1

Effect of Boron Nitride on the shear thickening behavior of

silica Polyethylene glycol system

By
Vyom Gupta
Entry no: 2019CH70203

A PARTIAL SUBMISSION OF A REPORT MEETING THE REQUIREMENTS FOR

THE MASTER OF TECHNOLOGY DEGREE IN

DEPARTMENT OF CHEMICAL ENGINEERING

Indian Institute of Technology Delhi
2024
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DECLARATION AND APPROVAL OF SUPERVISOR

I have prepared this report with inputs from my supervisor. I have taken care of the

formatting as per the guidelines circulated. I have not copied any section from any other

report, website, or article.

SIGNATURE OF STUDENT

The report entitled “Effect of Boron Nitride on the shear thickening behavior of

silica Polyethylene glycol system” has been approved

SIGNATURE OF SUPERVISOR
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Abstract

It has been discovered that adding more nanoparticles to a silica base increases the
strength of the resulting shear-thickening fluid. In addition, the insulating properties of
materials treated with h-BN/PEG against heat and cold were investigated in the literature.
The findings showed improved thermal insulating properties when compared to
conventional leathers. Here, We will talk about the method used in the current thesis to
manufacture silica nanoparticles in the lab and optimize the process in terms of the size
and time of the particles formed throughout this entire process. Additionally, an
experimental investigation into the physical properties of the shear-thickening fluids has
been conducted, using Boron nitride as the impurity present together with silica
nanoparticles in the polyethylene glycol dispersion medium. Besides this, we provide
theoretical background and explanations of the results obtained.
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Acknowledgment

This is my chance to express my profound thanks and appreciation to all of the wonderful
people who helped make this Master's program possible. I would like to thank Dr. Sudip
Kumar Pattanayek, my academic advisor, for all of his invaluable assistance and
guidance. His unwavering support and encouragement really aided me in the completion
of both my master's and this thesis. He was a friend and benefactor who supported me
through all of my hard times. I gained a lot of knowledge from him during my M.Tech
journey.
Additionally, I would like to express my gratitude to Mr. Nitin Kumar, Dr. Swati
Bishnoi, and IIT Delhi for their support and advice. I also want to thank all of my lab
partners for their support all the way through. I also want to express my gratitude to my
family for their support.
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Content
DECLARATION AND APPROVAL OF SUPERVISOR........................................2
Abstract.....................................................................................................................3
Acknowledgment......................................................................................................4
Content......................................................................................................................5
List of Figures...........................................................................................................7
1. Introduction...........................................................................................................8
1.1 Problem statement...................................................................................9
1.2 organization of thesis report ...................................................................9
2. Review of literature.............................................................................................11
2.1 Shear thickening mechanisms proposed................................................13
2.1.1 order-disorder transition..........................................................13
2.1.2 Hydroclustering.......................................................................13
2.1.3 Jamming theory........................................................................13
2.1.4 Friction contact theory.............................................................14
2.2 Shear thickening fluid composition.......................................................14
3. Material and methodology..................................................................................15
3.1 Materials required..................................................................................15
3.2 Methodology..........................................................................................15
3.2.1 Synthesis of silica nanoparticles..............................................15
3.2.2 Synthesis of shear thickening fluids........................................17
4. Characterization of nano-silica and STF.............................................................19
4.1 Nano silica.............................................................................................19
4.1.1 FTIR........................................................................................19
4.1.2 XRD analysis...........................................................................20
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4.1.3 TEM analysis...........................................................................20

4.1.4 Particle size analysis................................................................20
4.2 STF.........................................................................................................20
4.2.1 Rheological investigation of shear thickening fluids...............21
5. Results and Discussions......................................................................................22
5.1 Characterization of synthesized silica....................................................22
5.1.1 FTIR.........................................................................................22
5.1.2 XRD.........................................................................................23
5.1.3 TEM.........................................................................................24
5.1.4 Particle size and zeta potential analysis...................................25
5.2 Rheological evaluations of various STFs..............................................26
5.2.1 Steady shear rheology..............................................................26
5.2.2 Dynamic shear rheology..........................................................30
5.3 Interaction analysis between particles in the STF..................................33
5.3.1 Considering the case of unit cell..............................................34
6. Conclusions and scope for future work..............................................................37
7. References..........................................................................................................38
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List of Figures
Figure 1: Typical viscosity vs shear rate graph of shear-thickening fluids represented..12
Figure 2: Schematics of Silica nanoparticle synthesis.................................................17
Figure 3: Schematics of STF preparation...................................................................18
Figure 4: Fourier transform Infrared spectra (FTIR) of silica nanoparticles
synthesized...............................................................................................................23
Figure 5: X-ray diffraction (XRD) analysis of silica nanoparticles synthesized............24
Figure 6: Transmission electron microscopy (TEM) characterization of silica
nanoparticles.............................................................................................................25
Figure 7: Dynamic light scattering (DLS) characterization of silica nanoparticles
synthesized...............................................................................................................26
Figure 8: Rheology results of viscosity vc shear rate for samples with total solid content
70%..........................................................................................................................29
Figure 9: Rheology results of viscosity vc shear rate for samples with total solid content
68.5%.......................................................................................................................29
Figure 10: Amplitude sweep of samples with Boron Nitride and total solid weight
percent 70.................................................................................................................31
Figure 11: Frequency sweep of samples with Boron Nitride and total solid weight
percent 70.................................................................................................................31
Figure 12: Amplitude sweep of the sample with Boron Nitride and total solid weight
percent 68.5..............................................................................................................32
Figure 13: Frequency sweep of the sample with Boron Nitride and total solid weight
percent 68.5..............................................................................................................32
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Figure 14: Unit cell with silica nanoparticles at corners and Boron Nitride and
body-center...............................................................................................................35

CHAPTER 1

INTRODUCTION

First recognized in the 1960s, the shear thickening (ST) effect obstructs fluid velocity and
can cause uneven material coatings, clogs in pipelines containing crude oil, overloads in
high-speed agitators, and sporadic equipment damage. At first, this fascinating
phenomenon was not given much attention because it interfered with industrial processes.
However, the introduction of nanotechnology in the middle of the 1990s resulted in the
creation of a brand-new shear thickening fluid (STF), which has since attracted a lot of
attention for a range of uses. Concentrated particle suspensions are found in consumer
goods like food and cosmetics, natural processes like blood flow, and a variety of
formulations like paints, inks, ceramics, and concrete [2]. Numerous rheological
characteristics are seen in these systems, such as yielding, thixotropy, shear-induced
aggregation, and shear thinning and thickening.

Shear thickening was first thought to be an issue that complicated industrial processes
like slurry pumping and paper coating that required high shear rates and concentrated
suspensions. But lately, its special qualities have been used to make smart materials and
composites, which makes it perfect for a range of uses, such as liquid body armor.

To improve the ballistic and stab resistance characteristics of the fabric, researchers are
actively investigating the combination of Kevlar with STFs. The inclusion of STFs,
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which reversibly change from a liquid to a solid-like state under applied stress, enhances
the impact resistance of Kevlar, a material renowned for its great tensile strength and
durability. The rheological characteristics, stability, and overall performance of the STF
are being optimized through the investigation of several additions, including boron
nitride, polyethylene glycol (PEG), and silica nanoparticles. With these advancements,
materials that are highly protective, flexible, and lightweight will hopefully be developed
for use in sports equipment, personal armor, and other industries where enhanced impact
resistance is necessary. According to continuing research, these materials have the
exciting potential to offer improved protection without sacrificing comfort or mobility.

1.1 Problem Statement

According to the literature review, it has been discovered that adding more nanoparticles
to a silica base increases the fluid's shear-thickening capacity. One material that has been
demonstrated to increase a shear-thickening fluid's ballistic resistance is silicon carbide
when combined with fumed silica nanoparticles. Silicon carbide has been shown to be an
efficient strengthening addition to the mixture, despite the fact that it does not exhibit
shear thickening behavior on its own.

In addition, materials such as leather treated with h-BN/PEG [2] were investigated for
their ability to withstand heat and cold; the findings showed that these materials had
better thermal insulation qualities than conventional leathers. Higher storage modulus,
loss modulus, and tan δ values were found in the dynamic mechanical analysis of the
control and treated leathers, indicating an increased potential for energy absorption and
dissipation. This was confirmed by the low-velocity, low-weight impact resistance test.

This thesis presents research on the use of Boron nitride in conjunction with silica
nanoparticles distributed in polyethylene glycol to improve the shear thickening
capabilities. Therefore, in this work, we investigate how the addition of BN to silica and
PEG alters its mechanical characteristics. Because of its excellent thermal conductivity,
BN can dissipate heat efficiently and rapidly. By doing this, you can increase the
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material's resilience to heat by preventing overheating and thermal damage in

high-temperature situations. In addition, when the fluid is subjected to high shear rates,
BN particles can form strong interparticle connections and temporary solid-like
formations, which increases the fluid's viscosity.

1.2 organization of Thesis Report

This thesis is divided into 6 chapters. Chapter 1 consists of the introduction, the problem

statement, and the organization of the overall thesis

Chapter 2 contains the literature review of shear-thickening fluids. The mechanisms

related to the shear thickening effect are also discussed along with the composition

Chapter 3 contains the materials and methodology used in experiments related to this

thesis. The synthesis of silica nanoparticles is discussed using a modified Stober process.

After that, the synthesis of shear-thickening fluids is also discussed.

Chapter 4 discussed the various characterization methods used to analyze the silica

nanoparticles synthesized and the STF prepared using silica and boron nitride.

Chapter 5 contains the results and the discussions around that. The possible theoretical

background behind the results obtained is also discussed.

Chapter 6 contains the conclusion of this thesis and the scope of future work that can be

continued in the same area.

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CHAPTER 2

REVIEW OF LITERATURE

The viscosity of shear thickening fluids (STFs) increases in response to increased shear
rates or shear stress. A discontinuous shear thickening characteristic is seen in colloidal
dispersions, which is indicated by a sudden increase in viscosity above a critical shear
rate. Numerous interactions are thought to be involved in this phenomenon, with the
hydro-clustering effect being the main one. In this chapter, the theoretical background
related to the shear thickening phenomenon is discussed

Shear thickening was once thought to be an issue in industrial operations since it may
cause blocked and clogged machinery, which would limit the pace at which machinery
could operate. However, when combined with STFs in high-tensile strength fabrics, this
behavior was found to improve ballistic performance in the early 2000s. These
non-Newtonian fluids, referred to as dilatants, become more viscous as shear rates rise.
Since the shear thickening process is reversible, the fluid can continue to flow even in the
absence of shear pressures. Van der Waals forces govern the behavior of tiny particles at
equilibrium. Particles undergo a transition to a mobile state and then aggregate,
exhibiting a shear thickening effect, as the shear rate approaches a critical point where
shear forces triumph over intermolecular forces (Figure 1) [16]. Granular suspensions,
crosslinked polymers, micelles, and insoluble polymers are the four main types of STFs.
 12

Because different systems display shear thickening in different ways, it is still unclear
what exactly causes this behavior. A number of theories, however, have been put out to
explain the mechanics underlying shear thickening. When the stress is released, the
thickening phenomenon is reversible and the suspension returns to its initial liquid form.
A number of variables, such as the properties of the Newtonian liquid and suspended
particles, influence the thickening process. The performance of these suspensions is
controlled by factors such as particle size, distribution, shape; volume concentration;
medium viscosity; interactions between the particles and the suspending media, etc. A
shear thickening fluid (STF) typically exhibits three distinct zones in its rheological
curve: (i) a low viscosity region, also known as a shear thinning section; (ii) a transition
region where flow is arrested and viscosity increases; and (iii) a second shear thinning
region, where the viscosity decreases once more at higher shear rates. Viscosity first falls
at low shear rates, with a power-law-like relationship between viscosity and shear rate.
Until the liquid between the particles provides hydrodynamic lubrication and an aligned
particle microstructure is produced, this drop in viscosity continues. Particles are forced
closer together when shear forces rise, creating hydroclusters—local, transitory particle
fluctuations—that raise viscosity. The critical shear rate/stress is the shear rate or stress at
which viscosity starts to rise (the initiation of shear thickening). The viscosity neither
levels out to a new plateau value beyond the shear thickening zone nor rises to an
unreasonably high level that could fracture the sample.
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Figure 1: Typical viscosity vs shear rate graph of shear-thickening fluids represented

2.1 Shear Thickening Mechanisms Proposed

2.1.1 order-disorder transition

The order-disorder transition (ODT) theory is one of the conventional theories that is
frequently applied. According to Hoffman's proposal, an STF does not show shear
thickening behavior at low shear rates [7]. Rather, the particles self-organize into orderly
layers with a thickness ranging from one to several particles. The lamellae then break
down and collapse to form a disordered structure when the shear rate reaches a critical
value. This is the point at which the fluid's viscosity increases disjunctly.

2.1.2 Hydroclustering
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Another idea that receives a lot of credit for explaining shear thickening is
hydro-clustering. The system can handle particle movement at very low shear rates, and
the viscosity value is low. Shear thinning is detected as the shear tension between the
particles increases and starts to overcome the intermolecular interactions. Shear forces
entirely outweigh intermolecular forces at the critical shear rate, encouraging the
production of unstable hydro-clusters. When the shear stress is removed, these aggregates
significantly increase the fluid's viscosity, but they quickly return to their original,
undisturbed state through intermolecular forces and Brownian motion [2].

2.1.3 Jamming Theory

When the particle size of a solution is greater than four micrometers, the jamming theory
is typically applied. Particle contact is substantially higher in this size range due to the
absence of Brownian and intermolecular forces. A solution that exhibits jamming, as
reported by Olsson and Teitel [17], exhibits a sudden, discontinuous increase in viscosity
of several orders of magnitude because of the formation of scattered aggregates by the
particles, which propagate under shear stress and further obstruct the flow of other
particles. This finally results in a solution that is totally incapable of flowing when the
volume fraction of the scattered particles reaches a high enough value.

2.1.4 Friction Contact Theory

In order to reconcile the differences between continuous and discontinuous shear

thickening behavior, friction contact theory was put out. Low shear rates result in low
normal forces between the particles, which greatly influence the fluid's low viscosity due
to fluid lubricating forces. Because of the lubricating layer's destruction at high shear
rates, there is more contact and frictional force between the particles.

2.2 Shear Thickening Fluid Composition

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Colloidal mixtures, or STFs, are mainly made up of two components: a distributed

insoluble particle and a carrier fluid. In addition to connecting the particles and easing the
impregnation process into the fabric, the carrier fluid serves as a dispersing medium
between the particles. The primary dispersed particle in many experiments on ballistic
protection using STFs is silica, while the carrier fluid is PEG (polyethylene glycol).

Because PEG is non-toxic, heat stable, biocompatible, and can mildly wet the selected
cloth for impregnation, it is frequently preferred as a carrier fluid over water and other
solvents [2]. Shear-thickening fluids are also made with ethanol, which serves as a
dilutant and surfactant. It lessens shear thickening behavior when mixed with the
particles in the carrier fluid after being introduced. Furthermore, the surfactant qualities
of the substance facilitate the more efficient impregnation of the diluted shear-thickening
fluid into the fabric, which may then be removed without compromising the desired
properties of the solvent.

CHAPTER 3

MATERIAL AND METHODOLOGY

In this chapter, we have discussed the materials required for the experimentation related

to this thesis, and their source (purchased or prepared in the laboratory). The

methodology for the synthesis of the materials is also discussed.

3.1 Materials Required

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Fisher Scientific supplied the polyethylene glycol with a molecular weight of 200, while
GLR Innovations provided the ACS-grade ethanol and the 98% Tetraethyl orthosilicate
(TEOS). De-ionized water and 25% liquid ammonia from Thermo Fischer were used in
the experiment. Without additional purification, all compounds were used just as they
were obtained.

3.2 Methodology

In [Figure 2], the experimental procedures are shown schematically. The process is
divided into multiple phases: the preparation of shear-thickening fluid and the production
and optimization of silica nanoparticles from their precursor, Tetraethyl orthosilicate
(TEOS).

3.2.1 Synthesis of Silica nanoparticles

The modified Stober procedure is a well-established methodology [18][2] that was used
to produce silica nanoparticles. We prepared a solution with a volume ratio of 65:10:3
that included ethanol, 25% liquid ammonia, and deionized water. For two hours, this
mixture was agitated at 40 °C. The reaction mixture was then supplemented with
tetraethyl orthosilicate (TEOS) after that. TEoS and ammonia have a molar ratio of 1:6.
Based on the best-documented process, the aforementioned ratio [18] is calculated. The
reaction was kept moving forward by constant stirring at 40 °C for 24 hours.
Centrifugation was used to separate the reaction mixture once the reaction had finished.
Following centrifugation, the resultant particles underwent three separate ethanol rinses
before being dried for four hours at 120 °C in a hot air oven.

The process of creating monodisperse spherical silica nanoparticles using the Stober
method [18] involves hydrolyzing tetraethyorthosilane (TEOS) and then condensing the
resulting particles in ethanol with the use of ammonia as a catalyst. This yields particles
with sizes that span practically the whole colloidal range. Because of its effectiveness and
 17

simplicity, it is one of the most used processes for creating silica nanoparticles. In 1988,
Bogush et al. [18] looked at the relationship between the size of silica particles and the
amounts of water, ammonia, and TEOS within specified ranges. They came to the
conclusion that, for varying ammonia concentrations, particle size rises as TEOS
concentration increases; water concentration likewise influences size in the same way up
to 7.0 mol L-1, but at greater concentrations, the opposite happens, as also noted by
Stober. TEM testing was done on the particle sizes at various stages of the production
process. This was carried out in order to maximize the size and formation time of silica
nanoparticles.

Figure 2: Schematics of Silica nanoparticle synthesis

3.2.2 Synthesis of shear thickening fluids

PEG-200 (polyethylene glycol) and ethanol were combined to prepare the silica/PEG
samples, and then different percentages of silica were added. There were two sets of
samples. The overall solid content of the first set was 70 weight percent, and the second
set's total solid content was 68.5 weight percent. Three ratios (i) silica 70 wt%, (ii) Silica
 18

69 wt%, Boron Nitride 1 wt%, and (iii) Silica 68 wt%, Boron Nitride 2 wt% were taken
in the first set, with PEG 200 being set at 30 wt%. Two ratios were taken in the second
set: (i) Silica 68.5 wt% and (ii) Silica 67.5 wt%, Boron Nitride 1 wt%, with PEG 200
remaining at 31.5 wt%. Ethanol: Silica + PEG had a 3:1 (w/w) ratio. This choice of this
ratio is based on the extensively optimized protocols in our laboratory. This ratio was
selected using our laboratory's highly tuned-processes. The resulting mixture was then
used as the foundation for STF formulation after being thoroughly dispersed by both
manual and ultrasonic agitation. To remove any moisture, the silica particles were
oven-dried for two hours at temperatures higher than 80 °C before being used. The
mixture was manually stirred for 10 minutes, and then it was homogenized for 30
minutes using ultrasonication. To facilitate ethanol removal, the resultant composite of
silica, PEG, and ethanol was subjected to elevated temperatures of 80 °C for two hours.

Figure 3: Schematics of STF preparation

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CHAPTER 4

CHARACTERIZATION OF NANO SILICA AND STF

This chapter sheds light on the characterization methods utilized to analyze the

nano-silica prepared in the laboratory. Further, the shear-thickening fluids synthesized

using nano-silica are also analyzed and their methods are discussed.

4.1 NANO SILICA

Prior to STF formation, the produced silica nanoparticles underwent extensive

characterization. X-ray diffraction (XRD) was used to evaluate the morphology, and
Fourier-transform infrared spectroscopy (FTIR) was used to assess chemical functioning.
Transmission electron microscopy (TEM) and dynamic light scattering (DLS) were used
to assess the particle size, and a Zetasizer was used to analyze the surface charge.
Thermal stability was examined using thermogravimetric analysis (TGA).
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4.1.1 FTIR

Measurements of Fourier-transform infrared (FTIR) spectroscopy were performed with

the Nicolet iS50 NIR equipment from Thermo Scientific. During this procedure, an
infrared spectrum that clarifies the chemical functional groups included in the silica
nanoparticles that were produced was obtained. By simultaneously detecting every
infrared wavelength, FTIR creates a complete spectrum that makes it possible to
simultaneously resolve interferences and analyze every component with a single
measurement.

4.1.2 XRD analysis

The investigation of X-ray diffraction (XRD) entails exposing samples of nanomaterials

to collimated X-rays, which cause a sequence of interactions that result in the emission of
diffracted rays. Then, these diffracted rays are found, examined, and measured. The
intensity profile that results from the scattering of diffracted rays across various angles
within the material is the diffraction pattern. The equipment used in this study's
experimental setting was the Rigaku MiniFlex 600. This XRD equipment sheds light on
the amorphous properties and structural organization of the produced silica nanoparticles.

4.1.3 TEM analysis

Transmission electron microscopy (TEM) was used to assess the silica nanoparticles'
structural shape and mean particle dimensions. Transmission electron microscopy is the
preferred method for examining the smallest features found in materials (TEM). The
JEoL JEM-1400 device, which uses an electron from a tungsten filament and has a
maximum tilt angle range of ±70, was used in this investigation. This method makes it
possible to see and examine the nanoscale properties and features present in the samples.
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4.1.4 Particle Size Analysis

The Malvern Nano ZS90 Dynamic Light Scattering equipment was utilized to determine
the particle size (hydrodynamic radius) and evaluate its polydispersity index. The process
comprised measuring at a regulated temperature of 25C and dispersing the silica sample
in ethanol. The scattered light signal was detected at a scattering angle of 90 degrees
(right angle) using a detection system that used two detectors. The Zetasizer mode of the
device was used to determine the silica nanoparticles' final surface charge.

4.2 STF

4.2.1 Rheological investigation of shear thickening fluids

Shear thickening fluids (STFs) were the subject of a thorough rheological analysis using
parallel plate geometry and a range of shear rates from 0.01 to 10,000 s-1 in steady shear
circumstances. The used plates had a 25 mm diameter and a 0.1 mm space between them.
At a temperature of 25 °C, the continuous shear response of the STF compositions was
examined using the Anton Paar 302 Rheometer. Noteworthy, all STF samples
experienced full ethanol evaporation prior to the analysis of their rheological
characteristics. To verify that all ethanol residues were removed, the samples were dried
by heating them to 80 °C for two hours in a hot air oven. For every sample, rheology
analyses underwent both dynamic and stable shear conditions. Constant shear rheology
involves rotating the sample continuously, which makes it easier to study viscosity
changes with respect to temperature, time, and shear rate. This process could cause total
disruption or sample distortion. on the other hand, dynamic shear rheology applies
harmonically varying deformations—small- and large-amplitude, usually
sinusoidal—within a basic shear field. This non-destructive method works well for
identifying structural changes in the material under study and is used to characterize
viscoelastic behavior.
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CHAPTER 5

RESULTS AND DISCUSSIONS

In this chapter, we have provided with all the results obtained by performing multiple

tests of each sample. The tests include the characterization tests on nano-silica

synthesized in the lab and also the rheological tests done on the shear thickening fluid

synthesized. Besides this, theoretical explanations and background are also discussed

related to the results obtained.

5.1 Characterization of the synthesized silica

While FTIR is used to evaluate the chemical functionality of the silica surface, XRD is
used to verify the presence of silica nanoparticles and study their crystalline structure.
 23

5.1.1 | FTIR

The FTIR spectra of silica nanoparticles that were produced and distributed in ethanol are
shown in Figure 4[1]. The Si-O-Si bonding in silica exhibits an asymmetric vibration,
which is responsible for the band at 1061 cm-1. The symmetric vibration of the silanol
(Si-OH) group is indicated by the weak band at 936 cm-1. Furthermore, a bending
vibration of the Si-O group is seen at 801 cm-1. This proves that particles of silica are
generated. observed at 2900 cm-1 (-OC2H5) group. The stretching vibrations of the
silanol group and adsorbed water molecules on silica are seen in another broadband that
spans from 3084 to 3548 cm-1 (-OH) group.

Figure 4: Fourier transform Infrared spectra (FTIR) of silica nanoparticles synthesized

5.1.2 | XRD
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In Figure 5, the XRD pattern is displayed[1]. The material's amorphous form is shown by
the prominent diffraction broad peak, located at 23°. This is consistent with the JCPDS
data (card No. 01-086-1561), which was also previously reported by Swarna et al[16].

Figure 5: X-ray diffraction (XRD) analysis of silica nanoparticles synthesized

5.1.3 | TEM

Figure 6 illustrates the approximate 330 nm size of the produced silica particles via
transmission electron microscope (TEM) investigation[1]. The TEM's micrographs show
that the silica particles are clearly spherical in shape. Using ImageJ software, the average
 25

diameter of these spherical particles that are monodispersed was carefully calculated by
analyzing 50 measurements for every sample. This resulted in an average diameter of 330
nm[2]. This careful analysis confirms that the produced nanoparticles are uniformly
spherical.

Now, the initial development of the produced silica nanoparticles took place during a
24-hour period. Several samples were taken at various points during the preparation
process and examined for TEM examination in order to optimize for the amount of time
required, the size of silica nanoparticles, and their shape.

Figure 6: Transmission electron microscopy (TEM) characterization of silica

nanoparticles

5.1.4 | Particle size and zeta potential analysis

Figure 7 displays the particle size distribution of silica particles that were generated using
dynamic light scattering[1]. The polydispersity index (PDI) and Z-average particle
 26

diameter of the silica particle are 0.15 and 303 nm, respectively. As would be expected,
the mean diameter found by TEM examination is somewhat less than that found by DLS
analysis. This is due to the fact that DLS measures hydrodynamic radii, which are greater
than the actual size of the particle[ref]. As a result, in this work, the mean diameters
obtained from TEM micrographs were taken into consideration for additional
investigation. Zeta potential measurements of dispersed Silica nanoparticles in ethanol
were used to calculate the surface charge. The Zeta potential of the silica particle is -42
mV. A silica suspension that has stabilized is indicated by a high zeta potential.

Figure 7: Dynamic light scattering (DLS) characterization of silica nanoparticles

synthesized

5.2 Rheological evaluation of various STFs

5.2.1 | Steady shear rheology

Figures 8,9 display the steady shear test results. The normal shear thickening
characteristic, in which viscosity increases with the shear rate until it reaches a particular
 27

level known as critical shear rate, is exhibited by the Silica and Boron-Nitride-based STF.
After that, viscosity decreases in proportion to the shear rate. Because the rheological
behavior of STF is highly dependent on the particle form, concentration, and interactions
between these components, tuning the silica content is a frequent technique to modify this
behavior. Mono-dispersed silica nanoparticles come into contact and start to clump
together when shear stress is applied to the STF because of attraction forces between their
surfaces. These aggregates are called hydroclusters, and they are dynamic structures that
can alter in size and form in response to the degree of shear stress. The hydroclusters
align themselves in the direction of the shear as the shear stress increases, creating linked
structures. Viscosity rises as a result of the alignment's restriction on the fluid particles'
ability to move. The hydroclusters clog and get tightly packed at a critical shear rate,
which causes a dramatic increase in viscosity. At this stage, the fluid changes from a
low-viscosity to a high-viscosity condition, and the shear thickening behavior becomes
substantial. Figures 8 and 9 depict the rheological behavior of STF at total solid weight
percent percentages of 70% and 68.5%, respectively, in relation to the solid weight. The
majority of research teams have previously published STF formulations with PEG
concentrations of 35%–30% (w/w) and silica concentrations ranging from 65% to 70%
(w/w). We therefore created STF with two distinct silica concentrations based on it.
According to Figure 8, the peak viscosity is around 172 Pa.s, and the critical shear rate is
2.15 s-1 for the sample containing Silica 68 wt% and BN 2 wt%. The critical shear rate is
14.17 s-1 and the peak viscosity is around 141 Pa.s for the sample containing Silica 69
wt% and BN 1 wt%. The critical shear rate for the sample containing 70% Silica is 21.5
s-1, and the peak viscosity is approximately 69.5 Pa.s. When dealing with samples that
have a total weight of 68.5 wt% in solid content, the critical shear rate for the sample
containing 68.5 wt% Silica is 14.7 s-1, and the peak viscosity is around 50.3 Pa.s. The
critical shear rate is 21.5 s-1, the peak viscosity is approximately 59 Pa.s, and the sample
contains 67.5 wt% Silica and 1 wt% BN.

It is possible to conclude from experiments and multiple iterations that the shear
thickening ratio will decrease and 𝜸̇𝒄 will increase in an STF with a particle weight
fraction below its optimal value. This might be because there are more unreacted liquid
 28

polymer chains present, which causes a greater interparticle distancing. Greater external
forces are needed to overcome both the interparticle repulsion forces and this separation
distance at the same time. Conversely, by raising the weight fraction over the optimal
weight fraction, unreacted polymer chains deprive the STF of lubrication, which causes
particle clusters to become entangled and ultimately eliminates the shear thickening
effect. Additionally, a trend is evident in the data: while the sample's percentage of boron
nitride increases (assuming a fixed percentage of total solid weight), the critical shear rate
decreases, particularly for samples with a solid content of 70%. The reason for this is that
boron nitride functions as a heat sink. The hydrogen connection between the surface
groups of the particles and the carrier fluid polymer weakens with temperature. As a
result, there are more external shear pressures and interparticle repulsion forces, which
cause hydroclustering and shear thickening. The suspension of Boron Nitride decreases
the STF's effective temperature by acting as a heat sink. The shear-thinning section of the
curves indicates another tendency that may be deduced from the data. With an increase in
the proportion of Boron Nitride in the sample, there is a corresponding decrease in the
shear rate at which shear thinning begins after reaching maximum viscosity. This result
might be the result of the additives' interactions with the silica influencing the shape of
the particles. Differences in the way the hydro-cluster networks break could be caused by
additional particles with different shapes. Although the additive particles are not shaped
like the silica nanoparticles where the additives do not contribute to the connections
between particles, the silica nanoparticles nevertheless form a cluster network. It is well
known that the hydro-clusters' extended or elongated networks perform better in the
thickening process than the spherical aggregates[8]. The nanosize silica suspensions' vast
gaps occupied by the microsize additive particles prevent the clusters from growing. The
size of the additives' particles has an impact on how the silica particles interact with one
another. The size of the impediments inside the suspension gets closer to the silica
particles when the additive particle size is reduced, which lessens the disruption of the
clusters' expansion during thickening.
 29

Figure 8: Rheology results of viscosity vc shear rate for samples with total solid content
70%
 30

Figure 9: Rheology results of viscosity vc shear rate for samples with total solid content
68.5%
5.2.2 | Dynamic shear rheology

Amplitude Sweep, sometimes referred to as oscillatory Amplitude Sweep or Strain

Sweep, was carried out by progressively raising the strain amplitude while generating a
sinusoidal oscillatory shear deformation at a constant frequency. Gradually, we increase
the strain amplitude from a modest starting point until the material exhibits viscoelastic
or viscous behavior. The material exhibits predominately elastic behavior in the linear
viscoelastic region, where the storage modulus (G') predominates over the loss modulus
(G''). The material exhibits shear thickening behavior after a certain point, at which
particle interactions cause the complex modulus (G*) to grow dramatically. STFs are
interested in this area. In contrast, the material undergoes a sinusoidal oscillatory shear
deformation at different frequencies while maintaining a constant strain amplitude (1%),
in the frequency sweep test. This illustrates how the behavior of the material varies at
various deformation rates.

The amplitude sweep and frequency sweep curves of samples with a 70-weight
percent solid content are displayed in Figures 10 and 11. The amplitude sweep and
frequency sweep curves of samples containing 68.5 weight percent solid are displayed in
Figures 12 and 13. At low strain, the material's response is more elastic (G' > G'') in the
amplitude sweep graph. However, the material's reaction becomes noticeably more
viscous (G'' > G') at greater strain values. The crossing (G' = G'') occurs at the point
where G' and G'' intersect. A greater G' suggests that under deformation, the fluid stiffens
and becomes more solid-like. Higher G'' (loss modulus) values also imply that the
material is experiencing more intense internal friction and particle interactions since they
show that the fluid is losing more energy as heat during deformation. This energy loss
might cause the material to momentarily solidify and add to the general shear thickening
tendency. The material's behavior can be inferred from the frequency at which G' peaks
(storage modulus maximum) or G'' peaks (loss modulus maximum). The sample's higher
 31

G'' values in the frequency sweep analysis show that it is displaying stronger shear
thickening behavior.

Figure 10: Amplitude sweep of samples with Boron Nitride and total solid weight percent
70
 32

Figure 11: Frequency sweep of samples with Boron Nitride and total solid weight percent
70

Figure 12: Amplitude sweep of the sample with Boron Nitride and total solid weight
percent 68.5
 33

Figure 13: Frequency sweep of the sample with Boron Nitride and total solid weight
percent 68.5

5.3 Interaction analysis between particles in the STF

Particle dispersion and aggregation are two processes that occur in the suspension when a
result of the interactions between the particles. When there are no outside factors present,
the dispersed particle distribution in the STF is primarily influenced by electrostatic
repulsion on the particle surface, van der Waals interactions, and Brownian motion
between the particles [19] The silica particles tend to disperse due to electrostatic
repulsion and Brownian motion, whereas they try to aggregate due to the Van der Waals
force. The lubricating force between the particles in the STF system, which tends to
agglomerate the particles, also affects the distribution of scattered particles under external
stimuli. The combined action of several atoms or molecules is known as the van der
Waals force between particles. The following illustrates the van der Waals forces between
spherical particles of radii R1 and R2. where A being the Hamaker constant of particles in
the vacuum, R1 and R2 are the spherical particle's radii, and H is the distance between
particles. The adsorption layer on the dispersion system's particle surface will typically
 34

cause the particle distances to grow. Van der Waals force between the particles is also
decreased since the adsorption layer material constant is often lesser than that of the solid
particles. These forces between the nanoparticles can be disregarded in a shear thickening
system where the continuous phase is polyethylene glycol (PEG) and the dispersed phase
is nano-silica.
𝐴𝑅1𝑅2
𝐹𝑣𝑎𝑛 𝑑𝑒𝑟 𝑤𝑎𝑎𝑙𝑠 = 2 (1)
6𝐻 𝑅1+𝑅2( )

The homogenous particles resist one another when the silica particles in the
shear-thickening liquid approach one another and the overlapping of electric double
layers happen. The STF system is now producing an electrostatic repelling force.

2
2πϵ0ϵ𝑟ψ0·κ𝑎
𝐹𝑟𝑒𝑝 = 2
(2)

Particles in the laminar flow produce a lubricating force because the fluid is removed
when the STF is sheared. Particle size, shear rate, liquid viscosity, and spacing between
particles all affect how much force is exerted.
3
6πη0𝑎 γ˙
𝐹ℎ𝑦𝑑𝑟𝑜𝑑𝑦𝑛𝑎𝑚𝑖𝑐 = ℎ
(3)

In conclusion, the particles in the dispersed phase in STF are mostly impacted by
repulsion due to electrostatic forces when there are no external influences or low shear
rates, which preserves a stable layered structure distribution. The lubricating force
between particles rises with increasing shear rate, and the dispersed particles are forced to
move from their initial stable positions by shear stress. STF's stable layered structure
changes into a disordered structure, which raises the viscosity of the system. The STF
system is in the critical state of shear thickening transition when the intermolecular
lubricating force (10) generated by shear and the repulsive force between particles (9) are
equal. At this point, the shear rate equals the γ˙𝐶.
2
2πϵ0ϵ𝑟ψ0 𝑘 ℎ
γ˙𝐶 = 6πη0𝑟
· 2
· 𝑟
(4)
 35

5.3.1 Considering the case of a unit cell

Figure 14: Unit cell with silica nanoparticles at corners and Boron Nitride and
body-center

Assuming the distribution of silica and boron nitride particles in the suspension in the
form of a body-centered unit cell. In this case, we assume that the centered particle is the
closest to every other particle in the unit cell system. Assume that the closest distance
between atoms is h along the diagonal. Assuming the radius of the Silica nanoparticle to
be RSilica and the radius of the boron nitride particle to be RBN. Calculating Φ (the volume
fraction) for this packing.

Case 1: Assuming particle size of silica nanoparticle and boron nitride particles are
similar equals r

The number of silica atoms per unit cell is 1 (8 atoms with 8 sharing) and the number of
boron nitride atoms per unit cell is 1.

3
8π𝑟
ϕ= 3 (5)
𝑎

4𝑟 + 2ℎ = 𝑎 3 (6)
 36

1/3
ℎ
𝑟
= ( ) 3 3π
ϕ
− 2 (7)

2 1

( )
2πϵ0ϵ𝑟ψ0 𝑘 3 3π 3
γ˙𝐶 = 6πη0𝑟
· 2
·[ ϕ
− 2] (8)

Case 2: Assuming particle size of silica nanoparticle and boron nitride particles are of
different sizes (RBN and RSilica )

The number of silica atoms per unit cell is 1 (8 atoms with 8 sharing) and the number of
boron nitride atoms per unit cell is 1. r = (RSilica + RBN )/2 with r being the number
average radius of the unit cell. This value of r can be inserted into the above equation (8)
to get the value of critical shear rate when we consider the case that silica nanoparticles
and boron nitride particles are of different sizes. In conclusion, the expressions remain
almost identical, with the average radius of particle in the denominator, also enforcing
that the suspensions with bigger-sized particles have lesser critical shear rate, which is
experimentally found out as well.
 37

CHAPTER 6

CONCLUSIONS AND SCOPE FOR FUTURE WORK

Silica nanoparticles of uniform size were successfully synthesized using the modified
Stober process in reduced time. TEM micrograph revealed uniform spherical Silica
nanoparticles, with an average diameter of 330 nm. The Silica particle's Z-average
particle diameter is 303 nm. BN in silica with PEG showed better shear thickening ratios
than only silica nanoparticles in PEG. Apart from this, we did at least 3 rheology
experiments on every sample, and the results are replicable. The Boron Nitride as an
additive, increases the overall viscosity of the sample, but at the same time lowers the
critical shear rate.

More optimizations related to silica nano-particle preparation can be done, at various

times. A study related to the silica nanoparticle prepared at time t and its rheology study
can give an optimal time as per our requirements. Besides this, the samples containing
Boron Nitride impurity can be further tested on Kevlar fabric for improvements in impact
resistance properties. Other additives can also be tested and mixed with silica
 38

nanoparticles to compare their improvements in the overall rheology and impact

resistance properties.

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