Silica nanoparticles reinforced natural rubber latex composites: The

effects of silica dimension and polydispersity on performance

Lijian Xia, Jianhui Song, Hui Wang, Ze Kan
Key Laboratory of Biobased Polymer Materials, Shandong Provincial Education Department, School of Polymer Science and
Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China
Correspondence to: Z. Kan (E-mail: [email protected])

ABSTRACT: The nano-size autonomous monodisperse silica (AS) particles were prepared by hydrolysis and condensation of tetraethoxy-
silane using L-lysine as catalyst. The silica/natural rubber (NR) masterbatches were then produced via latex compounding, in which NR
latex was mixed with the above AS dispersion. The commercial precipitated silica (PS) was introduced as a control. The effects of both
AS and PS particles on the interfacial and mechanical properties of composites were systematically examined. It was found that the AS
formed bead-like morphology wherein the clear particle edges can be distinguished in rubber matrix. Compared with PS/NR, the AS/NR
composites were proved to possess more bound rubber and weaker filler–filler interaction resulting in higher tensile strength, abrasive
resistance, and resilience. Meanwhile, the efficiency of premodified AS and PS surfaces using bis-(3-triethoxysilylpropyl) tetrasulfide on
reinforcing the properties of silica/NR composites was studied. The results presented that the overall properties of modified silica/NR
vulcanizates were improved significantly. In special, the values of heating building-up and compression set showed an evident decline
which was of great significance for tire tread or other rubber products. For the dynamic properties, the magic angle spinning/NR com-
posites had lower rolling resistance. In short, AS may be applied as an ideal substitution of PS in rubber. © 2019 Wiley Periodicals, Inc. J.
Appl. Polym. Sci. 2019, 136, 47449.

Received 28 September 2018; accepted 2 December 2018

DOI: 10.1002/app.47449

INTRODUCTION (3-triethoxysilylpropyl) tetrasulfide (TESPT) is the most commonly

In the field of rubber processing, as being the largest representa- used silane coupling agent.14 The other problem that the tradi-
tive, natural rubber (NR) is usually required to be reinforced with tional blending technique may suffer is involving the low efficiency
fillers to satisfy necessary strengths and mechanical properties for and high processing temperature when adding silane coupling
most applications.1–5 The commonly used reinforcing fillers in the agent into bulk compound.10 The latex compounding technique
current industry are carbon black and silica. Silica features differ- can efficiently avoid the above limitations of proper time and pro-
ent specialties and it provides a much better combination of lower cessing conditions and is becoming a promising method.
rolling resistance and considerably higher wet-skid traction of tire For silica/NR compound prepared by latex compounding tech-
tread compounds compared with carbon black.6,7 As a conse- nique, several attempts have been made to explore the feasible and
quence, silica nanoparticles have attracted great attention in order advantageous process. First, the in situ silica particles prepared by
to replace carbon black since the introduction of “Green Tire in situ sol–gel method with silica precursor, and then co-flocculated
Technology” concept by Michelin in 1992.6,8 However, the exis- with rubber latex has been reported.15–18 Meanwhile, many efforts
tence of numerous hydroxyl groups and high polarity on silica sur- have been carried out focusing on the silica reinforce rubber in
face leads to tendentious aggregation which thus weakens the latex system by sol–gel method as well.19–21 Second, various types
filler–rubber interaction against its dispersion in rubber of commercial silica were used to prepare the silica slurry, which
matrix.6,9–12 Moreover, when a large amount of silica is added into was blended with NR latex to prepare the masterbatches
rubber, the viscosity increases dramatically, which gives rise to directly.22,23 For silica surface modification, some researchers have
troubles in processing compounds and even results in damages of developed two steps of premodification of silica with TESPT in
the instrument.6 In order to overcome these problems, different organic solution and then mixed the premodified silica (after dry-
kinds of coupling agents were widely used in shielding or reducing ing) with rubber in traditional blending way.7,9 As reported, partic-
the hydroxyl groups on silica surface.11,13 Among them, bis- ulate fillers are commonly used to improve mechanical properties

Additional Supporting Information may be found in the online version of this article.
© 2019 Wiley Periodicals, Inc.

47449 (1 of 11) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47449

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of tires in automotive industry.20 However, the final difference of silane modified silica into the NR latex. At last, the modified sil-
interfacial and mechanical performances within reinforcing NR ica/NR masterbatches were obtained. Paying special attention to
between the discrete silica particles and the commercial precipitated the mass of above masterbatches, there was almost no silica loss
silica (PS) which aggregated severely is not yet clear. It is worth during the coagulation and drying process even though AS con-
noting that Yokoi24 reported the periodic arrangement of silica tent was increased up to 30 phr. As contrast, the loss of PS was
nanospheres assisted by lysine which derived from the “StÖber proportional to the silica content filled NR masterbatches and
method”25 in 2006. Meanwhile, many researchers have verified that nearly lost 1 phr at the maximum content of 30 phr.
the lysine may be advantageous to NR in many models.26–28 Silica Surface Modification by Silane Coupling Agent
In this study, the nano-size autonomous monodisperse silica The hydroxyl groups on silica surface are well known to hinder
(AS) with ~28 nm was prepared from the hydrolysis and condensa- the dispersion of silica particles in NR matrix and lower the effi-
tion of tetraethoxysilane (TEOS) catalyzed by L-lysine first. In the ciency of reinforcement in mechanical properties.30 The surface
meantime, the PS was introduced to be used as a contrast. The modification of silica particles is the most common and effective
Brunauer–Emmett–Teller (BET) surface areas of these two kinds of way to improve the silica surface properties and reinforcement
silica were used as the comparison standard. The silica/NR master- efficiency.30 TESPT has been the commonly used silane coupling
batches were prepared by the latex compounding technique. At the agent in the modification process of silica.14 It was demonstrated
same time, the silica slurry was added after being concentrated into that premodification of silica by a novel two-step-method pre-
the hydrolysates of TESPT in water and ethanol mixed solution. As a sents significant advantages compared with the traditional way of
result, the salinized AS or PS obtained were mixed with NR latex, and blending silica, silane coupling agents, and rubber in open or
then the modified silica/NR masterbatches were prepared. Different internal mixer.9 Li et al. reported the hydrolysates of TESPT and
contents (10–30 phr) and types (modified or not) of silica were pro- the optimal reaction condition in liquid system.7,9 In our typical
grammed to prepare the silica/NR compounds and vulcanizates. The run, absolute ethanol 1000 mL and deionized water 30 mL were
difference of reinforcing effects between these two kinds of silica was first added into a beaker, and then hydrochloric acid was used to
characterized in detail. The overall properties of these compounds or adjust the pH value to ~4.5. TESPT (mass ratio of TESPT to sil-
vulcanizates were investigated and discussed thoroughly. ica = 8%) was added into the solution for the hydrolysis and pro-
ceeded for 10 h. After that, the AS solution or PS slurry with a
EXPERIMENTAL volume of ~400 mL after concentration was added into the for-
Materials mer solution of silane hydrolysates and then allowed to react for
L-Lysine (98%) was purchased from Aladdin Industrial Corpora- 24 h at 50
C. It is worth noting that large amounts of ethanol
tion (Shanghai, China). TEOS (98%) was produced by Tianjin can be recycled by using the rotary evaporator.
Beilian Fine Chemical Co. Ltd. (China) Commercial NR latex
Preparation of Silica/NR Compounds and Vulcanizates
(High ammonia grade, 0.7%; non-deproteinized) with 61% mass
In order to obtain the well-dispersed silica/NR compounds, the
fraction dry rubber content produced in Thailand was purchased
silica/NR masterbatches were masticated on the 6 in. two-roll
from Shanghai (China) Taijiao International Trade Co. Ltd.
mill (Dongguan Bolon Precision Testing Machines Co. Ltd.,
TESPT produced by Evonik Degussa (China) and obtained from
China), and the condensate water was flowed into the roller con-
Qingdao De Xinyuan Industry and Trade Co. Ltd. (China) PS
stantly to maintain the temperature at 55
C. Then, the zinc
(1165 MP, BET surface area 165 m2/g) was purchased from Sol-
oxide, stearic acid, 2-mercaptobenzimidazole, and N-tert-butyl-
vay white carbon black (Qingdao Co. Ltd.). All of the rubber
2-benzothiazolesulfenamide were uniformly blended with the
ingredients were industrial grade and used as received.
masterbatches. The sulfur was added into the compounds at last
Preparation of Silica Suspension and Silica/NR Masterbatches and the sheets with an approximate thickness of 1.5 mm were
The desired size of AS (28 nm, BET surface area 169 m2/g) was obtained. The whole mixing process took 20 min for each exam-
obtained from the method reported by Yokoi.29 The different ple. The scorch time (ts2) and optimum cure time (t90) of the
contents of synthetic silica suspension were concentrated utilizing compounds were measured by a rheometer vulcanization
the rotary evaporator to certain volume (400 mL) before adding machine (MDR-2000, Alpha) at 150
C. The oscillating fre-
to the mechanical agitated NR latex. quency was 1.7  0.1 Hz, with an amplitude of 3
. The volume
of each test specimen was ~5 cm3. The compounds were vulca-
Different qualities of PS were prepared to silica slurry by the fol- nized at 150
C and 10 MPa for t90 in a hydraulic press
lowing steps. A carefully weighted PS was added into the same (HS100T-RTMO, Shenzhen Jiaxin Co. Ltd., China), and the sil-
volume (400 mL) of deionized water and stirred well before used. ica/NR vulcanizations were then obtained. The cure rate index
After agitating for 0.5 h by overhead mechanical stirrer (double (CRI) was calculated using the following equation:
polytetrafluoroethylene agitator blade, 300 r/min), the master-
batches of silica/NR were coagulated using 3% w/w calcium ethy-

CRI min − 1 ¼ 100=ðt90 − ts2 Þ ð1Þ
late. Then, the flocculates were made to sheets form for next uses
and washed with water several times. The residual solution was
required to be centrifuged and the residual solids were collected
with the former washed compounds sheets. The resulting mix- Characterization
tures were dried at 55
C in the oven until a constant weight was Scanning Electron Microscopy (SEM) Analysis. SEM photo-
reached. The same operation was applied on the addition of graphs of silica slurry were taken using a Quanta FEG250 of field

47449 (2 of 11) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47449

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emission scanning electron microscope (FEI Co.) to distinguish (ASTM D2240) and resilience (ASTM D2632) tests were carried
the silica morphology between the AS and PS particles before out accordingly.
adding into the rubber latex. All of the silica samples were
The compression heat build-up test was performed in a GT-
dropped on silica wafer and sputter-coated with a thin layer of
RH2000 Flexometer (Gotech Testing Machines Co., Taichung
gold after dried to prevent electrical charging during the exami-
City of Taiwan) according to ASTM D623. Cylindrical rubber
nation. And the measurement was performed at an accelerating
specimens having 25 mm in height and 17.5 mm in diameter
voltage of 15 kV and operation distance was 10 mm.
were subjected to the repeated compression. The compressive
loading was 24.5 kg with the frequency of 30 Hz at the onset
Dynamic Light Scattering (DLS) Analysis. DLS instrument temperature of 55  1
C, and the inside temperature of the rub-
(Mastersizer 2000, Malvern, British) was used to measure the ber composites was recorded after 25 min. Three specimens were
particle size of silica suspension or slurry, corresponding with the measured for each sample, and the average values were calculated
characterization by SEM. A trace of emulsifier was of great use to and reported. As we know, the mechanical properties mentioned
make silica particles discrete when tested. above were related to the ability of resistance to deformation,
elasticity, and recovery capability. For instance, the tensile
Fourier Transform Infrared Spectroscopy (FTIR) Analysis. A strength is the ability of the vulcanizates to resist permanent
fraction of the modified silica was soaked in toluene for 24 h, deformation and damage under external forces. The resilience
then filtered and dried in vacuum oven at 60
C for 24 h. The represents the elasticity ability to recover the original shape after
difference in reactive groups between pure silica and modified sil- the external force disappears; the modulus and hardness repre-
ica was identified on a Tensor 27 FTIR spectrometer (Bruker Co., sent that the force required to produce a certain deformation of
Germany). the vulcanizates. The vulcanized rubber undergoes repeated com-
pression deformation, and most of the work consumed by com-
Determination of Bound Rubber Content (BRC). The BRC was pression deformation is converted into heat.
determined by extracting the uncured compound. Samples of The viscoelastic properties of the composites were measured on a
0.5 g of uncured rubber compound were cut into small pieces DMA242 (NETZSCH Co., Germany) in the tension mode. The
and transferred into a Nickel net cage with 200 mesh size, which temperature was varied from −75 to 80
C. The heating rate was
were then soaked with toluene for 72 h at room temperature and 3
C/min. The frequency was 10 Hz. The strain amplitude was
the solvent was renewed every 24 h. Finally, the residual com- 25 μm. The loss angle tangent (tanδ) was measured as a function
pound was dried at 60
C in vacuum oven to a constant weight. of the temperature for the samples under identical conditions.
The weight of the samples before and after extraction was mea- Long striped specimens were prepared from the specimens of
sured and the BRC was calculated according to the following dumbbell-shaped and cut off both the ends.
equation:

Dispersion Morphology Measurement. The filler dispersion was
w2 − w1 mf = mf + mr investigated on Tecnai G2 20 TEM (FEI Co.) with an accelerating
Bound rubber% ¼
× 100 ð2Þ
w1 mr = mf + mr voltage of 200 kV. The thin sections for TEM observations were
cut by a microtome at −100
C and collected on copper grids.

where w2 is the weight of sample after drying and w1 is the RESULTS AND DISCUSSION
weight of the sample before swelling. mf and mr are the fraction Characterization of Silica
of filler and rubber in the compound, respectively.31 The results SEM and DLS were used to observe the morphology and silica
were averaged over three samples. dimension of the particles added into the latex. Figure 1 presents
the SEM images and corresponding DLS results of silica. As can
Rubber Process Analyzer Analysis. The dynamic rheological be seen from Figure 1(a,b), the morphology of AS mainly showed
properties of the silica/NR compounds were analyzed using an closely packed spherical shape with the diameter of 25–30 nm. In
RPA2000 rubber process analyzer (Alpha Technologies Co.) at contrast, the PS from Figure 1(c,d) was observed to have multiple
60
C. The strain sweep amplitude was varied from 0.2 to 100% peaks, which indicated a broad distribution of particle sizes due
at the test frequency of 1 Hz. Curves of storage modulus (G0 )- to the severe aggregation.
strain (ε) were obtained.
FTIR Results of Modified Silica
The samples were pressed into pellets together with potassium
Mechanical and Dynamical Property Measurement. The
bromide (KBr). The spectra were recorded in the wavenumbers
physical–mechanical properties of the silica/NR vulcanizates such
range 400–4000 cm−1. The spectra were shown in Supporting
as the tensile properties including the tensile strength and modu-
Information Figure S1.
lus at 300% elongation (ASTM D410) were determined by a
CMT4104 Electrical Tensile Tester (AT-7000S, ZWICK Co., Ger- As can be seen from the results, the absorption peaks at 3440
many) at a tensile rate of 500 mm/min. The specimens were pre- and 1650 cm−1, corresponding to the stretching and deforming
pared to the dumbbell-shaped that were punched out from a vibration modes, respectively, were the H O H bonds of the
molded sheet. Five specimens were measured for each sample, adsorbed water; the absorbance ranging from 1000 to 1150 cm−1
and the average values were calculated and reported. Hardness was assigned to the Si O Si stretching mode. The surface

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Figure 1. SEM images and corresponding DLS results of the silica suspension; (a) AS; (b) the corresponding DLS results of AS with single peak and
~28 nm size; (c) PS; and (d) the corresponding DLS results of PS with multiple peaks.

grafting reaction was realized by the chemical reaction between prepared in the 6 in. two-roll mill as shown in Table I. Among
the hydroxyl groups of silica and the silanol groups of hydrolyzed them, the neat NR was introduced as control.
TESPT. Therefore, the appearance of characteristic bond, such as
the peak for methylene ( CH2 ) at 2850–2900 cm−1, in the
FTIR spectra of modified silica, proved that the reaction took Vulcanization Characterization of Silica/NR Compounds.
place successfully. Figure 2 and Supporting Information Table S1 show the vulcani-
zation characteristics of different silica/NR compounds. As can
be seen in Figure 2, the minimum torque ML value, correspond-
Application of Silica in the NR Latex ing to the compounds viscosity,3,23 was found to increase with
The fabrication process of all the samples was illustrated in Sup- increasing the loadings of silica. The ML values attained the max-
porting Information Figure S2. The silica/NR compounds were imum at 30 phr loading of silica. It can be attributed to the

Table I. Formulation of Silica/NR Compounds

Content (phr)a

Material Gum AS10b AS20 AS30 MAS30c PS10d PS20 PS30 MPS30e
f
Dried NR 100 – – – – – – – –
g
AS/NR masterbatch – 110 120 130 – – – – –
PS/NR masterbatchh – – – – – 110 120 130 –
AS/TESPT/NR masterbatchi – – – – 132.4 – – – –
PS/TESPT/NR masterbatch – – – – – – – – 132.4

Zinc oxide 5.0, stearic acid 2.0, sulfur 2.2.

2-Mercaptobenzimidazole 1.0, N-tert-butylbenzothiazole-2-sulfonamide 1.5.
a
Parts per hundreds of rubbers.
b
10 phr of AS filled NR latex was marked as AS10.
c
30 phr of AS modified by TESPT filled NR latex was marked as MAS30.
d
10 phr of PS filled NR latex was marked as PS10.
e
30 phr of PS modified by TESPT filled NR latex was marked as MPS30.
f
NR latex was coagulated and dried using the same method as the silica/NR masterbatch.
g
Different contents of AS filled NR latex, coagulated and dried.
h
Different contents of PS filled NR latex, coagulated and dried.
i
Silane coupling agent of TESPT was 8% w/w silica.

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Figure 2. Vulcanization curves of silica/NR compounds containing different silica contents and types: (a) AS; (b) PS. [Color figure can be viewed at
wileyonlinelibrary.com]

higher BET surface and the greater rigidity of AS. The ML values compounds were shown in Table S1. The more adsorption of
of AS filled NR compounds were higher than that of PS/NR com- curatives on silica surface, the less remained in rubber matrix,
pounds for all the same silica loadings. Meanwhile, it was and the cure rate decreased consequently.
observed a decrease in viscosity of compounds after adding
For delta torque (ΔM) of all composites, which represents the
TESPT into silica. This may be due to the plasticizing effect
crosslinking density,2,32,33 the silica-filled NR composites were
induced by the silane coupling agent and the chemical reaction
higher than that of the neat NR vulcanizates. On the whole, it
between TESPT and silanol group on the silica surface.4,13
was normal that the ΔM of AS/NR vulcanizates were lower than
In other aspects, the scorch time (ts2), cure time (t90), and CRI those of PS. This demonstrated that the AS filled NR hindered
represent the differences of cure characteristics between AS filled rubber crosslinking with surface properties having more adsorbed
NR compounds and PS ones, and these differences were due to of curatives.
the various surface properties of different silica types. Among
Comparing the silica before and after modification, that is, AS30
them, the processing is safer with the longer of the scorch time
and MAS30 filled NR compounds, the scorch time was shortened
ts2.6 The ts2 of AS/NR was longer than that of PS/NR at every
and curing rate was speeded up due to the introduction of extra
content of silica, and all ts2 decreased with increasing content of
sulfur of TESPT under heat. The final crosslinking density was
silica whether AS/NR or PS/NR. (Table S1). The silanol group on
observed to become larger at given loadings of silica and TESPT.
silica surface generally confers the acidity. The acidity on silica
Prasertsri et al. also reported the lower CRI and prolonged t90
surface retards the curing process by adsorption of curing agents
after PS modified by TESPT and filled NR compounds.23 This
and reacting with the activator as well as the accelerator.16,22,30
may be partially due to the special treatment mode of silica in
AS presented higher exposed interface and gave rise to more
aqueous system. Notably, the final crosslinking density of MPS
absorption of cure agents compared with PS. As a result, all of
filled NR vulcanizates was found higher than that of MAS/NR
the ts2 of AS/NR or PS/NR compounds decreased with increasing
composites.
content of silica, which was consistent with the previous work.23
Meanwhile, the ts2 of PS filled NR compounds were lower com-
Micromorphology of Silica/NR Vulcanizates by TEM. The
pared with AS/NR compounds, which indicated that this kind of
TEM images in Figure 3 show the difference of the silica disper-
compounds was easier to scorch. This can be explained that PS
sion in NR composites before and after silica modification at
has smaller exposed surface area and lower absorption of cura-
30 phr silica loading. It has been well-known that the filler dis-
tives, while more left in the rubber matrix.19 In the preparation
persion is one of the most important factors to determine the
of silica/NR masterbatches, all of the silica was moisture-treated
comprehensive properties of the rubber composites.7 The rubber
and the moisture existed on the silica surface promoted the
matrix will be with superior performance due to the higher uni-
hydrolysis of nitrogen-sulfur bonds of the accelerator NS, which
formity of silica dispersion. In the meantime, the filler agglomer-
then reacted to the formation of 2-mercaptobenzothiazole (MBT)
ates dispersing in the rubber matrix are more likely to induce
and resulted in faster scorch.22,23 In addition, in the crosslinking
stress concentration thereby resulting in the inferior mechanical
network of vulcanizates, effective crosslinking includes three
and dynamic properties.34
types: one type is the geometric tangles of molecular chains;
another one is the physical junction points, such as hydrogen Figure 3(a,b) illustrates the dispersion morphology of AS and PS
bonds and van der Waals force; and the last one is the C C, in NR matrix before modification, respectively. The filler was
C S, and S S chemical bonds and bonding rubber between rub- found aggregate in both of the composites as evidenced by the
ber molecule and silica. After the addition of silica, the number darker appearance compared to the rubber matrix. In addition, it
of crosslinking points increases; meanwhile, the molecular weight was observed that different distribution of the fillers was formed
between interconnecting points decreases, which also indicates for different samples. The size of filler aggregations in Figure 3
that the degree of vulcanization and the crosslinking density (a) was as small as 50 nm, and rose to the maximum of up to
increase. Furthermore, the CRI values of different silica filled NR 290 nm in diameter as indicated by the arrow. The same trend

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Figure 3. TEM images of silica/NR vulcanizates with different silica types at specific silica loading 30 phr. (a) AS; (b) PS; (c) AS modified by TESPT; and
(d) PS modified by TESPT.

on the filler was observed in Figure 3(b). Furthermore, the great particles. All these results may be due to the less aggregates
difference between these two types of silica lay in that the bead- between AS particles, which therefore gave rise to higher exposed
like morphology existed and clear particle edges could be verified interfacial area with rubber chains. After modification with TESPT,
even in the aggregations of AS in Figure 3(a). However, Figure 3 the decreased surface polarity of silica will be the major contribu-
(b) showed the distribution of a group of aggregations with vari- tion factor to both the higher bound rubber contents and stronger
ous shapes and it was difficult to identify the certain silica parti- interaction between the filler and nonpolar rubber. Considering all
cles. There was also a large blank between the aggregates in the the experiment results above, it is consistent with the theory that
rubber matrix. The max aggregates reached 500 nm in diameter. spherical silica particles with homogenous size and continuous net-
works strengthen rubber reinforcement.18
An improved dispersion of the filler was observed in Figure 3(c,
d) when silica was modified with TESPT. A lower number of
Dynamic Rheological Properties of the Silica/NR Compounds
agglomerates and homogeneous silica dispersion were visible in
and Vulcanizates by RPA. It is notably that the filler–filler inter-
the rubber matrix. It is worth noting that there was no obvious
action contributes to the strain-dependence of the modulus.1 With
aggregation and almost single silica particle could be seen clearly
the purpose for the analysis of the filler network structure, the
in MAS filled NR composites [Figure 3(c)]. The MPS/NR com-
curves of the variation in storage modulus (G0 ) were tested by
posites had an average smaller dimension aggregation which can
RPA of the silica/NR composites with strain amplitude (Figure 5).
be dozens of nanometer but with no distinct particle morphology
[Figure 3(d)]. All these above may indicate that the MAS filled As shown in Figure 5, the modulus decreased with increasing strain,
NR composites have lower filler–filler interaction and higher which demonstrated the so-called “Payne effect” arising from a par-
filler–rubber interaction compared with MPS/NR compounds. tially reversible break-down of the filler network.1 Figure 5(a,b)

Effect of Silica Contents and Types on BRC. It has been

reported that the significant interfacial interactions between filler
and rubber will lead to the formation of BRC.31,35 As a conse-
quence, the BRC is usually used to measure the strength of inter-
action between filler and rubber chains.31,36
Figure 4 illustrates the BRC of silica/NR compounds with different
silica contents and types. As readily shown in Figure 4, the BRC of
silica/NR compounds increased with increasing silica contents and
a rapid increment appeared with silica loading from 10 to 20 phr
while slow growth was shown from 20 to 30 phr. After adding
TESPT, the BRC of both the compounds further increased to the
maximum values. Particularly, the BRC values of the AS/NR com-
pounds at different silica loadings were always higher than that of
PS/NR compounds, which indicated the stronger interaction Figure 4. BRC of silica/NR compounds with different silica contents and
between rubber and silica and restrained the interaction of silica types. [Color figure can be viewed at wileyonlinelibrary.com]

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Figure 5. Effects of silica contents and silica types on the G0 -ε curves of compounds and vulcanizates. (a), (b) compounds and (c), (d) vulcanizates. Testing
conditions, both were at 60
C and 1 Hz. [Color figure can be viewed at wileyonlinelibrary.com]

exhibits the curves of storage modulus G0 versus strain of the com- different silica contents and types on the mechanical properties of
pounds, while Figure 5(c,d) shows the curves of vulcanizates. As is vulcanizates. As shown in Figure 6(a), for silica/NR composites, the
well-known, the lower “Payne effect” indicates the higher uniformity reinforce effect of silica was achieved and the tensile strength of all
of the filler dispersion and the weaker filler network structure in rub- composites was higher than that of neat NR vulcanizates. Among
ber matrix.7,37 Figure 5(a,b) and Supporting Information Table S2 them, the tensile strength propended to increase with increasing
showed that all the silica/NR compounds exhibited stronger “Payne loading levels of up to 20 phr, and then decreased when silica con-
effect” with increasing content of silica. While, the AS filled NR com- tent reached up to 30 phr for AS/NR composites. While, for PS
pounds illustrated much better filler dispersion, weaker filler network filled NR composites, it was inclined to increase with increasing
structures, and better filler–rubber interaction than those of PS ones. loading, when up to 30 phr, the highest value was attained. It was
These results were in well accordance with the above results of bound shown that larger aggregates were formed and acted as the stress
rubber contents as shown in Figure 4. Furthermore, in Figure 5(c,d) concentration points when the silica content was in a high level.23
and Supporting Information Table S2, the same trend is presented as For PS/NR composite, it presented more severe aggregation and
that the silica/NR compounds with respect to the strain amplitude stronger filler–filler network, which was supported by the Rubber
dependence of G0 of the silica/NR vulcanizates. The filler network Process Analyzer (RPA) shown in Figure 5 and Supporting Infor-
became stronger with the increase of silica loadings. mation Table S2. The tensile strength of AS filled NR composites
tended to be higher than that of PS/NR vulcanizates consequently.
Figure 5 also shows the comparison of “Payne effect,” which indi-
Also, the results also could be seen from the stress–strain curves in
cates the filler–filler interaction in different types of silica at a given
Supporting Information Figure S3.
loading filled NR compounds and vulcanizates in the presence or
absence of TESPT. As we known, TESPT used in silica/rubber com- Moreover, the tensile strength for both the modified silica/NR com-
pounds can be seen as a bridge between silica and rubber. The posites samples (MAS30 and MPS30) was improved by 6.0 and
silicon-oxyethyl groups have connected with silanol group by the 4.2% when compared with the AS30 and PS30, respectively. This
hydrolysis and condensation reactions. Then, when the silica/rubber can be explained that the interfacial binding force between the silica
compounds were heated, S S chemical bonds were formed through filler and rubber matrix was progressively improved.32 The follow-
TESPT and rubber. As a result, 30 phr of silica modified by TESPT ing factors are these that should not be the ignored significant ones,
filled NR, the “Payne effect” of the compounds and vulcanizates including the decreased surface polarity of silica, the higher cross-
were greatly lower than those without modification, which was in linking density, and better filler dispersion after modification. Also,
good agreement with the results reported by Sarkawi et al.38 it can be noted that the tensile strength of MAS30 was higher than
that of MPS30 sample. As shown in Figure 3(c), the filler dispersed
Effects of Silica Contents and Types on the Mechanical Proper- much better than that in Figure 3(d), which resulted in the stronger
ties of Silica/NR Vulcanizates. Figure 6 illustrates the effects of filler–rubber interaction and more superior tensile strength.

47449 (7 of 11) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47449

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Figure 6. Effects of different silica contents and types on the mechanical properties of vulcanizates. (a) Tensile strength; (b) elongation at break;
(c) modulus at 300% elongation; (d) volume loss; (e) heat build-up and hardness; and (f ) compression set and resilience. [Color figure can be viewed at
wileyonlinelibrary.com]

The effects of different silica contents and types on the elongation improved when under higher external stress.40 Thereafter, it
at break and modulus at 300% elongation were presented in became especially evident after silica modified by TESPT. All
Figure 6(b,c), respectively. The elongation at break of all compos- these could be ascribed to the higher crosslinking density and the
ites, which is related to the tensile strength while not completely limitation on the mobility of rubber molecular chain after addi-
same as the gradient trend, was found reduced with increasing tion of rigid silica.2 In the meantime, the modulus at 300% elon-
silica loadings. The silica, which is more likely to aggregate, gation of AS/NR or MAS/NR composites were lower than that of
added into the rubber latex to form the stress concentration PS or MPS filled NR composites, respectively, which was in well
points with poor dispersion in the matrix and weak interaction correspondence with the regularity of crosslinking density as cal-
with NR matrix.39 In detail, the elongation at break value of culated by the delta torque (ΔM) shown in Supporting Informa-
AS/NR composites was always lower than that of PS filled NR tion Table S1.
vulcanizates at every same silica loading. Specifically, the differ-
Notably, as shown in Figure 6(d), the abrasive resistance was pre-
ence was erased between MAS/NR and MPS/NR composites of
sented as volume loss of the vulcanizates. The greater the volume
elongation at break at last.
loss, the lower the abrasive resistance is.40 With the addition of
For the modulus at 300% elongation in Figure 6(c), as a whole, nanoparticles, the abrasive resistance of AS/NR vulcanizates was
with the addition of silica particles into NR matrix, the modulus improved, while only existed in 10 phr loading of PS filled com-
of silica/NR composites increased with increasing filler content. posites. Consequently, the volume loss with the minimum value
This indicated that the rigidity and deformation resistance were at 20 phr silica loading demonstrated the highest abrasion

47449 (8 of 11) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47449

 10974628, 2019, 18, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.47449 by Korea Institute Of Machinery & Materials (Kimm), Wiley Online Library on [03/12/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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Figure 7. Temperature dependence of storage modulus (G0 ) and loss factor (tanδ) for different types of silica/NR vulcanizates. [Color figure can be viewed
at wileyonlinelibrary.com]

resistance of AS/NR composites. Conversely, those PS/NR vulca- thereby leading to greater slippage of rubber chains.23 Further-
nizates presented inferior in abrasion resistance at the same silica more, it was found that the heat build-up of a vulcanizate was
loading. As a contrast, comparing the efficiency of wear- increased with decreasing crosslinking density.42,43 As shown in
resistance of the silica before and after modification, the modified Supporting Information Table S1, all of the crosslinking density
silica filler NR composites improved abrasion wear resistance of AS/NR or MAS/NR vulcanizates were lower than that of
performance significantly, and the MAS/NR composites pre- PS/NR and MPS/NR composites at same silica loading, and the
sented greater abrasion wear-resistance than that of MPS/NR corresponding heat build-up values were in agreement with the
composites. In such case, AS with higher exposed interfacial area above theory. Thereafter, with addition of TESPT, the MAS/NR
led to higher efficiency of modification, and the MAS/NR com- sample had the lowest temperature increment, which may be
posites showed weaker silica–silica interaction, stronger binding attributed to the greater efficiency of modification conferring a
force between silica and rubber, and the better dispersion of silica better dispersion of MAS and the weaker filler network. Accord-
in rubber matrix. ingly, the final dynamic compression net of MAS/NR composites
was maintained at the lowest with the best silica dispersion.
The temperature of tire tread will rise due to the friction and
dynamic deformation of tire moving the road. If the temperature Figure 6(e,f ) further illustrated the hardness and resilience of
rise is higher, it will be easier to deteriorate the mechanical prop- resulting composites with different silica contents and types,
erties of the tire trade.41 The effects of silica contents and types respectively. As can be seen, the hardness increased with increasing
filled in NR matrix on the heat build-up and dynamical compres- silica loading, and addition of TESPT, which was in corresponding
sion set were illustrated in Figure 6(e,f ), respectively. As shown with the former increased crosslinking density2 shown in Support-
in Figure 6(e,f ), the rising temperature of all silica filled NR com- ing Information Table S1. The same trend was found as 300%
posites were much higher than that of control sample neat NR modulus. Conversely, the resilience decreased with increase in sil-
vulcanizates, which was in accordance with the higher value of ica loading. This can be explained that the increasing silica content
dynamic compression set. Among them, AS/NR vulcanizates pre- could result in the limitation on the mobility of rubber chains. At
sented higher heat build-up and dynamic compression set than the same time, the higher crosslinking density will lead to the
those of PS/NR composites without TESPT. This may be due to lower elasticity of silica/NR composites. In addition, the resilience
the AS having higher exposed interfacial area with rubber chains of both the AS/NR and PS/NR composites were enhanced when

47449 (9 of 11) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47449

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TESPT was introduced. This was ascribed to the better dispersion natural rubber latex to prepare silica/NR masterbatches using the
of filler in rubber matrix and stronger filler–rubber interaction so latex compounding technique. As a control, the PS (BET surface
as to form a tighter network, which then slightly enhances the elas- area, 165 m2/g) was introduced into this latex mixing system to
ticity of the composites after addition of TESPT.23,44 investigate its reinforcing effect. Our main findings are summarized
as follows. First of all, based on SEM and DLS measurements, the
Effects of Silica Types on the Dynamic Properties of Silica/NR AS particles were proved to feature a monodisperse and uniform
Vulcanizates. The temperature dependence of viscoelastic proper- spherical shape while the PS formed severe aggregation. Second,
ties of silica/NR vulcanizates was measured by DMA. Figure 7 varying silica loadings were from 0 to 30 phr, exploring the perfor-
shows the temperature dependence of storage modulus (G0 ) and loss mance of silica/NR composites. The AS with greater exposed inter-
factor (tanδ) for different silica types, in which the loss factor tan δ facial area conferred the AS/NR vulcanizates with higher BRC,
is the ratio of loss modulus and storage modulus (G00 /G0 ).12,23,30 It weaker filler–filler interaction (Payne effect), higher tensile strength,
should be noted that the temperature at the maximum peaks of tan higher abrasive resistance and resilience, as well as lower modulus at
δ-T curves indicates the glass transition temperature (Tg) of silica/ 300% elongation. The AS/NR vulcanizates have a higher heat build-
NR composites. As can be seen in Figure 7(a1), MAS filled NR vul- up and compression set, which is attributed to the lower crosslink-
canizates showed the relative lower storage modulus G0 than other ing density compared with PS/NR vulcanizates. The addition of
composites below Tg whereas G0 dropped the slowest in rubber TESPT lowered the “Payne effect” of both vulcanizates significantly.
state, ending up the highest G0 value in the temperature range The corresponding mechanical performance of MAS/NR vulcani-
0–80
C. As we know, the rubber chains which were in frozen state zates was better than that of MPS/NR composites, except for the
gave little contribution to G0 due to the restriction of segmental modulus at 300% elongation. Especially, it is worth noting that the
movement. On the whole, all the contribution to G0 ’ may be MAS/NR composites showed lower crosslinking density compared
ascribed to the filler network structure, and that the MAS/NR pos- with those of MPS/NR vulcanizates. Finally, the highly uniform
sessed the weakest filler network structure compared with other MAS dispersion was revealed by TEM. The viscoelastic results of
composites.7 The rubber chains in the temperature range below Tg the vulcanizates showed that the MAS/NR vulcanizates presented
were in frozen state and their segmental movements were restricted. the decreased rolling resistance at 60
C. Considering the perfor-
As temperature increased above Tg, the rubber molecules thawed mance of monodisperse silica filled NR composites, the controllable
gradually, the rubber chain presented high mobility accordingly. As cost advantage, and to be used directly after slightly concentration,
the temperature was above 0
C, the filler–rubber interaction and the partial substitution of PS in rubber latex mixing application may
rubber crosslink network may be the main contribution to the stor- be promising in future.
age modulus G0 . In Figure 7(a2), from 0 to 80
C, the MAS/NR
composites with the highest G0 all through particularly demon- ACKNOWLEDGMENTS
strated that the vulcanizates had the most uniform dispersion of This work was supported by the National Natural Science
treated monodisperse silica and strongest filler–rubber interaction,7 Foundation of China (NNSFC Grants 51803104 and 21674055),
which was in agreement with the images shown in Figure 3. the Natural Science Foundation of Shandong Province
For the loss factor (tanδ) of silica/NR vulcanizates, the higher tanδ (ZR2016EMP03 and ZR2016XJ004).
peak corresponds to a weaker filler network.9,45 In Figure 7(b), all
Tg of the vulcanizates were ranged from −44 to −42
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47449 (11 of 11) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47449