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International Symposium on Advanced Materials (ISAM 2013) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 60 (2014) 012034 doi:10.1088/1757-899X/60/1/012034

Synthesis of silver nanoparticles by silver salt reduction and

its characterization

Muhammad Muzamil, Naveed Khalid, M Danish Aziz and S Aun Abbas

NED University of Engineering & Technology, Karachi, Pakistan

E-mail: muzamil_vir@hotmail.com, naveed_nawab@hotmail.com,

mdanishaziz@hotmail.com, aunabbas@live.com

Abstract. The wet chemical method route by metal salt reduction has been used to synthesize
nanoparticles, using silver nitrate as an inorganic salt, aldehyde as a reducing agent and amino
acid as a catalyst. During the reaction aldehyde oxidizes to carboxylic acid and encapsulates
the silver nanoparticles to prevent agglomeration and provide barrier in the growth of particle.
The existing work produces particles using lab grade chemical, here the presented work is by
using industrial grade chemicals to make the process more cost & time effective. The nano
silver powder has been studied for their formation, particle size, shape & compositional
analysis using Scanning Electron Microscope (SEM) equipped with EDS. The particles size
distributions were analyzed by Laser Particle Analyzer (LPA), structure & morphological
analysis using x-ray diffraction (XRD) and Fourier-transform-infrared Spectroscopy (FTIR)
confirmed the stabilization of particles by coating of carboxylic group. These studies infer that
the particles are mostly spherical in shape and have an average size between 70 to 350 nm.

1. Introduction
In the Synthesis of Silver Nanoparticles, Top down & Bottom up are the two fundamental synthesis
approaches for nanoparticles. Top down approach can be regarded as a process starting with a bulk
material and then breaking it into small size. Typical processes include attrition, milling, lithography,
mechanical & chemical manipulation tools [1].
The main advantages are universality and low cost. Even soft organic matter (e.g. grass) can be
ground by first freezing it in liquid nitrogen. The main disadvantages are irregular surface structure,
polydispersity of the final particles, and the introduction of many defects. The smaller the particle, the
worse is the contamination.
In bottom up approach, organic & inorganic structures are created atom by atom, molecules by
molecules, cluster by cluster. This technology synthesizes materials by from atomic or molecular
species via by chemical reactions. In this way biological & chemical reactors create conditions for
special growth and materials self-assembled together to form nano complex structure [1].
In this synthesization of silver nanoparticles the process is based on bottom up approach, which
basically relies on the chemical reduction of metal salts, electrochemical pathways, or the controlled
decomposition of metastable organometallic compounds in solution. Control over the growth of the
primarily formed nanoclusters depends upon the rate of mixing, two extreme situations yield the
desired monodispersity; ultrarapid mixing of very concentrated solutions, and ultraslow mixing of
very dilute solutions, and their agglomeration is effected by the use of a variety of stabilizers, in the
form of donor ligands, polymers, and surfactants [2].

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International Symposium on Advanced Materials (ISAM 2013) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 60 (2014) 012034 doi:10.1088/1757-899X/60/1/012034

In the precursors of process, propanal is known to be a weak reducing agent & it has no significant
reducing effect on AgNO 3, metallic salt, in the absence of a catalyst such as diethyl amine (DEA).
Without using DEA, propanal takes quarter of a day to reduce silver salt but in the presence of catalyst
reaction will complete in just 10 minutes. The silver precipitates can also be formed without using
propanal as in the case of silvering of mirror when ammonia (NH 3 ) reacts with silver nitrate (AgNO 3 )
and forms ammonium nitrate but the problem is that an excess amount of ammonia (NH 3 ) cause these
silver precipitates to get dissolves in aqueous solution. DEA has a tendency to produce hydroxyl ion
which reacts with aldehydes group and forms carboxylic acid which releases an electron in the
reaction that will reduce silver ion. The carboxylic acid encapcules the newly formed silver particles
stops the further growth of particles & prevent it from agglomeration with other particle.
The formed particles have very high surface energy due to high surface area but energy can also be
reduce through surface relaxation, surface restructuring, surface adsorption of chemical & physical
species and compositional segregation of impurities [3].
Protective layer plays a vital role in stabilizing a nanoparticle from further agglomeration. There are
two types of approaches which are commonly used to protect the particle from agglomeration.
Electrostatic stabilization is caused by the Columbic repulsion between particles, caused by the
electrical double layer formed by ions adsorbed at the particle surface and the corresponding counter
ions [2].
Steric stabilization also called polymeric stabilization which is widely used in stabilization of
colloidal dispersions. During the reduction of metal salt formation of carboxylic acid offers two
advantages particularly when narrow size distribution is required. It absorbs on the surface of particle
provide stabilization & diffusion barrier in the growth of particle.

2. Experimental Work
The starting precursors for synthesis are Silver Nitrate, propanal and diethyl amine. The aqueous
solutions with different concentrations of silver nitrate and propanal were mixed together in a
calculated volume of deionized water having TDS (total dissolved solid) of 0~5mgs/liter by mixing
through magnetic stirrer till the solution became homogenized. A pre calculated milli molar aqueous
solution of diethyl amine (DEA) was added to it quickly and stirred vigorously (Conc. of chemical
used in synthesis procedure mentioned in Table.1). The color change in solution is observed after 10 to
20 minutes, from black to brown and then finally a dark gray colored higher concentrated Silver
Nitrate precipitates were obtained and a yellowish-green colored suspension was obtained for lower
concentration of silver nitrate.
The experiment was repeated with argon environment of 0.1~0.2 atm, in a glove box to
homogenize the solution and observed that cluster of particles suspended in a solution. After filtering
the mixture and washing the residue repeatedly 2 to 3 times with distilled water, the residue was
collected and dried in a vacuum furnace at 50°–60°C.

Figure 1. Schematic diagram of the

experimental system, (1) Argon cylinder, (2)
Figure 2. Physical Experimental Setup
Control Valve, (3) Magnetic stirrer & (4)
Glove Box

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International Symposium on Advanced Materials (ISAM 2013) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 60 (2014) 012034 doi:10.1088/1757-899X/60/1/012034

This experiment consisted on 2 stages. In the first stage all the mixing of precursors were at
ambient conditions of the lab at 30°C by just stirring the solution at 20~30 RPM & in the second stage
a controlled environment is provided in the glove box by maintaining the inside working pressure & a
jet of argon gas is provided to homogenize & stabilize the particle by removing the trapped oxygen in
the solution. Physical arrangement of setup is shown in Figure 2.

Table 1. Concentrations Employed in Experiments for Different Samples

Conc.
Conc. AgNO 3 Conc. DEA Particle size SEM Mean
S.No. Propanal
(mM) (mM) (±10nm) (nm)
(mM)
1 150 60 80 350-300 325
2 150 60 80 325-275 300
3 100 50 85 300-250 275
4 100 50 90 300-225 260
5 75 45 100 200-150 175
6 75 40 100 200-150 175
7 50 40 120 150-100 125
8 50 35 120 150-70 110
The concentration of AgNO 3 & DEA has an inverse relation between them. When the
concentration of AgNO 3 goes on increasing & the concentration of DEA goes of decreasing the
outcome is large particles size with wide distribution & vice versa.

3. Results & Discussions

The scanning electron microscope is frequently used for topographical imaging of nanoparticles.
These images are typically used for investigating the size, shape, impurities & stabilization of
particles. In Sample preparation, nanoparticles attached on aluminum stub using double-sided carbon
tape for sample mounting, remove loose sample material by gently knocking the holder to a hard
surface. Transfer the stub with sample directly to the SEM for topographical imaging. The
characterization was carried in FEI SEM Quanta 200.
SEM images for the Sample No.7 (Table 1) are shown in figure 3 at magnification 10,000X &
figure 4 at magnification at 20,000X. The secondary electrons results indicate that particles are nearly
spherical identical in shape, dispersive & crystalline in structure. The diameters of the polycrystalline
particles can be measured by using the scale represented in the each micrograph & the calculated
range is written with each below mentioned figure.
Elemental compositional analysis has also been done through EDS (Energy Dispersive
Spectroscopy) to find out the purity of silver nanoparticles. Since there is a huge difference in atomic
number of oxygen & silver, atomic number contrast of these two element is a primarily tool in
identifying the weight percentage. Results are summarized in Table 2; shows 98.06% by weight &
88.11% by atom silver nanoparticles & just 1.96% & 11.89% respectively oxygen were present.
Graphically the results are represented in Graph.1 which is an automated generated graph by built-in
software of SEM shows the highest counts of silver. The presence of oxygen shows that some particles
got oxidized & agglomerate by forming silver oxide, but it’s a very minute quantity, rest of them are
still stabilized.
Quantitatively the particle size distribution is being best evaluated through Laser Particle Analyzer
characterization. To find the distribution, first run the standard solutions of known size distribution,
the detectors record the energy scattered & absorbed at particular angle & makes scattering patterns
then compares the values of samples with these standard values. BT-9300H Better Size Instrument had
been used for particle size analysis.
Eight different samples were being run to find out the mean particle distribution of silver particles
(as shown in Table 1).The recorded distribution of each individual sample is shown in the histogram

3
International Symposium on Advanced Materials (ISAM 2013) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 60 (2014) 012034 doi:10.1088/1757-899X/60/1/012034

(Graph 2), the result are on the basis of volume circulates in the chamber, for different samples
assume that circulating pumps took 100% volume to exposed chamber of x-rays.

Figure 3. Sample of Silver Nanoparticle at Figure 4. Sample of Silver Nanoparticle at

Magnification 10,000X & Size 100-150nm. Magnification 20,000X & Size 100-150nm.

Table 2. Compositional Weight Percentage of EDS

Element Weight % Atomic %
OK 1.96 11.89
Ag L 98.04 88.11
Totals 100.00 100.00

Graph 1. EDS compositional Intensity

For Sample 1 in Histogram (Graph 2), Result shows out of 100%, 50% in 300-310 nm, 5% in 310-
320nm, 30% in 320-330nm, 40% in 330-340nm & 5% in 340-350nm particles of silver were present,
same sequence of interpretation will also be followed for the distribution of particles in sample
2,3,4,5,6,7 & 8.
Fourier Transforms Infra Radiation (FTIR) serves as the molecular fingerprint for the identification
organic materials. This technique is extremely useful for the confirmation of the presence of
carboxylic acid on the silver nanoparticles as a coating. The obtained FTIR spectrum of the organic
material present in the sample compared for best matches with libraries of spectra that have been
cataloged for known materials. There are five broad peak can be seen in the figure 5 of silver particle
spectra at 3469, 2370, 1653, 1571, 1506 cm-1.
The first peak at 3469 & 1571 cm-1 must be assigned to hydroxyl group [8], because in the
oxidation some of the hydroxyl group remains unreactive & also some moisture get absorb on the
highly reactive surface of nanoparticles. The peak at 2370cm-1 belongs to (CH) stretching band of
aldehyde group [9], some solution not succeeded to oxidize to carboxylic acid & the peak at 1550 &
1506cm-1 was concluded to be Nitrate from AgNO 3 , which is starting metal precursor, when we
compared the standard FTIR spectra of silver nitrate.
The C=0 absorption is one of the most characteristic in the spectrum. Ketone is considered the root
compound while the aldehyde & carboxylic are the derived structures. The characteristic peak of
carboxylic acids is present at1653 cm-1 is shown in the enlarged spectra of figure 6. The carboxylic
acid frequency range is 1700-1300 cm-1. They are unique in signature, so far as the hydroxyl group has
direct interaction with the carbonyl group, by the formation of a stable hydrogen-bonded structure [7].

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International Symposium on Advanced Materials (ISAM 2013) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 60 (2014) 012034 doi:10.1088/1757-899X/60/1/012034

In the enlarged spectra Figure 6, when this section compared with standard spectra all major & minor
peaks should be matched, the carbonyl peaks are present with the hydroxyl group at 1571cm-1, which
confirm the presence of carboxylic acid on the silver particle surface.

60 sample 1 60 sample 2
40 40

20 20

0 0
300-310 310-320 320-330 330-340 340-350 275-285 285-295 295-305 305315 315-325

40 40
sample 3 sample 4
30 30

20 20

10 10
0 0
250-260 260-270 270-280 280-290 290-300 225-240 240-255 255-270 270-285 285-300

30 sample 5 40 sample 6
30
20
20
10
10
0 0
150-160 160-170 170-180 180-190 190-200 150-160 160-170 170-180 180-190 190-200

40 sample 7 40 sample 8
30 30
20 20
10 10
0 0
100-110 110-120 120-130 130-140 140-150 70-90 90-105 105-120 120-135 135-150

Particles size (nm) distribution

Graph 2. Histogram of Silver Nanoparticles distribution of 8 samples.

The structure of prepared silver nanoparticles has been investigated by X-Ray Diffraction (XRD)
analysis. The dry powder of the silver nanoparticles is used for XRD analysis. The diffracted
intensities were recorded from 20° to 80° at 2 theta angles. The XRD pattern of the sample, prepared
by the presented chemical method is shown in the Figure 7.
All diffraction peaks correspond to the characteristic crystalline Face Centered Cubic (FCC) silver
lines compared with the standard powder diffraction card of Joint Committee on Powder Diffraction
Standards (JCPDS), silver file No. 04–0783. No peaks from other phases are detected, indicating the
high purity of silver metal. Table 3 shows the experimentally obtained X-ray diffraction angle, d
spacing and the intensity count of Ag specimen.

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International Symposium on Advanced Materials (ISAM 2013) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 60 (2014) 012034 doi:10.1088/1757-899X/60/1/012034

Wavelength cm-1
Figure 5. FTIR spectra of Silver Nanoparticles from 4000 to 400cm-1 wavelength.

COOH

1571 1550 1506

1653

1720 1600 1480

-1
Wavelength cm
Figure 6. Enlarged FTIR spectra of Silver Nanoparticles capsuled with Carboxylic
acid in wavelength range of 1760-1440cm-1.

Table 3. Shows the values observed in XRD spectrum

Observed d Value Intensity Intensity

2Ө values Angstrom Count Percentage
38.331 2.34634 1239 100
44.488 2.03484 500 40.3
64.644 1.44068 372 30
77.56 1.22975 371 29.9
81.751 1.17707 176 14.2

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International Symposium on Advanced Materials (ISAM 2013) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 60 (2014) 012034 doi:10.1088/1757-899X/60/1/012034

1300
(111)
d=2.346

(200)
700

(220) (311)
d=2.034

(222)
d=1.44
d=1.229
100
d=1.177

10 20 30 40 70 80
2 Theta
Figure 7. XRD Result showing various peaks.

The Miller indices are calculated by using the observed 2Ө values corresponding to each peak and the
details are summarized in Table 4. The powdered silver nanoparticles show a cubic structure showing
peaks at 2Ө: 38.331 (111), 44.488 (200), 64.644 (220), 77.568 (311) and 81.751 (222). The high
intense peak for FFC material is (111), which is observed in the powdered sample. [8]

Table 4. Calculation Procedure for hkl Evaluation

Peak 1 x sin2Ө/ 2 x sin2Ө/ 3 x sin2Ө/
2Ө sin2Ө h2+k2 +l2 hkl
No. sin Ө min
2
sin Ө min
2
sin2Ө min
1 38.331 0.107 1.00 2.00 3.00 3 111
2 44.488 0.143 1.33 2.67 4.00 4 200
3 64.644 0.285 2.66 5.32 8.00 8 220
4 77.568 0.392 3.66 7.32 11.00 11 311
5 81.751 0.428 3.97 7.947 12.00 12 222

4. Conclusion
The Silver nanoparticles have been synthesized by wet chemical route and are characterized by using
SEM, LASER Particle analyzer, FTIR spectrometry and XRD techniques. The mean particle size is
found to be 120-325 nm. The concentration of DEA plays a vital role in controlling the size of
particles. This work also reveals a quick route to synthesize Silver nanoparticles economically on large
scale volumes using industrial grade chemicals and maintaining the purity and characteristics. In
future, these Silver Nano Particles can be further analyzed for its heat transfer properties and
application in nanofluids and conductive gels.

5. Acknowledgement
The authors are indebted to Dr. Muhammed Tufail, Dean faculty of Mechanical & Manufacturing and
Chemical & Processing Engineering, Dr. Mubashir Ali Siddiqui, Chairman Mechanical Engineering
Dept., Dr. Ashraf Ali, Chairman Materials Engineering Dept., NED UET, Mr. Mudassir Ahmed for
technical discussion, Mr. Sajid Ali Asghar for SEM work and Dr. Uzma Ashiq for FTIR analysis.

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International Symposium on Advanced Materials (ISAM 2013) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 60 (2014) 012034 doi:10.1088/1757-899X/60/1/012034

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