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Materials Today: Proceedings 4 (2017) 12054–12060 www.materialstoday.com/proceedings

ICNANO 2016

Synthesis and Characterization of Silver Nano Particles for EDM

Applications
Shivaji V Bannea*, M. S. Patilb . R. M. Kulkarnic, S. J. Patilb
aQuality Engineering and Software Technology (QuEST) Belagavi-591245 Karnataka India
bMechanicalDepartment KLS Gogte Institute of Techology, Belagavi-590008 Karnataka India
cChemistry Department KLS Gogte Institute of Techology, Belagavi -590008 Karnataka India

Abstract

Over the past few decades, nano particles research of noble metals such as silver exhibited as an intense area of scientific interest
due to their significantly distinct applications in biomedical, optical and electronic fields from their bulk counterparts because of
their smaller particle size, higher surface area and various other effects. These silver nano particles can be synthesized by various
methods: Reduction either by using Citrate or Sodium Borohydride, Ion Implantation and Biogenic Synthesis. Amongst these,
Sodium Borohydride is used in excess for reduction of silver nitrate and stabilize the silver nano particles. Sodium Borohydride
being a strong reducing agent may lead to secondary reaction. An ice bath facilitates to slow down the reaction rate and
eliminates secondary reactions. If agglomeration of nano particles occurs, PVP is added during reaction. To characterize the nano
particles Ultraviolet Visual Spectroscopy, Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) can be employed.
Borohydride reduction method produces 30-100 nm particles.
© 2017 Published by Elsevier Ltd.
Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON NANOTECHNOLOGY (ICNANO-
2016).

Keywords: Nano particle synthesis, Silver Nano particles, SEM, XRD, UV-Vis.

1. Introduction

Conventional monolithic materials are broadly classified into three categories: metals, ceramics and polymers.
Human evolution and civilization are closely related to the utilization of the said materials. In the Stone Age man
primarily relied on ceramics to make tools and weapons and on natural polymers. The usage of metals started with

* Corresponding Author
Email: [email protected]

2214-7853 © 2017 Published by Elsevier Ltd.

Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON NANOTECHNOLOGY (ICNANO-2016).
 Shivaji V Banne et al. / Materials Today: Proceedings 4 (2017) 12054–12060 12055

gold and continued with bronze, copper, and iron. Dependency on metals like steel and aluminum started only in the
last century and continue to the present. The newer development and application highlight man-made or engineered
materials whereas earlier man used natural forms of these materials. A new trend is now taking place where
ceramics, polymers, and composites are gaining a much significant importance.
A composite can be defined as “a material consisting of two or more insoluble constituents combined at a
macroscopic level whose mechanical performance and properties are designed to be superior to the constituent
materials independently. One of the constituent is called the reinforcement which is usually discontinuous, stiffer
and stronger while the less stiff phase which is continuous is called matrix”. The reinforcements may be either in the
form fibers or particulate material. The size of the particle may vary from micro to nano meter. This involves a close
conjunction of various branches such as material science, structural design and analysis, mechanics of materials,
nano technology and process engineering.
Nanotechnology is one of the important fields of modern research which involves design, synthesis and
manipulation of particles at the nano level. Nano-materials are the materials which are usually considered to be
materials with at least one external dimension/sizeof the particle measuring 1-100nm. The engineered nano particle
are designed and synthesized for specific properties relating to their shape, size, surface properties and chemistry.
These specific properties are well reflected in the form of colloids, aerosols and powders. The behavioral
dependency of nano particles on surface area is seen to be predominant than the composition of the material. Also,
the principle factor enhancing the strength, hardness, electrical properties and reactivity is observed to be dependent
on the relative surface area.
Production of nano materials is not simply miniaturization of materials. The production requires very different
approaches. There are various methods to produce nano materials. The methods/approaches are broadly classified
into top-down and bottom-up approach. Top down approach involves successive slicing or breaking of the bulk
material into nano particles. This can be achieved by attrition. The method includes various mechanism in which
macro or a micro sized particles are ground in a planetary ball mill, simple ball mill, or other size reducing
mechanism. The nano particles can be separated from the resulting particles by air separation. This method results in
a wide size distribution and diverse particle shape or geometry. Also the resulting particles are more prone to
contamination from impurities. Imperfect surface structure and significant crystallographic damage to the processed
patterns is a major drawback of this method. These imperfections result in additional challenges during design and
fabrication. However, in contrary this approach facilitates bulk production of nano materials. Regardless of the
defects seen in top down approach, they continue to play a significant role in the synthesis of nano particles.
Nomenclature

Notation Description units

m Atomic Mass gm
M Molar concentration molality
Dp Particle Size nm
ƛ Wavelength nm
β Half the Maximum Intensity cps
Bragg angle degree/rad
K Dimensionless shape factor ------

2. Experimentation

2.1 Experimental Setup

The experimental setup required for synthesis the silver nano particles by using wet chemistry method (Burst
method) is as shown in below figure (Fig. No.1). The setup includes 250 ml conical flask with 200 ml of 0.02 M
sodium borohydride solution, 50 ml burette filled with 0.01 M of silver nitrate solution and 2000 ml of ice bath in a
beaker. Conical flask containing sodium borohydride solution is placed in the ice bath for 25-30 minutes. Insert the
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magnetic bead into the conical flask and centre the assembly on to the magnetic stirrer. Adjust the speed of magnetic
stirrer to 700-900 rpm. The setup is as shown in below figure. (Fig. No.1)

Fig. 1 Experimental Setup

2.2 Pre-requisite for the Experiment

Need of Ice Bath and Excess NaBH4: Sodium Borohydride is a very strong reducing agent. At higher temperature
this could react with nitrate ions since reactivity increases with increase in temperature. Also, if hot water is used
hydrogen and borax would be formed and hydrogen would reduce silver ions instead of borohydride ions. In order
to slow down the reaction to an adequate rate and to avoid secondary reactions, cooling is required [2]. This result in
more complete reaction providing finer silver nano particles. Sodium borohydride (NaBH4) is used in excess. This is
required to stabilize the silver (Ag) nanoparticles.

2.3 Experimental Procedure:

• Glassware are cleaned using Alcoholic Potassium Hydroxide (KOH) bath.

• Take aqueous solutions of 0.01M silver nitrate (AgNO3) and freshly prepared 0.02M sodium borohydride
(NaBH4).
• Pour 150 ml of 0.02M sodium borohydride into 250 ml conical flask (Erlenmeyer) using a graduated cylinder.
• Place the conical flask into the ice bath and allow it to cool for about 25-30 min.
• Pour 50 ml 0.01M silver nitrate (AgNO3) in the burette supported by a clamp and ring stand.
• Place the magnetic bead into the conical flask, inline the assembly to the centre of the stir plate and begin the
stirring.
• Add the silver nitrate (AgNO3) solution drop by drop at a rate of about a drop/sec. (After addition of 2ml,
solution should turn dark yellow).
• Stop stirring after all the silver nitrate (AgNO3) solution is added and remove the stir bar.

2.4 Extraction of Silver Nano Particles:

Silver nano particles are denser than other reactants. The conical flask containing the titrated solution is kept
undisturbed for 6-8 hrs to settle the silver nano particles. Silver nano particles get settled down to the bottom of the
conical flask. The other compounds like sodium nitrate (NaNO3) being a salt gets dissolved in the water. Hydrogen
(H2) and diborane (B2H6) are obtained in gaseous state and are evaporated during the reaction is in progress. Hence
 Shivaji V Banne et al. / Materials Today: Proceedings 4 (2017) 12054–12060 12057

only silver nano particles and sodium nitrate (NaNO3) remain in the titrated solution. The solid particles are
separated from the solution by the centrifuge process. The obtained particles are rinsed three to four times by using
distilled water to separate the silver nano particles. The silver nano particles obtained from each titration are
collected in a 100 ml beaker. The particles contain some moisture. Hence to get silver nano particles in a powder
form, the beaker is heated at 70-80 ºC for 15- 20 minutes. Once all the water gets evaporated the fine powder of
silver nano particles remains in the beaker which can be collected into the sample tube.

2.5 Yield per Titration:

The amount of silver by weight which can be extracted per titration is calculated as below,
The amount of silver Nano Particles synthesized per 50 ml of silver nitrate solution titration =

= (107.86*0.16987)/169.87

= 0.108/2

= 0.054 gm.
Reduction of 50 ml of silver nitrate solution with sodium borohydride yields 0.054 gm of silver nano particles.
The time consumed per titration is around 30 minutes.

Chemical Reaction-

AgNO3 + NaBH4 Ag + ½ H2 + 1/2B2H6 + NaNO3 [2]

3. Results and Discussion:

3.1 Characterization of Silver Nano Particles:

The synthesized particles were characterized by various methods such as Ultraviolet–visible spectroscopy (UV-
Vis), Scanning Electron Microscopy (SEM), X-Ray Diffraction Method (XRD) and the results obtained with this
method are discussed below,

3.2 Ultraviolet–Visible Spectroscopy

Ultraviolet Visible Spectroscopy show a well-defined Plasmon band in the range of 800 to 200 nm and a
wavelength between 380 to 395. Shown in fig.-2

Fig. 2. UV-Vis Absorption spectra of silver nano particles solution

12058 Shivaji V Banne et al. / Materials Today: Proceedings 4 (2017) 12054–12060

3.3 Scanning Electron Microscope

The images obtained using scanning Electron Microscope for various magnification factors are as shown below
Fig. No. 3 to 5. The images show particles sizes ranging from 30 to 100 nm. The analysis of silver nano particles is
carried out at Shivaji University Kolhapur (Maharastra). The images obtained from the scanning electron microscope
it is observed that the particle size is in the range of 30-100 nm, this variation in the size is because of agglomeration
of silver nano particles the exact size of silver nano particle can be from XRD method by using scherrers equation
which is calculated and shown below.

Fig. 3. SEM Image indicating Ag particle size at 10000X Magnification

Fig. 4. SEM Image indicating 100nm particle size at 1000X Magnification

Fig. 5. SEM Image indicating Ag particle size at 20000X Magnification

 Shivaji V Banne et al. / Materials Today: Proceedings 4 (2017) 12054–12060 12059

3.4 X-Ray Diffraction

The below plot (Fig. No. 6 & 7) is obtained by plotting the results obtained from the X-Ray diffraction analysis.
The y-axis represents the intensity of light in cycles per second and x-axis represents the 2 angle. The analysis of
silver nano particles is carried out at Shivaji University Kolhapur (Maharastra). From the graph it is observed that
the maximum peak is observed at an intensity around 36950 cps and the maximum 2ө angle is 38.3°, the obtained
data can be used to calculate the silver nano particle size by using scherrers equation
4000
3500
Intensity (a.u.)

3000
2500
2000
1500
Series1
1000
500
0
0 20 40 60 80 100
2 Theta (degree)

Fig. 6 X-Ray Diffraction Plot

4000
Intensity (a.u.)

3000

2000
Series1
1000

0
37.5 38 38.5 39
2 Theta (degree)

Fig. 7 XRD Image of pure Silver Nano Particles showing Magnified Peak

3.5 Calculation of particle size from X-Ray Diffraction Plots:

The crystalline size is calculated from half-height width of diffraction peak of XRD pattern as shown in below
graph. After plotting XRD plots, the particle size of tested sample can be calculated by using scherrers equation:
Scherrers equation for calculation of particle size is

∗ƛ
Dp =
∗

Where k is a dimensionless shape factor,

ƛ is a X-ray wavelength;
β is the line broadening at half the maximum intensity,
ө is the Bragg angle.
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Substituting the values the calculations were preceded as follows-

ƛ= 0.154 x 10-9
k= 0.9
Intensity at maximum peak = 36900 cps
Angle at the peak 2 = 38.3°
Half of the intensity = 18450 cps
Full length at half maximum
β = 38.45-38.20 = 0.25°
= 4.363 x 10-3 radians

. .154 ^
Dp = . = = 33.63 X 10-9 = 33.63 nm
.
So, the particle size of the silver nano particle obtained from the X-Ray diffraction method is 33.63 nm.

4. Conclusion

In this study it is investigated that the Burst method is suitable process to synthesize silver nano particles. It has
been studied that agglomeration of the obtained silver nano particles can be avoided by addition of small amount of
polyvinylepyrrolidone (PVP) solution. The rate of reduction of silver nitrate using sodium borohydride as a reducing
agent can be controlled by placing sodium borohydride in an ice bath prior to the experiment. Silver nano particles
can be characterized by various method which include Ultraviolet Visible Spectroscopy, X-Ray Diffraction and
Scanning Electron Microscopy. Ultraviolet Visible Spectroscopy show a well-defined Plasmon band in the range of
800 to 200 nm and a wavelength between 380 to 395. Scanning electron microscopy shows the synthesized nano
particle size to be in the range of 30 to 100 nm. Using X-Ray diffraction technique report plots for intensity versus
2θ angle peak is observed at an angle 38.3º. Using this data into scherrers equation the particle size is found to be
33.6nm.

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