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IC-MAME 2021 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1225 (2022) 012053 doi:10.1088/1757-899X/1225/1/012053

Effect of Surface Modification of Silica Nanoparticles with

Thiol group on the Shear Thickening Behaviors of the
Suspensions of Silica Nanoparticles in polyethylene glycol
(PEG)

Shuchi Sharmaa, Yogesh Kumar Waliaa* , Gunjan Groverb, Sanjeev K.

Vermab*,.
a
Career Point University, Hamirpur, 176041,India
b
Terminal Ballistics Research Laboratory, DRDO, Chandigarh,160030, India
[email protected],

ABSTRACT. The Fine-tuning of Shear Thickening Fluids (STFs) by surface modification of silica particles
has fascinated scientist's interest worldwide as it results in performance enhancement of STF based on armor
systems. In the current study, surface modified Silica nanoparticles (average diameter of 600 nm) possess thiol
functional groups which were attained through a reaction with 3-mercaptopropyl-trimethoxysilane in absolute
ethanol at 90 °C. Shear thickening fluid of Thiol functionalized Silica nanoparticles were prepared by
sonochemical method in polyethylene glycol (PEG-200). The rheological parameters of STFs (modified and
unmodified silica Nano particles) were measured using Rheometer MCR 52, Anton Par, Germany. The shear
thickening behavior of thiol-based STF shows shear thickening at a higher shear rate compared to only silica-
based STF with the decrease in viscosity maximum.

Keywords: Bullet Impact; Shear Thickening Fluid; Strain-Thickening; Particle Dispersion;

Rheology.

1. INTRODUCTION:

The guardians of our country are provided with body armors, which are designed to weaken slashing or
penetrating attacks by resisting the low-velocity bullet penetration. Multiple layers of high modulus,
high strength, and low-density fabrics eg. Kevlar & Dyneema have been reported to be used for making
soft armor panel (SAP) for protection against 9 x 19mm ammunition[1–4]. However, increases the
weight of the armor observed because of large number of layers of ballistic materials, thereby posing
restrictions to the comfort and mobility of the user. A lot of work has been reported in lliterature cites
for the reduction in the areal density of the armor. One such potential method is application of liquid
armor or shear thickening fluid (STF) on high strength fabric like Kevlar. [5. 6].

A large number of reports have been published on shear thickening phenomena of colloidal suspensions
[7-9]. Under sudden impact the liquid armor or the colloidal suspension of hard particles in polymer
matrix converts to a solid-alike state, however, at low shear rates STF flows easily because of lower
viscosity. A number of methods have been put forward in literature to elaborate the Non-Newtonian
behavior of concentrated suspensions. In one of the early studies, a rise in viscosity is proposed by
Hoffman because of order-disorder transition of particles [10, 11].

Nonetheless, shear-induced hydro clusters formation is the most widely accepted mechanism, in
which inter particle repulsive forces was completely overcome by hydrodynamic lubricating forces that
results to increase in viscosity. This simulation studies, rheological and optic-SANS supported this
hypothesis. [12-15]. The possibility to control rheological property of STFs for desired applications
makes STF a suitable candidate for a lot of applications in different fields such as damping devices,

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IC-MAME 2021 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1225 (2022) 012053 doi:10.1088/1757-899X/1225/1/012053

body armors, medical devices smart structures etc [16- 21].

The shear thickening behaviour of STF depends on different parameters such as particle shape, particle
size, particle concentration, and polydispersity of dispersed particles, the method of preparation of STF
and the molecular weight of polymeric matrix. The ST behavior of STF is considerably influenced by
the surface properties of dispersed particles [22-29]. The surface modification of silica nanoparticles
significantly alters particle–media and the particle-particle interactions.. Thus, shear thickening fluids
consisting of surface-modified silica nanoparticleshas bee in interest worldwide specially for its energy
absorption behavior with potential application in base protective system.
Mahfuz et al. prepared STF using surface-modified silica particles with aminopropyl triethoxy silane
and its application to Kevlar fabric was analyzed [30,31]. The performance of the resulting armor
composites was observed to improve significantly in comparison to that of the neat fabric. Butola et al
reported that a reduction in surface hydroxyl group increases the energy absorption behavior of shear
thickening fluids [32,33]. This paper includes the synthesis of thiol-modified Silica Nanoparticles based
shear thickening fluid and its rheological behaviors in continuation of our earlier research works related
to fine-tuning of shear thickening fluids. To the best of our knowledge, the STF of Thiol modified Silica
particles has not been reported in literature. This study also believes in the development of STF based
armor systems [1, 2, 15, 34-36].

2. EXPERIMENTAL:

2.1 Materials

The spherical silica nanoparticles of particle size 600nm and PEG 200 were used for the synthesis of the
Shear Thickening Fluids. The average particle size of unmodified and surface- modified silica nanoparticles
was measured through DLS (Fig. 1a), and also through SEM (Fig. 1b). 3-Mercaptopropyltrimethoxysilane
(MPTMS) was used for the modification of dispersed particles (silica particles 600nm). The absolute ethanol
99.9 % was used in synthesis of STFs.

2.2 Synthesis of Thiol-modified Silica Nanopartilcles.

Thiol-modified Silica nanoparticles with different concentration of surface thiol groups were synthesized by
dispersion of the nanoparticles (10g) in a solution of 3- Mercaptopropyltrimethoxysilane (MPTMS) (25-100
mmol) in toluene (400.0 mL) as shown in table 1. The mixture was reflux for 12 hours. The final centrifuged
product was left for another 2 hours and than washed with toluene, ethanol, and dried under vacuum.
Ellman's reagent and Emmett–Teller (BET) surface area is used to determine the quantity of thiol group
( SH) per particle of functionalized silica nanoparticles.

Table 1. Mercaptopropyltrimethoxysilane (MPTMS) mmols added to silica nanoparticles of average

particle size 600nm.

S. No. Sample Code. Silica Nanoparticles -600nm MPTMS

(grams) (mmol)
1 Silica-SH-25 mmol 10 25
2 Silica-SH-50 mmol 10 50
3 Silica-SH-75 mmol 10 70
4 Silica-SH-100 mmol 10 100

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IC-MAME 2021 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1225 (2022) 012053 doi:10.1088/1757-899X/1225/1/012053

2.3 Synthesis of Shear thickening fluid

In this study, shear thickening fluid with 70 wt% of modified and unmodified silica nanoparticles were
synthesized using sonochemical & homogenization method with ethanol solvent. The treated and untreated
silica nanoparticles (70% w/W) were dispersed in ethanol (excess) using homogenisation at 5000 rpm for
10 minutes followed by sonication at a frequencyof 24 kHz, 75 W/cm2 for 10 min. After it the polyethylene
glycol (PEG-200) (liquid, 30 % w/W) was added and the mixture is homogenised for 10 minutes at 5000
rpm followed by sonication. The reaction mixture was maintained below 40°C. Ethanol was evaporated
under vacuum and product is collected as pale yellow or white coloured liquid.

2.4 Rheology of Shear thickening fluid

ST behavior of the synthesized STF samples was analyzed by rheological studies with MCR-52 Rheometer,
Anton Paar, Germany, with cone angle of 1 º in cone–plate geometry plate diameter of 40 mm and a gap
of 0.08 mm. All the rheology experiments were performed at 25 oC with shear rate in the range of 0 - 2000/s
.All the STF samples were subjected to 6 seconds pre-shearing at 0.1 to 1 S-1 to set up an equilibrium
structure of the sample and to remove any air bubble in the system.

3. RESULTS AND DISCUSSION

The dispersed silica nanoparticles of average size 600 nm were treated with different concentration of
Mercaptopropyltrimethoxysilane (MPTMS) (25-100 mmol) to achieve different concentration of surface
thiol groups (Table 2). Mercaptopropyltrimethoxysilane is usually used for surface modification of
nanoparticles with thiol groups as shown in figure 1. Huang and co- workers functionalized mesoporous
silica materials with MPTMS [34].

Ellman’s reagent-5,5’-dithiobis-
(2- nitrobenzoic acid)

Figure 1. Schematic representation of surface modification of silica nanoparticles with thiolfunctional group.

The morphology and average diameter of unmodified and modified silica nanoparticles (Silica- SH-100mmol)
was studied by SEM (Scanning Electron Microscope) analysis as shown in Figure 2. It was observed that
functionalization of silica nanoparticles doesn’t result to significant change in particles size.

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IC-MAME 2021 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1225 (2022) 012053 doi:10.1088/1757-899X/1225/1/012053

Unmodified Silica Nanoparticle Modified Silica Nanoparticle (Silica-SH-100mmol)

Figure 2.SEM analysis on unmodified and modified Silica Particles with thiol group

The BET (Brunauer–Emmett–Teller) surface area of unmodified silica particles and thiol functionalized
silica nanoparticles were evaluated. Based upon the results it was further utilized along with Ellman’s
reagent 5,5’-dithiobis-(2-nitrobenzoiac acid)] (DTNB) (figure 1) to calculate the number of thiol groups
per silica nanoparticles (Table 2) [35].
The surface charges of unmodified and modified silica particles dispersed in ethanol were evaluated using
the zeta potential at pH of 6.7. The unmodified silica shows zeta potential of -7.1 ± 2 mV due to the
deprotonation of surface hydroxyl groups (Table 2). Whereas, after modification with M3-
Mercaptopropyltrimethoxysilane (MPTMS), the zeta potential of the thiol functionalised silica particles
was observed at -11.1 to -17.4 mV.

Table 2. Zeta potential/surface area and Thiol group per particles of modified and unmodified shear
thickening fluids.

S. Sample Zeta Potential(mV) Surface area per Thiol (-SH) group

No. particle (nm2) per Particle

1 Unmodified Silica -7.1 ± 2 5.20 x 105 0

2 Silica-SH- -11.1± 2 4.50 x 104 1.20 x 106

25mmol

3 Silica-SH-50 -14.2± 2 4.35 x 104 1.90 x 106

mmol
4 Silica-SH- -17.1± 1 4.20 x 104 2.21 x 106
75mmol
5 Silica-SH- -17.4 ± 1 4.15 x 104 2.23 x 106
100mmol

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IC-MAME 2021 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1225 (2022) 012053 doi:10.1088/1757-899X/1225/1/012053

Table 3. Rheological parameters of surface modified shear thickening fluids of different Thiolconcentration

S. Sample Name Critical Critical Shear Viscosity

No Shear Rate Viscosity Max Max
. (s-1) (Pa.s) (s-1) (Pa.s)
1 Unmodified Silica 2.23 7.7089 81.7 238
2 Silica-SH-25mmol-70% 4.82 4.5176 37.7 187.39
3 Silica-SH-50mmol-70% 13.5 2.007 48.8 143.84
4 Silica-SH-75mmol-70% 16.1 3.4073 48.8 128.47
5 Silica-SH-100mmol-70% 29.2 2.9346 106 67.433

Figure 3. Steady state viscosity as a function of shear rate of STF of unmodified and surfacefuntionalised
silica particles.

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IC-MAME 2021 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1225 (2022) 012053 doi:10.1088/1757-899X/1225/1/012053

Figure 4. Viscosity max profile and Critical shear rate of the STFs with different SH concentration.

The steady viscosity as a function of shear rate from 0 to 1000 s-1 of STF of unmodified and surface
functionalised silica particles was depicted in Figure 3. It can be seen that all the STFs of both kind of
particles show a similar rheological behaviour to the applied shear stress. At lower shear rates the viscosity
of STFs decreases. It is followed by a spontaneous rise in viscosity aftera critical value of shear rate. It
exhibits shear thickening response of both kind of shearthickening fluids. This is an important aspect for
the impact energy absorption of shear thickening fluids . Steady-shear rheological analysis (Figure 3)
also shows the effect of SH onthe steady shear response of the synthesized STFs. It was observed from
Figure 3 & 4 and Table3 that with increasing –SH concentration of modified silica nanoparticles, a fall in
the maximum viscosity and rise in shear rate was observed. The maximum viscosity value decreases from
238 to 67.43 Pa.s as the thiol concentration on the surface of silica particles was increased to 2.23 x 106 per
particle. It was also observed that the critical shear rate value increases from 2.23 to 29.2 sec-1 with increase
in thiol concentration on silica nanoparticles.
In case of the thiol modified silica nanoparticles, the STF formed shows lesser attraction between hydrophilic
polyethylene glycol and hydrophobic thiol modified silica particles This results to increase in critical shear
rate (29.2 s-1) with the lowering of the peak viscosity (67.43 Pa.s) for the onset of shear thickening of
STFs.

Previous studies have reported that the hydroxyl density on silica influences the inter-particle interactions
of particles [30-32]. It is understandably obvious from Fig. 3 that modified silica based STF shows
significant increase in the critical shear rate profile compared to that of silica- based STFs. In our study, it
was found that the STF of -SH functionalized silica nanoparticles have shown a lesser inter-particle
attraction as compared to unmodified silica particles due to lower surface hydroxyl density. It will result
to increase in value of critical shear rate. Butola etal [36] also found increase in performance of shear
thickening fluid with decrease in surface hydroxyl group. It was also observed that with the decrease in
surface OH group, the viscosity max of the STF decreases with increase in critical shear rate. The critical
shear rate is one of the important parameter for ballistic performance of armor panels. The STF with higher
shear rate maintain the flexibility of armor panels and results in shear hardening at higher shear rate. The
developed STF of thiol modified silica particles with higher critical shear rate and lower surface hydroxyl
group is therefore a plausible candidate for STF based armor systems.

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IC-MAME 2021 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1225 (2022) 012053 doi:10.1088/1757-899X/1225/1/012053

4. CONCLUSION

This study opine a method in which silica nanoparticles of different concentration with surface thiol groups
were synthesized by the reaction of silica nanoparticles with average particle size of 600nm and MPTMS.
Shear thickening fluid of thiol functionalized silica nanoparticles were characterized using steady state
rheology. It was observed that thiol functionalized silica nanoparticle based STFs shows shear thickening at
higher shear rate compared to unmodified silica nanoparticles. Therefore, the STFs of modified silica NP is
well-advised as more suitable fluid for STF based armor system.

Conflict of interest

The authors declare that they have no conflict of interest.

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IOP Conf. Series: Materials Science and Engineering 1225 (2022) 012053 doi:10.1088/1757-899X/1225/1/012053

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