A MSC Physics Project
A MSC Physics Project
A MSC Physics Project
Entitled
“SYNTHESIS OF SILVER NANO PARTICLES AND THE EFFECT OF NaCl
ON THE ZETA POTENTIAL”
By
Dip Chatterjee
Exam roll no. - MPE1632005
M.Sc. Physics
JADAVPUR UNIVERSITY
1
Acknowledgement
I would also like to thank Mr. Animesh Halder and Mr. Pabitra Maity for
their endless help, support and cooperation. I am deeply indebted to him.
I would like to express my heartfelt thanks to other lab members for their
support and many useful suggestions.
I would also like to thank all the members of Physics Department for giving
me such a wonderful opportunity to work here.
2
Department of Physics, Jadavpur University, Kolkata – 700032.
Certificate
This is to certify that the project entitled “Synthesis of silver nano particles and the effect
3
CONTENTS:
Chapter 1
Introduction
Silver nanoparticles
Uses of silver nano particles
Chapter 2
Chapter 3
Experimental Techniques
Dynamic Light Scattering
4
Chapter 4
References
5
Chapter 1
Introduction
Nanoparticles are of great scientific interest as they are
effectively a bridge between bulk materials and atomic
or molecular structures. A bulk material should have
constant physical properties regardless of its size, but at
the nanoscale, size-dependent properties are often
observed. Thus, the properties of the materials change
as their size approaches the nanoscale and the
percentage of atoms at the surface of a material
becomes significant. For bulk materials larger than one
micrometre the percentage of atoms at the surface is
insignificant as compared to the number of atoms in the
bulk of the material. Over the last decades silver
nanoparticles have found applications in catalysis,
optics, electronics and other areas due to their unique
size-dependent optical, electrical and magnetic
properties. Currently most of the applications of silver
nanoparticles are in antibacterial/antifungal agents in
biotechnology and bioengineering, textile engineering,
water treatment, and silver-based consumer products.
6
Silver nanoparticles
8
Zeta potential
9
between the dispersion medium and the stationary layer of fluid
attached to the dispersed particle. The zeta potential is caused
by the net electrical charge contained within the region bounded
by the slipping plane, and also depends on the location of that
plane. Thus it is widely used for quantification of the magnitude
of the charge.
11
addition of a suitable polymer. However it can be difficult to
subsequently flocculate the system if this is required, the
polymer can be expensive and in some cases the polymer is
undesirable e.g. when a ceramic slip is cast and sintered, the
polymer has to be ‘burnt out’. This causes shrinkage and can
lead to defects.
Electrostatic or charge stabilization has the benefits of
stabilizing or flocculating a system by simply altering the
concentration of ions in the system. This is a reversible
process and is potentially inexpensive. It has long been
recognised that the zeta potential is a very good index of
the magnitude of the interaction between colloidal particles
and measurements of zeta potential are commonly used to
assess the stability of colloidal systems.
12
The magnitude of the zeta potential gives an indication of
the potential stability of the colloidal system. A colloidal
system is when one of the three states of matter: gas, liquid
and solid, are finely dispersed in one of the others. For this
technique we are interested in the two states of: a solid
dispersed in a liquid, and a liquid dispersed in a liquid, i.e. an
emulsion. If all the particles in suspension have a large
negative or positive zeta potential then they will tend to repel
each other and there is no tendency to flocculate. However, if
the particles have low zeta potential values then there is no
force to prevent the particles coming together and flocculating.
The general dividing line between stable and unstable
suspensions is generally taken at either +30mV or -30mV.
Particles with zeta potentials more positive than +30mV or
more negative than -30mV are normally considered stable.
13
(1) pH
In aqueous media, the pH of the sample is one of the most
important factors that affects its zeta potential. A zeta potential
value on its own without defining the solution conditions is a
virtually meaningless number. Imagine a particle in suspension
with a negative zeta potential. If more alkali is added to this
suspension then the particles tend to acquire more negative
charge. If acid is added to this suspension then a point will
bereached where the charge will be neutralised. Further
addition of acid will cause a build up of positive charge.
Therefore a zeta potential versus pH curve will be positive at
low pH and lower or negative at high pH. There may be a point
where the plot passes through zero zeta potential. This point is
called the isoelectric point and is very important from a practical
consideration. It is normally the point where the colloidal
system is least stable. A typical plot of zeta potential versus pH
is shown in figure. In this example, the isoelectric point of the
sample is at approximately pH 5.5. In addition, the plot can be
used to predict that the sample should be stable at pH values
less than 4 (sufficient positive charge is present) and greater
than pH 7.5 (sufficient
negative charge is present). Problems with dispersion stability
would be expected at pH values between 4 and 7.5 as the zeta
potential values are between +30 and -30mV.
Figure :Typical plot of zeta potential versus pH showing the position of the isoelectric point and the
pH values where the dispersion would be expected to be stable
2. Conductivity
14
ions will also influence double layer thickness. A trivalent ion such
as Al3+ will compress the double layer to a greater extent in
comparison with a monovalent ion such as Na+. Inorganic ions
can interact with charged surfaces in one of two distinct ways (i)
non- specific ion adsorption where they have no effect on the
isoelectric point. (ii) specific ion adsorption, which will lead to a
change in the value of the isoelectric point. The specific
adsorption of ions onto a particle surface, even at low
concentrations, can have a dramatic effect on the zeta potential
of the particle dispersion. In some cases, specific ion adsorption
can lead to charge reversal of the surface.
Electrokinetic Effects
An important consequence of the existence of electrical
charges on the surface of particles is that they will exhibit
certain effects under the influence of an applied electric field.
These effects are collectively defined as electrokinetic effects.
There are four distinct effects depending on the way in which
the motion is induced. These are: Electrophoresis : The
movement of a charged particle relative to the liquid it is
suspended in under the influence of an applied electric field.
Electroosmosis : The movement of a liquid relative to a
15
stationary charged surface under the influence of an electric
field. Streaming potential : The electric field generated when
a liquid is forced to flow past a stationary charged surface.
Sedimentation potential : The electric field generated when
charged particles move relative to a stationary liquid.
Electrophoresis
When an electric field is applied across an electrolyte,
chargedparticles suspended in the electrolyte are attracted
towards the electrode of opposite charge. Viscous forces acting
on the particles tend to oppose this movement. When
equilibrium is reached between these two opposing forces, the
particles move with constant velocity. The velocity is dependent
on the strength of electric field or voltage gradient, the dielectric
constant of the medium, the viscosity of the medium and the
zeta potential. The velocity of a particle in a unit electric field is
referred to as its electrophoretic mobility. Zeta potential is
related to the electrophoretic mobility by the Henry equation:-
16
molar salt. For small particles in low dielectric constant media
(eg non-aqueous media), f(ka) becomes 1.0 and allows an
equally simple calculation. This is referred to as the Huckel
approximation.
Chapter 2
17
AgNO3 + NaBH4 → Ag + 1/2H2 + 1/2B2H6 + NaNO3
The method used in the procedure for this experiment
produces
nanoparticles that are about 10-14 nm in diameter.
Procedure
18
Step 7: Now AgNO3 solution is taken in a clean bottle &
placed on the Stirer then 10 cm3 NaBH4 solution is added drop by
drop.
Aggregation of Ag nanoparticles
The Ag nanoparticles that form are stabilized by a protective
layer of borohydride ions.
Salts such as NaCl or KI shield the negative charges allowing
the particles to clump
together to form aggregates. To prevent aggregation the
nanoparticles can be coated with a polymer such as polyvinyl
pyrrolidone (PVP) .
19
Chapter 3
Experimental Techniques
20
purposes of size measurement (but not thermodynamics!) the
distinction between a molecule (such as a protein or macromolecule)
and a particle (such as nanogold) and even a second liquid phase
(such as in an emulsion) becomes blurred. Dynamic light scattering
can also be used as a probe of complex fluids such as concentrated
solutions. However, this application is much less common than
particle sizing.
21
η is dynamic viscosity (we know this)
The calculations are handled by instrument software. However, the
equation does serve as important reminder about a few points. The
first is that sample temperature is important, at it appears directly in
the equation. Temperature is even more important due to the
viscosity term since viscosity is a stiff function of
temperature. Finally, and most importantly, it reminds the analyst
that the particle size determined by dynamic light scattering is the
hydrodynamic size. That is, the determined particle size is the size of
a sphere that diffuses the way as your particle.
For those who work with protein sizing and other areas where
hydrodynamic radius is more commonly used, note that the
development here is around diameter. Radius calculations are the
same except for a factor of two.
Also, a note to those interested in polymer size. The hydrodynamic
radius is not the same as the radius of gyration. Hydrodynamic sizes
are more easily measured than radii of gyration and can be
measured over a wider range of sizes. The conversion from
hydrodynamic radius to radius of gyration is a function of chain
architecture (including questions of random coil vs. hard sphere,
globular, dendrimer, chain stiffness, and degree of branching.
22
Chapter 4
Experimental Results
23
Figure: Size distribution by intensity of Ag nano particle
24
Figure: zeta potential distribution of Ag nano particles
Preperation:
Step 1: Silver nano particles are prepared by above mentioned
Chemical Reduction method.
25
Step2: A 500 mM stock solution of NaCl has been prepared by
adding 584 mg NaCl with 20 cc water.
Step3: Different concentration of NaCl solution of Silver nano
particles has been prepared by adding the different volumes of NaCl
stock solution drop by drop to the newly prepared Ag nano particles
solution.
Added volume of Ag Added volume of Concentration of
nano particles NaCl stock solution NaCl in new solution
solution
4.9 ml 0.1 ml 10 mM
4.5 ml 0.5 ml 50 mM
4.0 ml 1.0 ml 100 mM
3.0 ml 2.0 ml 200 mM
2.0 ml 3.0 ml 300 mM
1.0 ml 4.0 ml 400 mM
26
Conc. Of Mean zeta Average size Stability
NaCl in potential of of Ag nano behaviour
Ag nano Ag nano particles in
particle particle nm
solution in solution in
mM mV
0 -38.2 233.7 Moderate stability
10 -28.8 272.0 Incipient instability
50 -43.5 135.1 Good stability
100 -21.3 - Incipient instability
200 -14.5 274.9 Incipient instability
300 -15.1 459.5 Incipient instability
400 -18.1 858.4 Incipient instability
From the above table it can be seen that the zeta potential is
highest at 50 mM NaCL solution of Silver nano particles. And
after that increase in ionic strength led to increased aggregation
of the chemically synthesized nano particle. This experiment
was to observe the stability of size of the Silver nano particles so
it was done after some days of preparation and it can be
osreved from the table above that higher the zeta potential the
stability is good and the size of the nano particles is lesser.
27
Figure: Zeta potential distribution graph of 0 mM NaCl solution of Ag nano
particles
28
The graph of zeta potential vs Conc. of NaCl in Ag nano particle
solution is shown below
29
From the two graphs above it is clear that when zeta potential is
higher the size of the nano particles is much lesser so we can
see that zeta potential plays a very important role in determining
the stability of the nano particles. The nanoparticles were stable
after the addition of aqueous solution of NaCl till 50 mM solution
but too much aqueous NaCl solution would reduce the stability
of the nano particles. As the ionic strength increases, the
electrical double layer around the AgNP s might be more tightly
compressed by screening the surface charge of the AgNP s,
which allows greater degree of particle particle interaction
resulting in an increase in the level of aggregation for particle
setting.
Conclusion
Nanotechnology has helped in overcoming the limitations of
size and can change the outlook of the world regarding science.
Synthesis of silver nanoparticles has become possible using
NaBH4 as a reducing agent and using AgNO3as a reductant.
These gave dark yellowish colour when synthesised by a
protective layer of borohydride ions. The Ag solution became
yellowish in colour because of absorption of wavelength at
386nm. As Silver nanoparticles are very delicate to the absorption
of light, they interact with light due to very high dielectric constant
that makes the light response occur in the visible region. Particle
size distribution measurements reveal the re-crystallization of the
primary silver nanoparticles occurs after the addition of aqueous
NaCl solution (over 100 mM). Silver nanoparticles are harmful to
the environment. Many consider silver to be more toxic than other
metals when in nanoscale form and that these particles have a
different toxicity mechanism compared to dissolved silver.
Scientists have concluded that nanoparticles can pass easily into
cells and affect cellular function, depending on their shape and
30
size. Silver nanoparticles are a continuous source of ions that
could be toxic for aquatic organisms that are swimming around or
in the sediment. Silver nanoparticles are the most common
commercialized nano technological product on the market. But it
should be used in a controlled manner.
References
★ Antimicrobial Effects of Silver Nanoparticles”. Center for
Nanoscale Chemical-Electrical-Mechanical Manufacturing
Systems.
★ http://pubs.rsc.org/en/Content/ArticleLanding/2011/CE/c0ce007
76e#!divAbstract
★ Zetasizer Nano series technical note Malvern
★ Intermolecular and surface forces,3rd edition by Jacob
Israelachvili
★ K.S.Chou, C.Y. Ren/ Materials Chemistry and physics 64(2000)
241-246
★ Z Khan et al. / colloids and Surfaces B: Biointerfaces 82(2011)
513-517
★ H Wang et al. / Colloids and Surfaces A: Physicochem. Eng.
Aspects 256(2005) 111-115
★ MEHR et al., Orient. J. Chem., Vol. 31(3), 1831-1833 (2015)
★ Berne, B.J.; Pecora,R /Dynamic Light Scattering Courier Dover
Publications (2000)
★ Shaw, D.J. (1992) Introduction To Colloid And Surface
Chemistry,Butterworth Heinemann, UK
★ Ross, S. and Morrison, I.D. (1988) Colloidal Systems and
Interfaces ,John Wiley and Sons, USA.
★ Influence of silver nanoparticles on neurons and blood-brain
barrier via subcutaneous injection in rats. (Applied Surface
Science, 2008
31
32