preferable. Ashtiani et al.[19] reported in his work that uniform
coating thickness can be obtained by electroless process, which leads to reduction in corrosion due to absent of
galloan effect. Deposition of metals on the nonconductive and conductive materials without the source of electricity
is electroless process. Ashassi-Sorkhabi et al.[20] reported in his work that increased in coating time helps in
decreasing corrosion rate. Electroless coating technique is appealing because of its low cost, high quality thin films
[21]. Jaroslav[22] observed that electroless coating is the best method for coating graphite with copper to obtain
uniform coating. Caturla[23] reported that most of Graphite pores covered after electroless coating and amount of
coverage depends on thickness of copper coatings on graphite particles.

The objective of this work is to optimize the conditions to coat 2-10m size graphite particles with adherent uniform
and continuous coatings of copper for use in preparing polymer composite as reinforcement which increases
Thermal Conductivity. However not much work done to find optimum conditions for coating copper on graphite
particles based on coating Thickness and Thermal Conductivity. Taguchi orthogonal method is used to design the
optimum number of experiments to be conducted for Electroless copper coatings on Graphite. The amount of copper
coated on graphite depends on composition of bath, which is comprised of Copper sulphate, Graphite, Zinc.
Sensitization time is the amount of time graphite particles soaked in acetone. As all these parameter have effect, so
they were choosen as process parameters. Grey Taguchi method used for solving multiple response problems [24].
ANOVA further employed to find optimum level of factors based on maximum Grey relational Grade values.
Moreover the copper coating on graphite particles are characterized by SEM to understand the microstructural
characteristics.

2. Experimental Details

2.1. Design of Experiments

In full factorial design, all the factors with its various levels are studied. As there are four factors and each factor
has got four levels, so 44 i.e. 256 experiments has to be performed, to know the effect of these factors on the
responses. There is a chance of experimental error creeping because of variation in material and background
conditions [25]. Dr. G Taguchi developed Taguchi techniques, from which effect of input parameters on output can
be known with minimal number of experiments. Optimum number of experiments can be obtained through Taguchi
technique [26-30].In present study Taguchi OA (L16) is obtained using Minitab software. The four factors with their
four levels shown in the Table 1.
 Author name / Materials Today: Proceedings XX (2017) XXX–XXX 3

Table 1. Design factors and their levels.

Design factors Units Levels
1 2 3 4
Zn concentration gm 19.5 21.5 23.5 25.5
CuSo4 concentration gm 67.5 75 82.5 90
Gr concentration gm 19.5 21.5 23.5 25.5
Sensitization time minute 5 10 15 20

2.2. Specimen Preparation

According to C B Lin [31], Graphite is coated with copper by cementation process, in which the copper ions are
replaced by zinc via heterogenous secondary nucleation process .Graphite particles of size 2-5 micron is taken and
dipped in Acetone solution. The contents are oscillated with the help of Ultrasonic Oscillator. Impurities on the
graphite particles are removed in this process. Copper sulphate solution is prepared by mixing 90 gm of CuSo 4 in
distilled water. Glacial acetic acid which acts as wetting agent is added to the bath. This serves as electrolyte. Dried
Graphite particles are added into the electrolyte. Zinc of particle size 12-14 m is immersed in the electrolyte bath
and agitated with the help of ultrasonic oscillator. During this period copper gets coated on the graphite particle. The
experimental setup is shown in fig.1.Coated particles are separated from electrolyte bath through filter papers of
diameter 125 mm and then dried in furnace.

Fig. 1 Specimens in Ultrasonic oscillator.

Pallets are made out of the dried copper coated samples by compacting with hydraulic press at a pressure of
30KPa. The compacted pellets are sintered at a temperature of 300C for 10 min. Gaurav Awasthi et al.[32] in his
studies concluded that the rise in sintering temperature helps in obtaining uniform microstructures at the interface.
He contributed this because of formation of many meshes of grain boundary and their interactions with the
interwoven pores. He added that sintering temperature is directly proportional to coefficient of the atomic diffusion
within the particle.

2.3. Output variables

The output parameters that will be analyzed are Thermal conductivity and coating Thickness. Particle Thickness is
measured by Particle Analyser. Thermal Conductivity is calculated from Electrical conductivity from Franz law
shown in Eq. 1, where K and L are thermal conductivity and proportionality constant(Lorenz number) respectively.
4 Author name / Materials Today: Proceedings XX (2017) XXX–XXX

Lorenz number at room temperature equals to 2.44e-8 WΩK-2. The results of coating thickness and thermal
conductivity for the 16 experiments are shown in Table 2.

K (1)
 LT


Table 2. Values of coating thickness and thermal conductivity for different samples.

Exp No. Thickness Thermal Conductivity

(mm) (W/mK)
1 0.03 3.159
2 0.25 3.736
3 0.25 13.6
4 0.51 5.713
5 0.44 5.02
6 0.69 5.524
7 0.48 6.989
8 0.32 5.72
9 0.19 6.04
10 0.41 9.545
11 0.42 16.18
12 0.7 8.63
13 0.42 9.42
14 0.91 5.39
15 0.25 7.38
16 0.83 13.8

Grey Taguchi analysis is employed to convert multiple responses into single response, shown in Table 3. The
standard formulas are used for calculating grey relational coefficient [25].Further ANOVA is employed to find the
optimal levels from Grey Relational Grade, shown in Table 4. The parameters where highest coating thickness and
thermal conductivity registered are at 25.5 gm of Zinc, 90 gm of Copper sulphate, 19.5 gm of Graphite and 15
minutes of sensitization time.

Table 3. Calculations of Grey Relational Grade for coating thickness and thermal conductivity.

Exp.No. Normalised data oi Grey Relational Grey

Coefficient Relational
Grade
Coating Thermal Coating Thermal Coating Thermal
thickness Conductivity thickness Conductivity thickness Conductivity
1 0 0 1 1 0.5 0.5 0.5
2 0.61 0.1 0.39 0.9 0.72 0.53 0.625
3 0.62 0.89 0.38 0.11 0.72 0.9 0.81
4 0.83 0.36 0.17 0.64 0.85 0.61 0.73
5 0.78 0.28 0.22 0.72 0.82 0.58 0.7
6 0.92 0.34 0.08 0.66 0.93 0.6 0.765
7 0.81 0.49 0.19 0.51 0.84 0.66 0.75
8 0.69 0.36 0.31 0.64 0.76 0.61 0.685
 Author name / Materials Today: Proceedings XX (2017) XXX–XXX 5

9 0.54 0.4 0.46 0.6 0.68 0.63 0.655

10 0.77 0.68 0.23 0.32 0.81 0.76 0.785
11 0.77 1 0.23 0 0.81 1 0.905
12 0.92 0.62 0.08 0.38 0.93 0.72 0.825
13 0.77 0.67 0.23 0.33 0.81 0.75 0.78
14 1 0.33 0 0.67 1 0.6 0.8
15 0.62 0.52 0.38 0.48 0.72 0.68 0.7
16 0.97 0.9 0.03 0.1 0.97 0.91 0.94

Table 4 ANOVA for Grey Relational Grade

L1 L2 L3 L4
Zn 0.66625 0.725 0.7925 0.805
CuSo4 0.65875 0.74375 0.79125 0.795
Gr 0.7775 0.7125 0.7375 0.76125
Time 0.71875 0.74875 0.80875 0.7125

Graphite which is flake like structure can be observed in Fig. 2a. After electroless coating copper gets deposited on
graphite, which covers the graphite flakes shown in Fig. 2b. Uniform microstructure was formed at interface after
sintering copper coated graphite shown in Fig. 2c.
a b c

Fig. 2. SEM images of a) pure graphite b) copper coated graphite c) copper coated and sintered graphite.

3. Conclusion

Taguchi Orthogonal array (L16) designed using Minitab software. Copper gets coated on Graphite using
electroless coating process. The coating thickness is measured by Particle Analyzer. The maximum coating
thickness obtained at the 25.5 gm of zinc, 75 gm of copper sulphate and 23.5 gm of graphite and sensitization time
being 5 minutes. It was observed there is an increase in Thermal Conductivity of coated Graphite compared to
noncoated Graphite. The maximum Thermal conductivity registered at 23.5 gm of zinc, 82.5 gm of copper sulphate
and 19.5 gm of graphite and sensitization time being 10 minutes. Grey Relational Analysis Technique is employed
to know the optimum parameters for multiple responses. The optimal parameters for multiple responses are 25.5 gm
of Zinc, 90 gm of Copper sulphate, 19.5 gm of Graphite and 15 minutes of sensitization time. Through SEM
photographs difference between coated and noncoated graphite particles was observed.
6 Author name / Materials Today: Proceedings XX (2017) XXX–XXX

References:

[1] S. K. Biswas, Friction and wear of PTFE-a review,Wear.158 (1992) 193-211.

[2] Jaydeep Khedkar, Ioan Negulescu, Efstathios I. Meletis, Sliding wear behavior of PTFE composites, Wear. 252 (2002) 361–369.
[3] http://www.cp-ltd.co.uk/wp-content/uploads/2011/09/PTFE-Sliders.pdf, accessed on 15th December 2016.
[4] Ich-Long Ngo, Sangwoo Jeon, Chan Byon ,Thermal conductivity of transparent and flexible polymers containing fillers: A literature
review, Int. J. of Heat and Mass Transfer 98 (2016) 219–226.
[5] H.N. Hashemi, J.T. Blucher, J. Mirageas, Fraction and Wear Behavior of Aluminum-Graphite Composites as a Function of Interface
and Fiber Direction ,Wear. 150 (1991) 21–39.
[6] G. Goller, D.P. Koty, S.N. Tewari, M. Singh, A. Tiken, Wear and Friction Behavior of Metal Impregnated Microporous Carbon
Composites, Metall. Trans.27A (1996) 3727–3738.
[7] P.G. Gibson, A.J. Clegg, A.A. Das, Wear of cast Al-Si alloys containing graphite,Wear 95 (1985) 193–198.
[8] A.G. Wang, I.M. Hutchings, Wear of alumina fibre-aluminium metal matrix commina fibreposites by two-body abrasion, Mater. Sci.
Technol. 5 (1989) 71–76.
[9] S.F. Moustafa, S.A. El-Badry, A.M. Sanad, Effect of graphite with and without copper coating on Consolidation behaviour and
sintering of copper-graphite composite ,Powder Metallurgy. 40 (3) (1997) 201–206.
[10] Fei Li, Feng-yuan Yan, Lai-gui Yu, Wei-min Liu, The tribological behaviours of copper coated graphite filled PTFE composites,
Wear. 237 (2000) 33–38.
[11] T. Doi, T. Fukutsuka, k. Takeda, T. Abe, K. Miyazaki, Z. Ogumi, Surface modification of graphitized carbonaceous thin film
electrodes with silver for enhancement of interfacial Lithium-Ion transfer, J Phys. Chem. C 116 (2012) 12422-12425.
[12] Jie Yang,Yunjing Zhang,Xiaoqin Zhao,Yulong An,Huidi Zhou,Jianmin Chen,Hou Guoliang,Tribological behaviors of plasma sprayed
CuAl/Ni-graphite composite coating, tribology international. 90 (2015) 96–103.
[13] R.Karthigeyan, S.Ezhil vannan, G.Ranganath, S.Paul Vizhian, K.Annamalai, Effect of coating parameters on coating morphology of
basalt short fiber for reinforcement preparation of Al/Basalt metal matrix composites, Int. j. Electrochem. Sci. 8 (2013) 10138-10148
[14] BP Dileep,V Ravikumar, Mrudula prashanth, MV Phanibhushana.Effect of Zinc coating on Mechanical Behavior of Al 7075, Applied
Mechanics and Materials. 592-594 (2014) 255-259
[15] K.Rajkumar, S.Aravindan, Microwave sintering of copper-graphite composites, Journal of materials processing technology.209
(2009) 5601-5605.
[16] S.F. Moustafa, S.A. El-Badry, A.M. Sanad, B Kieback, Friction and wear of copper-graphite composite made with Cu-coated and
uncoated graphite powders, wear. 253 (2002) 699-710.
[17] W.Lu, VS.Donepudi, J.Prakash, J.Liu, K.Amine, Electrochemical and thermal behaviour of copper coated type MAG-20 natural
graphite, Electrochimica Acta .47 (2002) 1601-1606.
[18] Jaroslav Kovacik, Stefan Emmer, Jozef Bielek, Thermal properties of cu-graphite composites, Kovove materialy.42(2004) 365-374.
[19] Amir Ahmadi Ashtiani, Soheila Faraji, Sepideh Amjad Iranagh, Amir Hossein Faraji, The study of electroless Ni–P alloys with
different complexing agents on Ck45 steel substrate, Arabian Journal of Chemistry.(2013)
[20] Ashassi-Sorkhabi.H, Rafizadeh.S.H, Effect of coating time and heat treatment on structures and corrosion characteristics of electroless
Ni–P alloy deposits, Surf. Coat. Technol. 176 (2004) 318–326.
[21] Valery M. Dubin,Yosi shacham-Diamand, Bin Zhao, P. K. Vasudev, Chiu H. Ting, Selective and Blanket Electroless Copper
Deposition for Ultralarge Scale Integration, J. Electrochem. Soc.144 (1997).
[22] Jaroslav Kovacik, Stefan Emmer, Jozef Bielek, Lubomir Kelesi, Effect of composition on friction coefficient of Cu–graphite
composites, Wear. 265 (2008) 417-421.
[23] F. Caturla, F. Molina, M. Molina-Sabio, F. Rodriguez-Reinoso, Electroless Plating of Graphite with Copper and Nickel, J.
Electrochem. Soc. 142(1995).
[24] Suman Kalyan Das, Prasanta Sahoo, Tribological characteristics of electroless Ni-B coating and optimization of coating parameters
using Taguchi based grey relational analysis, Materials and design. 32 (2011) 2228-2238.
[25] K.Krishnaiah, P.Shahabudeen, Applied Design of experiments and Taguchi methods, PHI Learning private limited, New Delhi 2012.
[26] Y.P.Deepthi, K.Prakash Marimuthu, K.Raghavendra Ravi Kiran, Performance Test of Cryogenically treated and coated tungsten
carbide cutting inserts , Applied Mechanics and Materials.813-814 (2015) 575-580.
[27] G.Taguchi, Introduction to Quality Engineering, Asian productivity organisation,1990.
[28] P.J. Ross, Taguchi Techniques for Quality Engineering, 2nd ed., McGraw-Hill,Newyork,1996.
[29] D.C.Montgomery, Design and Analysis of Experiments,Wiley,Newyork,2001
[30] P. .M.Mrudul, .Upender, T., Tarun, V., Balachandran, M., and Mini, K. M., “Study on Silica Infused Recycled Aggregate Concrete
Using Design of Experiments”, Journal of Engineering science and Technology, vol. 12, no. 10, 2017.
[31] C.B.Lin, T.C.Wang, Z.C.Chang, H.Y.Chu, Tribological Analysis of Copper Coated Graphite Particle-Reinforced A359 Al/5 wt% SiC
composites, Journal of Materials Engineering and Performance. 22(2013) 94-103. M
[32] Gaurav Awasthi, T.K.Mishra, Atish Sanyal, Ajay Tiwari, Study of Graphite content and sintering temperature on Microstructure
properties of Iron based powder perform, Int. Journal of Engineering Research and Applications. 3(2013) 1789-1796.