M.Sc.

Project Report
On
A STUDY ON CONCENTRATION VARIATION OF
DIFFERENT MOLECULAR WEIGHT AND NaCl
VARIATION OF AQUEOUS POLYACRYLAMIDE
SOLUTION USING DYNAMIC LIGHT SCATTERING
METHOD
Submitted for

Partial Fulfilment of the Requirement for the Degree of

Master of Science In Physics
By

PRADOSHA KUMAR SAHOO

M.Sc. 4TH Semester
Roll No.-2021PHM017
Department of Physics
Indian Institute of Engineering Science and Technology, Shibpur
Under the supervision of

DR. MOJAMMEL HAQUE MONDAL

Department of Physics
Indian Institute of Engineering Science and Technology, Shibpur

1
 Declaration

I, PRADOSHA KUMAR SAHOO, a student of the Fourth semester of two years

M.Sc. course in Physics, have carried out the project paper entitled “A STUDY
ON CONCENTRATION VARIATION OF DIFFERENT MOLECULAR
WEIGHT AND NaCl VARIATION OF AQUEOUS POLYACRYLAMIDE
SOLUTION USING DYNAMIC LIGHT SCATTERING METHOD”, under
the supervision of Dr. Mojammel Haque Mondal, as a part of my M.Sc. course in
the Department of Physics, Indian Institute of Engineering Science & Technology,
Shibpur, Howrah.

IIEST,Shibpur Pradosha Kumar Sahoo

26th JUNE, 2023 2021PHM017

2
 CERTIFICATE
This is to certify that the term paper entitled “A STUDY ON
CONCENTRATION VARIATION OF DIFFERENT MOLECULAR
WEIGHT AND NaCl VARIATION OF AQUEOUS POLYACRYLAMIDE
SOLUTION USING DYNAMIC LIGHT SCATTERING METHOD” is a
bonafide record of work, done by PRADOSHA KUMAR SAHOO (Roll No.-
2021PHM017), a student of fourth semester of the two years M.Sc. course in
Physics, under the supervision of Dr. Mojammel Haque Mondal. This report is
submitted for the partial fulfilment of the requirements for the degree of M.Sc. in
Physics of Indian Institute of Engineering Science and Technology, Shibpur.

Dr. Mojammel Hauqe Mondal

Supervisor,
Department of Physics
IIEST, Shibpur

Dr. Syed Minhaz Hossain

Head of the Department,
Department of Physics,
IIEST, Shibpur

3
 ACKNOWLEDGEMENT
It is my pleasure to acknowledge all the help, inspiration & encouragement
received during the progress of this report and I take this opportunity to express my
heartfelt gratitude to Dr. Mojammel Haque Mondal, Assistant Professor,
Department of Physics, Indian Institute of Engineering Science and Technology,
Shibpur, for his valuable advice, resourceful guidance, active supervision, and
constant encouragement. I am thankful to Mr. Subrata Mahata, PhD Scholar,
IIESTS for his kind help and guidance during experiment and analysis of results. I
am also thankful to my seniors and classmates for useful information and advice.

IIEST, Shibpur Pradosha Kumar Sahoo

26th JUNE,2023 M.Sc. 4th Semester
2021PHM017

4
 CONTENTS

1. Introduction
2. A Brief Recapitulation of DLS
3. Experimental
A. Sample Preparation
B. Dynamic Light Scattering
4. Results and Discussion
5. Conclusion
6. Reference

5
1.Introduction
In the arsenal of techniques for characterizing polymers and suspensions of solids, dynamic light
scattering (DLS) is one of the more powerful weapons. Dynamic light scattering (DLS) has been
widely used in physical chemistry, colloid chemistry, polymer science, biochemistry and
biophysics, medical science, etc., as well as product development and quality inspection in
industry. Although its most common use may be for determining the hydrodynamic radius of
particles in suspension, its major strength lies in its ability to measure molecular weights and
interactions of polymers in solution. As the name suggests, dynamic light scattering deals with
the study of how coherent light, scattered by a solution containing diffusing particles, changes
with time. The time-correlation function of these scattered intensities provides information about
not only the diffusivity of the suspended particles but also their size.
In the 1960s, Hanbury Brown and Twiss were the first to realize that the time-correlation
function of scattered laser light could be used to determine the radii of radio stars. The rapid
improvement in and availability of continuous lasers and fast photon detectors then promoted the
rapid development of DLS for measurement of the size or radius of gyration of colloids,
macromolecules, viruses or synthetic and biological molecules in the range of a few nm up to a
few μm in diameter.
In typical DLS method a well-defined parallel beam of coherent laser light is directed onto a
sample solution. Most of the beam will travel through the sample and hit the screen, placed a
definite distance away from the sample. One might assume that the intensity imaged on the
screen will decay away smoothly from the center, but this is not what is seen for a fluid sample
containing scattering particles. Instead, there will be many speckles, which are tiny but
macroscopically visible light dots that move continuously around the screen. Moreover, these
speckles will be visible at all scattering angles, 𝜃, that lie in the plane of the incoming and the
un-scattered outgoing beam, and also out of plane. The appearance of speckles is caused by
constructive interference of the incoming light scattered by individual particles. As the particles
diffuse in time, the conditions for constructive interference change, making the speckles move.
The heart of DLS lies in measurement of the intensity of a speckle in time with a fast, 'point-like'
detector under a fixed scattering angle, 𝜃.

Fig 1.1 Schematic diagram of DLS setup

6
Experimental studies of dilute, semi-dilute, and concentrated polymer solutions in past few
decades have been investigated by Dynamic Light Scattering technique that measures the
correlation functions of the scattered light intensity with certain delay times. One can extract the
relaxation times that characterize the dynamics of the process from these correlation functions.
Polymer gels are three-dimensional polymer networks swollen by solvent. They can be prepared
by polymerization of multifunctional monomers or by cross-linking of existent polymer chains.
Depending on whether the cross-links are formed by physical junctions or covalent bonds, the
resulting network is termed a physical gel or a chemical gel. In contrast most of the existing
scientific literature of polymer solutions are concentrated on hydrodynamic size distribution.
Basically, DLS applications on polymer solutions are done varying the molecular weight or
concentration of the solution. In this report, the concentration was varied of polymer solution
with constant molecular weight for application of DLS. The polymer solution lies in three
different regions based on the concentration of the solution. They are respectively dilute, semi-
dilute and concentrated region. The solution in dilute region have concentration not more than 2
mg/ml. Solution with 2-3 mg/ml concentration lies in overlapping region and more than that lies
in semi-dilute region. In the experiment measurements in dilute and semi-dilute regions are taken
as well as varying scattering angle. In dilute region the chosen concentrations for experiments
were 0.3,0.9 and 2 mg/ml and 4,6 and 7 mg/ml in semi-dilute region. One more type of synthesis
was done, with adding different molar solutions of NaCl in polymer solution of different
concentration of dilute and semi-dilute regions. All the measurements were done with two
scattering angles, 175⁰(front scattering) and 90⁰(side scattering). Temperature during all the
measurements was 25⁰C.

7
2. A Brief recapitulation of DLS
What is DLS?
When light “hits” a small object (a particle or a molecule), and thereby changes its direction, the
thing that happens is called light scattering. If, on the other hand, the light disappears by the
encounter with the particle we call the phenomenon absorption. So, in essence, you can say that
light – like all other kinds of electromagnetic radiation (radio waves, micro waves, heat
radiation, ultraviolet radiation, X-rays, gamma radiation) – em interacts with matter in two ways:
1. Absorption: the photons (the light) disappear, 2. Scattering: the photons change their direction.
Here we shall deal only with scattering. And only scattering from particles placed (and moving)
randomly in relation to each other i.e. dissolved in a solvent. If light is being scattered from
ordered particles this can cause such phenomena as reflection, refraction or diffraction. Both of
the abovementioned interactions will cause a light beam to be attenuated when passing through a
solution of particles. It doesn’t matter whether light is being attenuated by scattering or
absorption, in both cases the transmitted intensity will decrease exponentially with the thickness
of the material the light is passing through.
Dynamic Light Scattering (sometimes referred to as Photon Correlation Spectroscopy or Quasi-
Elastic Light Scattering) is a technique for measuring the size of particles typically in the
submicron region. DLS measures Brownian motion and relates this to the size of the particles.
Brownian motion is the random movement of particles due to the bombardment by the solvent
molecules that surround them. Normally DLS is concerned with measurement of particles
suspended within a liquid. The larger the particle, the slower the Brownian motion will be.
Smaller particles are kicked further by the solvent molecules and move more rapidly. An
accurately known temperature is necessary for DLS because knowledge of the viscosity is
required, because the viscosity of a liquid is related to its temperature. The temperature also
needs to be stable, otherwise convection currents in the sample will cause non-random
movements that will ruin the correct interpretation of size. The velocity of the Brownian motion
is defined by a property known as the translational diffusion coefficient D.
What can be measured by DLS?
• Hydrodynamic radius. Range: 1 to 1000 nm
• Relaxation times in gel systems
How DLS works?
In dynamic light scattering, the speed at which the particles are diffusing due to Brownian
motion is measured. This is done by measuring the rate at which the intensity of the scattered
light fluctuates when detected using a suitable optical arrangement.
Imagine if a cuvette, containing particles which are stationary, is illuminated by a laser and a
frosted glass screen is used to view the sample cell. A classical speckle pattern would be seen.
The speckle pattern will be stationary both in speckle size and position because the whole system
is stationary. The dark spaces are where the phase additions of the scattered light are mutually
destructive and cancel each other out. The bright blobs of light in the speckle pattern are where
8
the light scattered from the particles arrives with the same phase and interfere constructively to
form a bright patch.

Fig 2.1 Schematic representation of a speckle pattern

For a system of particles undergoing Brownian motion, a speckle pattern is observed where the
position of each speckle is seen to be in constant motion or fluctuating. This is because the phase
addition from the moving particles is constantly evolving and forming new patterns. The rate at
which these intensity fluctuations occur will depend on the size of the particles.
The reason for these fluctuations is that the particles (molecules) that scatter the light, move
randomly relative to each other through diffusion or Brownian motion. Small particles move fast
and large particles move slowly. The intensity of scattered light fluctuates: Rapidly if the
particles are small and slowly if the particles are large. The characteristic fluctuation time is
directly related to the size of the particles. Size here means physical dimensions, not mass or
molecular weight. What is actually determined in a dynamic light scattering measurement is the
so-called diffusion coefficient D of the particles, a measure of how fast they move about in the
solution. The unit of the diffusion coefficient is m2.s-1. Of course, the diffusion coefficient can in
turn be related to the size of the particles.
DLS employs measurement of the scattered intensity at very short time intervals (e.g. 200 ns). A
measurement usually takes 1-10 minutes and thus implies the measurement of the intensity
1,000,000,000 times. The measurement is normally done only at one scattering angle. The
weight concentration of the dissolved particles does not need to be known. The only information
extractable from such a measurement is the diffusion coefficient of the dissolved particles. Or
actually, the distribution of diffusion coefficients if there are more than one type of particles
present in the sample. The diffusion coefficient(s) can be interpreted in terms of particle sizes
(i.e. dimensions, not molecular weight) if the temperature and the viscosity of the solvent is
known.

9
Experimental Setup
The laser passes through a collimator lens and then hits the sample cell with the solution. The
light is scattered and detected by a photomultiplier that transform a variation of intensity into
a variation of voltage.

Fig 2.2 Schematic diagram of DLS experimental setup

The DLS setup uses a LASER as a monochromatic source of light. Sample is placed between the
laser source and detector. There are multiple detectors in a single DLS setup for flexibility.
Multiple detectors are incorporated with the same instrument to expand dynamic ratio. i.e. the
ratio of largest to smallest particle size. There are detectors at 15⁰,90⁰ and 175⁰ to measure
forward, side and backward scatterings respectively. A correlator is basically a signal
comparator. It is designed to measure the degree of similarity between two signals, or one signal
with itself at varying time intervals.
Basically, to extract the useful information from the intensity fluctuation we have to do
calculation in a large basis i.e., about 1,500,000,000 multiplications and 1,500,000,000 additions
in every second. This cannot yet be done by an ordinary PC so it is necessary to use specialized
hardware, a digital autocorrelator which is connected to a PC. Autocorrelators can be made as
expansion boards for desktop PS’s or as stand-alone boxes.
How a correlator works
If the intensity of a signal is compared with itself at a particular point in time and a time much
later, then for a randomly fluctuating signal it is obvious that the intensities are not going to be
related in any way, i.e., there will be no correlation between the two signals. However, if the

10
intensity of signal at time = t is compared to the intensity a very small time later (t+ẟt), there will
be a strong relationship or correlation between the intensities of two signals. The two signals are
strongly or well correlated.
If the signal intensity at t is compared with itself then there is perfect correlation as the signals
are identical. Perfect correlation is indicated by unity (1.00) and no correlation is indicated by

zero (0.00).
Fig 2.3 Schematic showing the fluctuation in the intensity of scattered light as a function of time
If the signals at t+2ẟt, t+3ẟt, t+4ẟt etc. are compared with the signal at t, the correlation of a
signal arriving from a random source will decrease with time until at some time, effectively t
=ꚙ, there will be no correlation. If the particles are large the signal will be changing slowly and
the correlation will persist for a long time. If the particles are small and moving rapidly then
correlation will reduce more quickly.

Fig 2.4 Typical correlogram from a sample containing large particles(left) and small particles(right)

11
Correlation function and Siegert Relation
According to the semi-classical light scattering theory, when light
impinges on matter, the electric field of the light induces an oscillating polarization of
electrons in the molecules. Hence the molecules provide a secondary source of light and
subsequently scatter light. The frequency shifts, the angular distribution, the polarization, and
the intensity of the scatter light are determined by the size, shape and molecular interactions
in the scattering material. With the aid of electrodynamics and theory of time dependent
statistical mechanics, we can get information about the structure and molecular dynamics of
the scattering medium through the light scattering characteristics of the system. Different
methods can be used to study the dynamics of a system with particles in Brownian motion,
depending on the time scale of the molecular fluctuations. The dynamic information of the
particles is derived from an autocorrelation of the intensity trace recorded during the
experiment. The second order autocorrelation equation is generated from the intensity trace
as follows:
<𝐼𝑠 (𝑞,0)𝐼𝑠∗ (𝑞,𝜏)>
g(2)(q,τ)= <𝐼𝑠 (𝑞,0)2 >

The first order correlation function is given by

<𝐸(𝑞,0)𝐸 ∗ (𝑞,𝜏)>
g(1)(q,τ)= <𝐼𝑠 (𝑞,0)>

The two correlation equations are related as

g(2)(q,τ)= 1+ β(g(1)(q,τ))2
where the parameter β is a correction factor that depends on the geometry and alignment of the
laser beam in the light scattering setup.
The functional form of the decay of g(1)(q,τ) depends on the dynamics of the scatterers. Different
dynamical processes leads to different functional forms for the decay of g(1)(q,τ). E.g. for a
diffusive process in a monodisperse system
2
g(1)(q,τ)=𝑒 −𝐷𝑞 𝜏 .
2
So g(2)(q,τ)=1+β(𝑒 −𝐷𝑞 𝜏 )2
Here 𝜞=Dq2, where 𝜞 is the decay rate.
4πn
q is the scattering vector defined by q= sin(θ/2)
λ

where λ is the incident laser wavelength, n is the refractive index of the sample and θ is angle at
which the detector is located with respect to the sample cell.
Here D is the diffusion coefficient and we can get the hydrodynamic size of the diffusing particle
from it by Stokes-Einstein relation given by

12
 𝑘 T
𝐵
D= 6𝜋𝜂𝑅
ℎ

Where 𝑘𝐵 is Boltzmann's constant, T is the temperature in K, and η is the solvent viscosity.

In most cases, samples are polydisperse. Thus, the autocorrelation function is a sum of the
exponential decays corresponding to each of the species in the population. So,
g(1)(q,τ)=∑∞
𝑖=0 𝐺𝑖 (Γ𝑖 )𝑒
−Γ𝑖 𝜏
=∫ 𝐺(Γ)𝑒 −Γτ 𝑑Γ
Since G(Γ) is proportional to the relative scattering from each species, it contains
information on the distribution of sizes.

3.Experimental
A1. Sample Preparation-I
Polyacrylamide (PAM) is a polymer with formula (-CH2CHCONH2-). It has a linear-chain
structure. PAM is highly water-absorbent, forming a soft gel when hydrated. It has chemical
formula (C3H5NO)n.

Fig 3.1 Structure of Polyacrylamide

The test tubes, funnels, cuvettes and containers were washed at first with potassium
permanganate (KMnO4) and then with ethanol and then with distilled water. At first as
per the desired concentration of the solution certain amount of PAM of a particular
molecular weight was weighted in the weight measuring instrument. Here the molecular
weight of the polymer used is 5 − 6 × 106 gm/mole. Then it was added into appropriate
amount of water taken in a container. The mixture was stirred well and kept for 5-6 days
to dissolve the solute perfectly. Then the different concentration solutions were marked
with their concentration for identification. In this process solutions of different
concentrations of NaCl prepared and mixed with prepared polymer solution of two
different concentrations of polyacrylamide in dilute and semi-dilute regions and stirred
well. Different molar solution of NaCl like 0.05,0.5 and 2 M solutions were prepared in
this process.
At the time of experiment cuvettes are washed properly (2-3 times) with distilled water to
confirm there is no dust particle inside it. Then required amount of polymer solution was

13
 taken in the cuvette. It was made sure that no air bubbles are inside the cuvette and it was
placed in the cuvette holder of DLS instrument.

A2. Sample Preparation-II

Here Three types of polyacrylamides were taken of different molecular weights. They are named
PAM1,PAM2 and PAM4 having molecular weights of 5-6 × 106 ,1.5 × 105 ,4 × 104 gm/mole,
respectively. The test tubes, funnels, cuvettes, plastic containers, and other necessary
components were washed at first with potassium permanganate (KMnO4) and then with ethanol
and then with distilled water. The desired amount of solvent that is deionized water, was taken in
respective plastic containers. Then calculated amount of polyacrylamide was measured with
weighing machine and was added with water. The solution was stirred well and kept for a week
to dissolve. For this experiment three concentrations of polyacrylamide respectively 0.3,0.5 and
0.7 mg/ml were prepared for all three types of molecular weights mentioned above.
Before taking measurements, cuvettes are washed properly (2-3 times) with distilled water to
confirm there is no dust particle inside it. Then the required amount of polymer solution was
taken in the cuvette. It was made sure that no air bubbles were inside the cuvette, and it was
placed in the cuvette holder of DLS instrument.

Fig 3.2 Sample Solution in containers

14
 Fig 3.2 Sample solution in a cuvette

B. Dynamic Light Scattering

The dynamic light scattering experiments were performed using Litesizer 500. In this instrument
laser light of wavelength 658 nm from a single frequency laser diode, providing 40 mW was
used. The instrument setup, data record and analysis were done using ISO 22412 model in
Kalliope software. Measurements were taken with 175⁰ (back scatter) and 90⁰ (side scatter) with
all the samples. Temperature was set to 25⁰C and same for all the samples. Cuvettes used were
made of polystyrene. Cuvettes were filled up to half with respective samples and put in the
cuvette holder of the DLS instrument. Equilibration time for temperature was set to 10 minutes.
A single dataset consists of hundred numbers of measurements of 10 second runtime each. And
one data set is for one scattering angle. So, for all samples stated above, two datasets were
recorded for each (175⁰ and 90⁰).

Fig 3.3 Litesizer 500 Particle Analyzer

15
The software measures the second order or intensity correlation function g(2)(t). The second order
correlation function is related with first order or electric field autocorrelation through Siegert
relation. Several experimental DLS studies on complex polymer systems have revealed the
existence of two relaxation modes, and the nonexponential behavior of the autocorrelation
function can be analyzed by a stretched exponential function. Even in dilute polymer solutions,
the decays of the correlation functions have been found to be bimodal because of crosslinking
reaction. In this experiment, both modes exhibit a nonexponential feature, and therefore the
correlation functions were fitted to a double stretched exponential function given by
2
(2) 𝑡 𝛽 𝑡 𝛾
𝑔 (𝑡) = 𝑦0 + 𝑐 (𝐴1 exp [− ( ) ] + 𝐴2 exp [− ( ) ])
𝜏1 𝜏2

Where c is an instrumental parameter. The parameters A1 and A2 are the amplitudes of first and
slow relaxation modes respectively with A1+A2=1. The variables τ1 and τ2 are relaxation times of
two respective modes. And β (0 < β ≤ 1) and γ (0 < γ ≤ 1) measure of the widths of the
distributions of relaxation times known as stretch exponential. The width of the distribution
decreases as the stretched exponent approaches 1. The mean relaxation times are given by
τ1 1 τ2 1
τ1m= 𝛽 Γ (β) τ2m= γ Γ (γ)

1 1 1 1
Where Γ (β) and Γ (γ) are the Gamma functions of and . In the analysis of the correlation
β γ
function data, a nonlinear fitting algorithm (a modified Levenberg-Marquardt method) was
employed to obtain best-fit values of the parameters A1, A2, τ1, τ2 and γ. The values of β
determined in this study were always close to 1 (β > 0.8), but in order to account for
polydispersity effects, this parameter was allowed to float in the fitting process. The values of the
stretched exponent γ, representing the slow relaxation mode, depends upon the concentration of
polymer solution as well as concentration of NaCl in polymer solution. Hence, fast relaxation
mode is characterized by narrow distribution of relaxation times and slow mode is sometimes
narrow and sometimes wide distributions depending upon the concentration of polymer and
NaCl.
Analysis of the time correlation functions of the concentration fluctuations have shown that the
relaxation time related to slow mode is related to diffusion coefficient, D(τ-1=Dq2). Where q is
the scattering vector. The Stokes-Einstein relation is modified as D=kBT/6πηξ, where kB is the
Boltzmann constant, η is the viscosity of the solvent at temperature T, ξ is the hydrodynamic
correlation length, which is inversely proportional to the polymer concentration and independent
of the molecular weight. Also, relaxation time of fast mode is related to a diffusion coefficient,
which will give the hydrodynamic radius of the mesh of the particles, not of individual particles.
This mode basically represents the intraparticle interactions.

16
4.1. Results and Discussion-I
Fig 4.1(a) and 4.1(b) shows the autocorrelation functions of PAM+NaCl solution with variation
of NaCl concentration in dilute (0.3 mg/ml) and semi-dilute (6 mg/ml) regions of polymer
solutions.

Fig 4.1(a) Autocorrelation functions in dilute (0.3 mg/ml) region at 175⁰

Fig 4.1(b) Autocorrelation functions in semi-dilute (6 mg/ml) region at 175⁰

17
Table 4.1, 4.2 shows the values of different parameters of double-stretch fitting function in the
dilute (0.3 mg/ml) and semi-dilute (6mg/ml) regions of polymer concentration with variation of
NaCl concentration for scattering angle 175⁰. The parameters are a1, a2,b1,b2,t1,t2. Here a1 and
a2 represent the amplitudes of fast and slow modes. b1, b2 represent the measure of the width of
the distributions of relaxation times.t1, t2 represent relaxation times of fast and slow modes.

Solution(dilute)
(PAM+NaCl) a1 a2 b1 b2 t1 t2 a1/a2
0.3mg/ml 0.73 0.22371 0.90265 0.58121 2.42E-04 0.00382 3.263153
0.3mg/ml+0.01M 0.67 0.28625 0.90442 0.46355 2.54E-04 0.01098 2.340611
0.3mg/ml+0.05M 0.435 0.52817 0.90659 0.2647 3.01E-04 0.62935 0.823598
0.3mg/ml+0.1M 0.71 0.25224 0.90124 0.30174 2.67E-04 0.07881 2.81478
0.3mg/ml+0.5M 0.67 0.29469 0.90224 0.24994 2.79E-04 0.19693 2.273576
0.3mg/ml+1M 0.43 0.52642 0.90492 0.84114 1.83E-04 5.01E-04 0.816838
0.3mg/ml+2M 0.71 0.2531 0.90377 0.26616 3.06E-04 0.05548 2.805215

Table 4.1 Fitting parameters for solution in dilute (0.3 mg/ml) region of polymer concentration with
variation in NaCl concentration

Solution(semi-dilute)
(PAM+NaCl) a1 a2 b1 b2 t1 t2 a1/a2
6mg/ml 0.65 0.3271 0.90102 0.35774 1.29E-04 0.01564 1.98716
6mg/ml+0.01M 0.57 0.39863 0.90216 0.34652 1.33E-04 0.03153 1.429897
6mg/ml+0.05M 0.42 0.45 0.90151 0.30311 1.43E-04 0.08433 0.933333
6mg/ml+0.1M 0.51 0.44272 0.90509 0.35481 1.33E-04 0.038 1.15197
6mg/ml+0.5M 0.46 0.47719 0.90141 0.39131 1.29E-04 0.03767 0.963977
6mg/ml+1M 0.48 0.46 0.9 0.34 1.39E-04 0.57167 1.043478
6mg/ml+2M 0.3 0.64 0.9 0.48 1.35E-04 0.02866 0.46875

Table 4.2 Fitting parameters for solution in dilute (6 mg/ml) region of polymer concentration with
variation in NaCl concentration

18
Variation of b1 and b2 in dilute and semi-dilute region
b1 and b2 are the measures of width of the distribution of relaxation times of first and slow
modes respectively. Basically, these two parameters show the polydispersity of the solution. b1
is related to the fast mode. From the table we can see that b1 is almost same for all type of
solutions in both dilute and semi-dilute regions and it is nearly equal to 1. So, we can say that the
fast modes in all cases for both the regions are almost monodisperse.

Fig 4.2 Variation of b2 with change in concentration of NaCl in dilute (left fig) and semi-
dilute(right fig) region
The above figure shows the variation of b2 with change in concentrations of NaCl in the solution
for both the regions. In the dilute region i.e. for 0.3 mg/ml polymer concentration b2 decreases
with increasing in NaCl concentration. Greater is the b2 value, lesser is the polydispersity. So
with increasing NaCl concentration from zero to 0.5M the polydispersity of slow mode
increases. But at a specific concentration i.e. at 1M, b2 value is at peak, even greater than the b2
value at 0M NaCl solution. So, the solution is more monodisperse with 1M NaCl concentration
than the solution without NaCl. We can say that 1M NaCl concentration helps the
polyacrylamide to properly dissolve in water. Then again with increasing NaCl concentration to
2M, b2 decreases. This is because at 2M concentration the solution is said to be supersaturated,
hence polydispersity increases.
In the semi-dilute region(6 mg/ml PAM solution), b2 has a variation with NaCl concentration,
but is very little in comparison with dilute region. So b2 is almost constant in semi-dilute region.
We can say that NaCl does not affect the polydispersity of slow mode in this region.

19
Variation of a1 and a2 in dilute and semi-dilute region
a1 and a2 are the amplitudes of the first and slow modes. We know that a1+a2≅1. So, if a1
increases a2 decreases and vice versa. Fig 4.2 shows the variation of ratio of a1 and a2 with the
change in NaCl concentration.

Fig 4.3 Variation of a1/a2 with change of NaCl concentration in dilute (up fig) and semi-dilute
(down fig) regions
The variation of a1/a2 in dilute region (0.3 mg/ml PAM solution) with NaCl concentration
happens in some ranges. From 0-0.05 M concentration of NaCl, a1 decreases and a2 increases.
This may be due to the fact that the successive growth of NaCl layers over the polymers with
increasing its concentration. Then a sudden increase in a1 is seen at 0.1 M, which may be due to
the fact that the individual particles come very close to each other that hydrodynamic size of the
cluster is even smaller than the hydrodynamic size of individual ones. Further, on increasing
NaCl concentration, a1 starts decreasing in the range 0.1-1 M. i.e. intra-particle interaction (slow
mode) dominates over interparticle interactions (fast mode). On further increasing of NaCl
concentration to 2 M, the amplitude of fast mode increases. But in semi-dilute region (6 mg/ml
PAM solution), a1 decreases with increasing molarity of NaCl from 0-0.05. But the variation is

20
small compared to the dilute region. Then in the range 0.1-1 M, a1 is almost same. This shows
the less dependance of amplitudes of first and slow modes on concentration of NaCl in semi-
dilute region. Further increasing the molarity of NaCl, amplitude of slow mode increases, which
may be due to the super saturation of the solution.

Variation of t1 and t2 in dilute and semi-dilute region

t1 and t2 are relaxation times of fast and slow modes respectively. Relaxation time is related to
diffusion coefficient as D=(q2t)-1. So less is the relaxation time, more is the diffusion coefficient
and vice versa. Fig 4.3 shows variation of t1 and t2 with change in concentration of NaCl in
dilute and semi-dilute regions.

Fig 4.4 Variation of t1 and t2 with change in concentration of NaCl in dilute and semi-dilute
region(upper left and right fig show variation of t1 and lower left and right fig show variation of
t2 in dilute and semi-dilute regions respectively)

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In dilute region (0.3 mg/ml), both t1 and t2 increase with increase in NaCl molarity in the range
0-0.05 M. This implies hydrodynamic radius is increasing, which may be due to growth of layers
of NaCl over polymers. Then in the range 0.1-1 M both t1 and t2 are decreasing. At 1M
concentration, t1 and t2 have their lowest values which implies the highest diffusion coefficient
can be gained at this concentration. Then on further increasing NaCl concentration, t1 and t2
increases, because of super saturated concentration. One thing to note that t1 value is always less
than t2, which implies fast mode is more diffusive than slow mode.
In semi-dilute region (6 mg/ml) t1 and t2 are almost independent of NaCl concentration,
although a little variation in the range 0-0.05 M can be seen from fig 4.3, which implies almost
independence of relaxation times from NaCl concentration in semi-dilute region. Also, it can be
seen that the relaxation time of fast mode in semi-dilute region is always less than that of in
dilute region. So, we can say that fast mode of semi-dilute region is more diffusive.

4.2. Results and Discussion-II

The below figure shows all the autocorrelation functions for three concentrations of three
molecular weights.

Fig 4.5 Autocorrelation functions for concentrations 0.3,0.5,0.7 mg/ml with three different molecular
weights.

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Fig 4.6 Autocorrelation function for 0.3 mg/ml concentrations in different molecular weights of PAM

Fig 4.7 Autocorrelation function for 0.5 mg/ml concentrations in different molecular weights of PAM

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 Fig 4.8 Autocorrelation function for 0.7 mg/ml concentrations in different molecular weights of PAM

Basically, in this part of experiment the molecular weight of polyacrylamide was varied. Also for
a particular molecular weight, the concentration of polymer is varied in dilute region. The three
concentrations taken were 0.3,0.5 and 0.7 mg/ml. And the molecular weights are 5-6 × 106 ,1.5 ×
105 ,4 × 104 gm/mole for PAM1, PAM2 and PAM4 respectively.
The autocorrelation functions got from the data were fitted with double stretched exponential
function and the fitting parameters were obtained. The parameters we got describe the amplitude
of relaxation modes(a1,a2), the relaxation times(t1,t2) and width of distribution of relaxation
times(b1,b2). b1 is related to the fast mode. b1 is almost same for all type of solutions in dilute
region and it is nearly equal to 1. So, we can say that the fast modes in all cases for both the
regions are almost monodisperse. The amplitudes of both the modes(a1,a2) are varying with
different trends while changing molecular weights in all three concentrations. This may happen
as we are dealing in dilute region.
Also, in the dilute region, we expect the translational diffusion to dominate. That means we can
see mostly fast mode of relaxation. So, we need to focus on fast mode relaxation time t1. We can
also calculate diffusion coefficient and hydrodynamic radius of the polymer from t1. The below
table shows t1 values for all autocorrelation functions.

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Concentration PAM1 PAM2 PAM4
0.3 mg/ml 3.19E-4 2.92E-4 2.06E-4

0.5 mg/ml 6.65E-4 2.7E-4 1.86E-4

0.7 mg/ml 3.54E-4 2.8E-4 2.07E-4

Table 4.3 Values of t1(in sec) for different concentrations and molecular weights

Calculation of diffusion coefficient(D)

We know that 𝜞=Dq2, where 𝜞 is the decay rate.
4πn
q is the scattering vector defined by q= sin(θ/2)
λ

where λ is the incident laser wavelength, n is the refractive index of the sample and θ is angle at
which the detector is located with respect to the sample cell.
Here, λ= 658 nm, n=1.33 and θ = 900
Calculating for q we obtain q= 0.0179×109/m
Also, 𝜞=1/t1
e.g. t1=3.19×10-4 sec
D= 𝜞/q2 =1/(t1×q2)= 9.79624×10-10

Similarly, diffusion coefficient for all t1 values is calculated and shown in the below table.

0.3 mg/ml 0.5 mg/ml 0.7 mg/ml

PAM1 9.79624E-10 4.69925E-10 8.82768E-10

PAM2 1.07021E-9 1.15741E-9 1.11607E-9

PAM4 1.51699E-9 1.68011E-9 1.50966E-9

Table 4.4 Values of Diffusion coefficient(D) for different concentrations and molecular weights

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 Fig 4.9 Variation of Diffusion coefficient with molecular weight in different concentrations

It is observed that diffusion coefficient in dilute region not only depend on molecular weight but
also on concentration. The diffusion coefficient increases with decreasing molecular weight for
every concentration. And Diffusion coefficient is inversely proportional to hydrodynamic size of
𝐵 𝑘 T
the polymer coil. We can verify the same from Stoke-Einstein relation, D= 6𝜋𝜂𝑅 .So, with
ℎ
decreasing molecular weight hydrodynamic size of particle will decrease.
For lower molecular weight, number of monomers are less for a particular polymer
concentration. As a result hydrodynamic size of the coils become smaller for lower molecular
weight.
If we look at the behavior of diffusion coefficient(D) with change in molecular weight, it is seen
that D is concentration dependent in the dilute region. We have seen the dependency of
molecular weight for three concentrations in dilute region.

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From fig 4.9 it can be seen that for concentrations 0.3 and 0.7 mg/ml the change in D with
molecular weight is almost same. But for concentration 0.5 mg/ml change is large as compared
to previous two. Which reflects that 0.5 mg/ml may the critical concentration for molecular
weight variation in dilute region.

5. Conclusion
In the experiment the effect of variation of NaCl concentration over polyacrylamide solution was
studied. A double stretch exponential function was introduced for fitting of the correlation
curves. There were some parameters associated with the fitting function. We found the
morphological changes of the polymer in the aqueous solution. We found that NaCl
concentration variation affects the hydrodynamic diameter of polyacrylamide in dilute region
and almost independent in semi-dilute region. Here the viscosity and refractive index of NaCl
solutions were not calculated, otherwise we could measure the exact hydrodynamic radius of
polyacrylamide macromolecules or clusters in the solutions.
Infinite dilution is useful for particular size determination in a solution using DLS method. Here
we saw the size of the polymer is dependent on the concentration of polymer in the dilute region
for each molecular weight. So, it may be predicted that infinite dilution is appropriate for
nanoparticle size determination. But in case of polymer when we dilute the concentration the
tendency of uncoiling of the polymer chain increases, which gives us the concentration
dependency of polymer chains in a solution. But in a same concentration when we decrease the
molecular weight of the polymer, the diffusion coefficient increases resulting in decrease of size,
which shows the molecular weight dependency.

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