Accepted Manuscript

Influence of gel content on the physical properties of unfilled and carbon black filled
natural rubber vulcanizates

Adun Nimpaiboon, Sureerut Amnuaypornsri, Jitladda Sakdapipanich

PII: S0142-9418(13)00135-9
DOI: 10.1016/j.polymertesting.2013.07.003
Reference: POTE 4083

To appear in: Polymer Testing

Received Date: 23 May 2013

Accepted Date: 9 July 2013

Please cite this article as: A. Nimpaiboon, S. Amnuaypornsri, J. Sakdapipanich, Influence of gel content
on the physical properties of unfilled and carbon black filled natural rubber vulcanizates, Polymer Testing
(2013), doi: 10.1016/j.polymertesting.2013.07.003.

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 ACCEPTED MANUSCRIPT

Material Properties

Influence of gel content on the physical properties of

unfilled and carbon black filled natural rubber
vulcanizates

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ADUN NIMPAIBOON1, SUREERUT AMNUAYPORNSRI2,
JITLADDA SAKDAPIPANICH1,2*

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Department of Chemistry and Center of Excellence for Innovation

in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400,
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THAILAND
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Institute of Molecular Biosciences, Mahidol University at Salaya Campus,
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Nakhonpathom 73170, THAILAND

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*Corresponding author. Tel.: +66 2889 3116; fax: +66 2889 3116.
E-mail address: jitladda.sak@mahidol.ac.th (J. Sakdapipanich).

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Abstract
Recently, gel content has been considered as a standard property for evaluating
commercial grade natural rubber (NR). In this study, NR containing various amounts of gel
was prepared by accelerated storage hardening as a model to clarify the influence of gel
content on the physical properties of both unfilled and carbon black filled vulcanizates.

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Furthermore, the NR samples were investigated to determine the effect of gel fraction on
Mooney viscosity and the structure of the gel after mastication. The results revealed that
Mooney viscosity was related to the percentage of gel fraction that has been proven to be the

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result of interactions between proteins and phospholipids at chain ends. After mastication,
although the gel fraction of NR can be decomposed to ~0% w/w, the interactions of proteins

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and phospholipids at the chain ends still existed, corresponding to the gel content of the raw
rubber. In the case of unfilled vulcanizates, the gel content showed no effect on cure

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characteristics, crosslink density and ultimate tensile strength, whereas the upturn of stress
occurred at a smaller strain when the gel content increased. However, in the case of carbon
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black filled vulcanizates, the gel content played a dominant role in the carbon black
dispersion, which was poorer when gel content increased, contributing to a decrease of
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crosslink density and ultimate tensile strength.
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Keywords: Natural rubber; Gel content; Physical properties

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1. Introduction
Natural rubber (NR) from Hevea brasiliensis contains about 94% rubber
hydrocarbons (cis-1,4 polyisoprene) and 6% non-rubber constituents such as proteins, lipids,
carbohydrates, etc. [1]. The rubber hydrocarbon is composed of a long-chain branched
polymer and the gel fraction. Although the gel fraction is insoluble in non-polar solvents for

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NR, i.e., toluene, cyclohexane, etc., it can be partially dissolved in a mixture of polar and
non-polar solvents [2]. Therefore, the gel fraction of NR is a complicated structure unlike a
simple cross-linked network [2,3]. Structural characterization of NR by selective enzymatic

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scission and chemical decomposition reveals the presence of proteins and phospholipids at
the initiating ω-terminal and terminating α-terminal of NR, respectively [4-6], The interaction

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of proteins and phospholipids at those chain-ends possibly forms branching and gel [2,7-8] as
a naturally occurring network [9], within which the intermolecular interaction of proteins via

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hydrogen bonding can be decomposed by deproteinization, and the association of
phospholipids can be decomposed by transesterification [2,7-8]. The gel fraction of NR can
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be classified into two types, designated as soft gel and hard gel. The former can be soluble by
treatment with protease, polar solvents and transesterification, while the latter remains after
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such the treatments. The hard gel is formed inside the lactiferous cell within a rubber tree
which has never been tapped as the rubber obtained from a virgin tree consists almost totally
of gel that is insoluble in any rubber solvents [10]. This finding suggests that this highly
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cross-linked gel fraction originates from radical cross-linking in the rubber tree before
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tapping[10]. In addition, it has been reported that some additives for NR latex, such as
tetramethyl thiuram disulfide (TMTD) as a preservative and diammonium hydrogen
phosphate ((NH4)2 HPO4) as a precipitant of Mg2+ presenting in NR latex, also cause hard gel
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formation [11].
Prolonged storage of NR progresses the hardening, referred to as the storage
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hardening phenomenon, which increases the gel content of crude NR or even commercially
produced NR using a carefully controlled procedure such as STR-XL, STR-5L, or STR-
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CV60 [12]. The standards for these commercial grade rubbers have been established for ash
content, nitrogen content, volatile matter, Wallace plasticity, Mooney viscosity and color
index. These values are well-known to influence the properties of rubber products. Recently,
the International Organization for Standardization (ISO) considered gel content a standard
value for producing commercial grade rubbers [13]. Therefore, it is reasonable to clarify the
effects of gel content on NR properties. Although a few researchers elucidate the role of gel
content, there are only reports about the effect of gel content on the properties of
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unvulcanized NR [14-17]. In this work, NR containing various amounts of gel was prepared
by accelerated storage hardening at high temperatures and dry conditions to study the
influence of gel content on the physical properties of unfilled and carbon black filled NR
vulcanizates.

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2. Experimentation
2.1 Rubber sample
STR-5L, a commercially produced NR from latex, was kindly provided by Pan Star

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Co., Ltd., Thailand.

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2.2 Preparation of rubber samples containing various amounts of gel
The samples containing various amounts of gel were prepared by accelerated storage

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hardening [17]. The rubber samples were placed in a preheated desiccator (60˚C, 30 min)
with phosphorus pentoxide (P2O5) under the hold plate for placing samples. The desiccator
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was sealed and kept at 60˚C in an oven. The incubated rubbers were collected at 0, 6, 12, 24,
48, 72, 96, and 168 h.
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2.3 Deproteinization and transesterification of NR [7]
Deproteinization of NR was carried out by incubating 30% DRC of fresh NR latex
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with 0.04% w/v proteolytic enzyme (KP-3939, Kao Co., Japan) and 1% w/v sodium dodecyl
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sulphate (SDS) at 37°C for 12 h, followed by centrifugation twice. The cream phase was cast
on a glass plate and dried in an oven at 70°C for 24 h. Transesterification of NR was
conducted as follows: Small pieces of the rubber were dissolved in toluene and then treated
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with freshly prepared sodium methoxide (NaOCH3) under a nitrogen atmosphere at room
temperature for 3 h. The resulting rubber solution was neutralized by methanolic-HCl and
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then subjected to centrifugation to remove any precipitates. The supernatant was purified by
reprecipitation in methanol twice, followed by drying in a vacuum oven at 40°C for 24 h.
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2.4 Preparation of vulcanized NR samples

The rubber samples with varying gel content were vulcanized using an accelerated
sulfur system for both unfilled and carbon black-filled vulcanizates. The compounds were
prepared to the formulations shown in Table 1. The preparation of compounds was carried
out using an internal mixer (Haake Plasticorder®) at 50°C with a rotor speed of 40 rpm. For
the unfilled compounds, the rubber was first charged to the mixer and masticated for 3 min,
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followed by the addition of stearic acid and ZnO. The mixing was continued for 5 min, sulfur
and CBS added and further mixed for 2 min. Finally, the compound was discharged and
sheeted on a cold mill. The carbon black filled compounds were prepared using the same
procedure except for the addition of carbon black prior to stearic acid and ZnO. The optimum
cure time (tc90) used in preparation of vulcanized samples was the time required for the torque

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of the Rheometer to increase to 90% of the final torque at 150°C.

2.5 Characterizations and properties measurement

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Determination of gel content was carried out in accordance with ISO/DIS 17278:2012
[13]. The rubber, approximately 1 mm³ from a bale without milling, was weighed to the

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nearest 1 mg as mo. Then, the prepared rubber was placed in the centrifuge tube and 30 ml of
toluene was added, followed by shaking manually for a few seconds. The tube was allowed to

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stand for 20 h at 25°C without stirring. After soaking, the tube was shaken vertically by hand
for 60 sec to disperse the jelly-like fraction. The solution was centrifuged to precipitate the
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gel fraction at 14,000 rpm for 2 h. The sol fraction was removed from the tube and 1 ml of
acetone was added to the precipitate at the bottom of the tube. This was subsequently
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transferred to a clean container which had been weighed to the nearest 1 mg as m1. The
container with the precipitate was dried in an oven at 110°C for 1 h and then weighed as m2.
The gel content was calculated as per the following equation.
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Gel content (%) = × 100

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Mooney viscosity (ML1+4) was determined using a TECHPRO Mooney Viscometer

based on ISO 289-1.
The weight-average molecular weight ( M w ) of the rubber samples was determined
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by size exclusion chromatography (Jasco-Borwin). Calibration was carried out using

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synthetic cis-1,4 polyisoprene standard (Polymer Standard Service GmbH, Germany).

Strain sweep tests were performed using a Rubber Process Analyzer (RPA)
(RPA2000; Alpha Technologies, Ohio, USA). The rubber samples were measured for storage
modulus (G') at 100ºC by varying the strain from 0.5% to 1200% at a frequency of 1 rad/s.
For carbon black filled compounds, the different storage moduli at low and high strains (∆G')
ascribed to the ‘‘Payne effect” indicates the degree of filler–filler interaction [18, 19].

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The measurement of bound rubber is the representation of rubber-filler interaction.

Approximately 0.2 g of the pre-weighed rubber compounds was immersed in 25 ml toluene
for 7 days at room temperature (25°C). The insoluble black-gel part was filtered and then
dried for 1 day in air at room temperature, and further dried in an oven at 70ºC until constant
weight was obtained. The bound rubber content was determined from [20]:

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Rb =

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where Rb is bound rubber content, Wfg is the weight of black-gel, W is the weight of
specimen, and mf and mp are the weights of filler and polymer in the compound, respectively.

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Cure characteristics, i.e., scorch time (ts2) and optimum cure time (tc90), were
determined using a moving die Rheometer (TechPro MD+) at 150°C.
In order to determine crosslink density, the vulcanizates were cut with a thickness and

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weight of approximately 1 mm and 0.7 g, respectively. The samples were immersed in 100
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ml of dried toluene at room temperature for 1 week kept in a dark place. The swollen samples
were blotted with filter paper to absorb the excess toluene, and the weight of each sample was
then determined. The crosslink density was calculated using the modified Flory-Rehner
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equation [21-23].
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ν = -[ln(1-V0r) + V0r + χV0r2]/ [2ρrV0(V0r1/3-V0r/2)]

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ν represents crosslink density per gram of rubber, V0r is the volume fraction of rubber, χ is the
Huggins interaction constant, ρr is the density of rubber, V0 is the molar volume of the
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solvent, and ρs is the density of the solvent. The volume fraction Vr was calculated as follows:

V0r = [(ρr/ρs) ((ws-wu/wu)) + 1]-1

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ws represents the weight of the swollen rubber at equilibrium, and wu is the weight of the
unswollen rubber. The values of the constant used in the above calculation were ρr = 0.93
g/cm3, ρs = 0.886 g/cm3 for toluene, V0 = 106.9 cm3/mole, χ =0.39 for gum NR, and 0.42 for
carbon black filled NR. For carbon black filled rubber Vr is substituted which can be
determined from:
V0r / Vr = 1-[3c(1- V0r1/3)+ V0r-1]

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where c is the parameter for carbon-rubber interaction (c =1.17), and is the volume fraction
of carbon black.
The tensile properties of the vulcanizates were determined using an Instron Universal
Tester (Model 5566) at room temperature according to ISO 37. The thickness of the samples
was 0.5 mm. A test was carried out using a crosshead speed of 500 mm/min with a load cell

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of 1 kN, and at least 5 specimens were used for each measurement.
The cryogenic fracture surfaces of vulcanizates were prepared for examination of the
morphology of carbon black dispersion. The samples were coated with Pt-Pd and the

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morphology observed using a scanning electron microscope (SEM) (model S-2500; Hitachi,
Tokyo, Japan) under an accelerated voltage of 15 kV.

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3. Results and discussion

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Storage hardening is an important characteristic of NR, where the hardening of NR
increases during long storage. It has been reported that the gel content and Mooney viscosity
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of commercial NR such as STR-XL, STR-5L and STR-CV60 increased after storage for 14
months, caused by this phenomenon [12]. In order to shorten the preparation time for the
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varied gel content NR samples, accelerated storage hardening was carried out by keeping the
rubber at 60ºC, drying over a desiccant, according to our previous study [17]. Fig. 1 exhibits
the gel content and Mooney viscosity of rubber samples at various accelerated storage
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hardening times. It was found that gel content increased with increasing accelerated storage
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hardening times up to 72 h, at which point the different gel contents, i.e., ~0.5, ~4, ~6, ~12
and ~17% w/w were successfully reached. The soft gel of NR has been reported to form via
the hydrogen bonding of proteins and association of phospholipids at initiating and
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terminating chain ends of NR, respectively [2, 7-8]. On the other hand, Tarachiwin, et al.
deduced that the hard gel can be formed as a result of the addition of the chemicals for rubber
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latex, such as TMTD/ZnO as a normal preservative, which provokes the reaction between the
polyisoprene chains and sulfur atoms of TMTD [11]. Since the rubber sample contains the
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chemicals mentioned above, it possibly forms hard gel as well. In this work, it is apparent
that the gel content of rubber samples containing the highest gel content obviously decreased
from ~17% to ~0% w/w after transesterification treatment. If the gel of the rubber samples
includes some hard gel, the cross-linked network formed by carbon-carbon and carbon-sulfur
bonding cannot be decomposed by transesterification. Therefore, it can be deduced that the
type of gel in the rubber samples after accelerated storage hardening is soft gel, similar to the
gel formation during actual conditions of long storage [14].
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Mooney viscosity is an important parameter used as a standard indicator for

producing commercial NR. As shown in Fig.1, a similar trend for gel content and Mooney
viscosity was observed wherein they both increased with increasing accelerated storage
hardening times up to 72 h and then were constant. This indicates that the increase in Mooney
viscosity might be due to the occurrence of networks as the increased gel content during

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progressive storage hardening obstructs the mobility of rubber chains. However, it should be
noted that the Mooney viscosity of NR is governed by not only the gel content but also the
molecular weight and molecular weight distribution of the rubber molecules [24-26].

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Moreover, the addition of some chemicals to control the constant viscosity (CV) grade, such
as hydroxylamine, also affects the Mooney viscosity of the rubber [27, 28]. Therefore, it is

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impossible to predict or compare the Mooney viscosity of the rubber samples from different
bales or grades using just the gel content value.

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Owing to the high toughness and viscosity of NR, it is necessary to soften the rubber
before compounding in order to improve the dispersion of filler and chemicals. The process
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of softening by mechanical shearing is known as mastication. Even though many rubber
technologists have investigated the effects of mastication on the reduction of molecular
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weight and viscosity of NR under various conditions [30-34], studies on gel structure and gel
content are still ambiguous [35-36]. In order to clarify the role of mastication on gel structure,
NR samples containing various amounts of gel were subjected to mastication in an internal
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mixer under the same conditions as the procedure for compounded rubber (at a rotor speed of
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50 rpm, at 50ºC). The gel content of rubber samples at various mastication times are given in
Fig. 2. The gel content of samples 1, 2, and 3 reduced to almost 0% w/w after mastication for
5 min, while the gel content of samples 4 and 5 were completely soluble after mastication for
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15 min. This indicates that the mastication time for decomposing the gel relates to the initial
gel content of the rubber. To elucidate the effect of mastication on the gel structure, the
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rubber samples before and after mastication were characterized for gel content, Mooney
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viscosity and M w , as shown in Table 2. The results reveal that the gel content of all samples
decreased to ~0% w/w after mastication for 15 min. Reduction of gel content can be caused
by two circumstances. The first is random chain scission of the rubber as evidenced by the
obvious decrease of M w . The second is the decomposed interaction of proteins and
phospholipids at the chain ends, which was supported by the ~0% w/w gel content of
deproteinized-transesterified NR (DPTE-NR) (Table 2). The absence of gel fraction in
DPTE-NR is due to the removal of proteins and phospholipids at the chain ends by

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deproteinization and, subsequently, by transesterification (~0% w/w of N-content and ~0

mmol/kg of ester content) [2,7]. It has been reported that the DPTE-NR is comprised of linear
molecules, which was proposed according to the results of Huggins’ k' constant [2, 8]. k'
values of about 0.45-0.65 refer to branched molecules whereas values around 0.3 correspond
to linear polymer [29]. The k' value of DPTE-NR in the range of 0.3-0.4 indicates that the

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molecular structure of DPTE-NR is linear, similar to the observation of linear synthetic
polyisoprene synthesized by a lithium initiator. Schematic representations of branching and
the gel of NR after deproteinization and subsequently transesterification are demonstrated in

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Fig. 3. The changed structure of NR after mastication led to a change of rheological
properties seen as the decrease of Mooney viscosity of each sample to a similar level (Table

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2). Although using Mooney viscosity as steady-state viscosity can frequently provide key
information regarding the processability of the rubber, it also has inherent limitations, such as

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lacking information about microstructure and structurally sensitive hydrogen-bonded
structures.
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Using RPA under oscillating shear conditions is considered to be a powerful
technique to overcome the drawbacks of steady-state measurement. Such characteristics of
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unvulcanized NR derived from the networking role of proteins and phospholipids can be
detected by strain sweep testing [37]. Therefore, an oscillatory shear experiment using a
strain sweep test was applied in this study to elucidate the structural change of rubber
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samples after mastication. Fig. 4 demonstrates logarithmic plots of G' as a function of %

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strain of the rubber sample after mastication for 15 min (gel content of all samples ~0% w/w)
and DPTE-NR measured at a frequency of 1 rad/s. Different G' values for each masticated
rubber sample in the linear viscoelastic region were found, in spite of the same Mooney
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viscosity and gel content after mastication. Even though M w of the masticated rubber
samples, which is the major factor affecting the modulus of a polymer on the rubbery plateau,
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were quite similar, the G' at the linear viscoelastic region of the rubber sample was larger
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when the initial gel content was higher. This probably indicates that the initial gel content
correlates with the interactions of proteins and phospholipids at the chain ends, which appears
to influence the rheological properties of NR. This can be supported by the observation of
DPTE-NR which is a model for linear molecules without proteins and phospholipids. DPTE-
NR showed the lowest G' at the linear viscoelastic region, although the M w and Mooney
viscosity of DPTE-NR were higher than those of all masticated samples (Table 2). This
confirmatory evidence signifies that the interactions of proteins and phospholipids at chain

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ends exhibit a dominant effect on the G' at the linear viscoelastic region of the rubber.
Consequently, the effect of mastication on the gel fraction of NR was proposed to be that the
shear force during mastication breaks down the rubber chains and some interactions of the
proteins and phospholipids at the chain ends. This might transform the gel phase to sol phase
where proteins and phospholipids as active functional groups at chain ends still exist and

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possibly form so-called branched molecules as well as interactions with each other. A
schematic representation of the gel fraction of NR with low gel content and high gel content
after mastication is illustrated in Fig. 5 based on these findings. After mastication, both low

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gel content and high gel content NR were completely soluble, leading to the 0% w/w gel
content. However, the process of measuring gel content can detect only the large networks of

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NR, which are insoluble in toluene. The microstructure, i.e., small networks or branched
molecules still present at different quantities, relates to the initial gel content.

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To investigate the effect of gel content on the physical properties of both unfilled and
carbon black filled NR vulcanizates, the rubber samples containing various amounts of gel
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were compounded with carbon black and rubber chemicals, followed by vulcanization as
described in the experimental part. Fig. 6 shows the cure characteristics, i.e., scorch time and
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cure time, as well as the crosslink density of unfilled vulcanizates prepared from NR
containing various amounts of gel. It is apparent that the scorch and cure times of the rubber
samples are similar. This result indicates that the cure characteristics of NR appear to be
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unaffected by the gel content. However, there was a report showed that the gel character was
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a crucial influential factor in the excess crosslink phenomenon of gum styrene butadiene
rubber (SBR) [38]. The crosslink density of SBR containing gel was greater than that of
regular SBR. It was postulated that the gel phase might concentrate the curatives in the
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rubber-matrix phase. This occurs because the solubility of the curatives would be greater in
the rubber-matrix than in the more ordered (thermodynamically) gel phase. Thus, the
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increased crosslink density of SBR containing gel originated from the constricted gel phase
that was enclosed within the higher curative concentration of the rubber-matrix. From Fig.
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6b, the result is different from that observed in SBR. The crosslink density of the NR
vulcanizates did not change when the gel content was increased. This might be attributed to
the dissimilarity of gel structure between NR and SBR. The gel of SBR, a cross-liked
network derived from carbon-carbon bond via the side reaction of radical polymerization, is
considered to be more dense and harder than the gel of NR formed by the interactions of
proteins and phospholipids at chain ends. A homogeneous dispersion of the curatives usually

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occurs for NR compounds, contributing to similar cure characteristics and crosslink density,
although the gel content of raw rubber obviously increases.
Fig. 7 shows the stress-strain curves of unfilled vulcanizates prepared from NR
containing various amounts of gel. The ultimate tensile strength of the vulcanizates changed
insignificantly with increase in the amounts of gel. This indicates that the strength of

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vulcanizates might be governed mostly by chemical bond networks derived from the
vulcanization process [39]. This explanation is consistent with the obtained results wherein
all vulcanizate samples revealed a similar crosslink density. Even though it is well known

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that crosslink density plays a strong role with regard to several properties of vulcanized NR,
the onset of strain-induced crystallization (SIC) is almost independent of crosslink density

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[40-42]. From Fig. 7, it can be seen that the vulcanizates revealed different stress-strain
behavior than that ascribed to SIC, regardless of similar crosslink density levels. The stress

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upturn occurred at smaller strains when the gel content was increased. As mentioned before,
the initial gel content is related to the interactions of proteins and phospholipids at chain-
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ends. The onset strain of SIC might be dominated by such interactions that still exist in spite
of being processed, i.e., mixing and vulcanization. This is in agreement with the results
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observed from the comparative study of sulfur cross-linked NR and a synthetic analogue of
SIC in which the sulfur cross-linked NR crystallized at a smaller strain [43], and the upturn of
stress in vulcanized NR and un-vulcanized NR is very similar [44].
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For many applications, NR is reinforced with carbon black to enhance the end-use
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performance. The cure characteristics of carbon black filled NR are shown in Fig. 8a. The
results revealed that the rubber samples containing different gel content levels exhibited
unchanged scorch and cure times, similar to the behavior of the unfilled rubber. However, the
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crosslink density of all samples decreased when the gel content increased to ~12% and
further to ~17% w/w, as shown in Fig. 8b. Since the strong bonding of rubber molecules to
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the surface of carbon black particles resists swelling and enhances the degree of crosslinking
[45, 46], the decreased crosslink density of rubber containing ~12% and ~17% w/w gel
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might be due to the lower rubber-filler interactions as a result of poor dispersion of the carbon
black in these vulcanizates. In order to verify this hypothesis, the results of bound rubber are
shown in Fig. 9, wherein the degree of rubber-filler interaction was measured by bound
rubber content. It can be seen that bound rubber content significantly decreased for the rubber
compounds containing gel contents up to ~12% and further to ~17% w/w, indicating that the
rubber-filler interaction was reduced by the increased gel content.

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The poor dispersion of carbon black when the rubber contains ~12% and ~17% w/w
gel was confirmed by the results of strain-dependent modulus testing, as shown in Fig. 10,
where ∆G' indicates the ‘‘Payne effect” whereby the higher ∆G' infers an increasing filler–
filler interaction and poorer filler dispersion [18-19]. It can be seen that ∆G' of the rubber
compounds prepared from the rubber containing ~0.5% to ~4% w/w of gel were similar,

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while ∆G 'slightly increased when the gel content increased to ~6% w/w, and remarkably
increased when the gel content was increased up to ~12% and further to ~17% w/w. These
results confirmed that the gel content influences the dispersion of carbon black. These results

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are likely due to the presence of gel during mixing with carbon black. The existing gel
fraction might obstruct the incorporation of carbon black and rubber. Based on gel character,

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it is difficult to force the gel into the interstices of the carbon black agglomerates which are
ineffectively encapsulated by the rubber. Consequently, this causes the poor filler-rubber

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interaction and also the low degree of carbon black de-agglomeration in the compound,
wherein the gel would concentrate carbon black agglomerates in the reinforced phase where
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carbon black can form a 3-dimensinal network of its own, held together by van der Waals
forces. The degree of carbon black dispersion was also indicated by the morphology of the
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cryogenic fracture surfaces of vulcanizates, as displayed in Fig. 11. It can be seen that the
carbon black dispersion of rubber samples containing gel contents of ~0.5% to ~6% w/w was
not much different, while agglomerations on the scale near 1 µm were detected within the
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rubber samples containing gel contents at ~12% and ~17% w/w. These results are in
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agreement with the results of carbon black dispersion predicted by the measurements of the
Payne effect and bound rubber.
The stress-strain measurement of carbon black filled vulcanizates is given in Fig. 12.
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In spite of the difference in gel content, the stress upturn of all rubber samples was quite
similar. Furthermore, all carbon black filled vulcanizates revealed a stress upturn at a smaller
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strain than the unfilled samples. This indicates that the stress-strain behavior of carbon black
filled vulcanizates is governed by the substantial effect of filler, regardless of the networking
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role of proteins and phospholipids. Apart from the crosslink density, the dispersion of filler in
rubber compounds is generally known to significantly influence the performance and failure
properties of rubber products [47-48]. Drawing from the results, the ultimate strength of
rubber samples tended to drop when the gel content increased, as can be seen in the case of
the rubber samples containing gel content at ~12% and ~17% w/w. This is attributed to the
lower crosslink density and poorer carbon black dispersion in the vulcanizates. These

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findings suggest that increasing the gel content of raw rubber lowers the tensile strength of
carbon black-filled NR vulcanizates.

4. Conclusions
NR samples containing various amounts of gel, from ~0.5% to ~17% w/w, were

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successfully prepared by accelerated storage hardening for 72 h. Increasing the gel content
during accelerated storage hardening was confirmed to be an important factor contributing to
the increase in Mooney viscosity, as the presence of networks obstructs the mobility of

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rubber chains. The gel fraction of NR can be decomposed into a sol fraction by shear force
during mastication. The quantities of the interactions between proteins and phospholipids at

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the chain ends correlate with the initial gel content of that raw rubber. The cure
characteristics and crosslink density of unfilled NR vulcanizates was found to have no

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influence from the gel content. The ultimate tensile strength of unfilled NR vulcanizates was
dominated by the crosslink density, while the stress upturn was dependent on the gel content.
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For carbon black filled vulcanizates, the gel content plays a detrimental role on the carbon
black dispersion that contributes to the reduction of the crosslink density and the ultimate
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tensile strength of the vulcanizates. Consequently, the gel content should be considered as an
important factor affecting the physical properties of NR.
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Acknowledgements
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The authors would like to express their gratitude for the financial support from the
collaboration between Mahidol University and Royal Golden Jubilee (RGJ) Ph.D. program:
PHD/0257/2550, as well as the Center of Excellence for Innovation in Chemistry (PERCH-
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CIC), Commission on Higher Education, Ministry of Education. Sincere appreciation is

extended to Pan Star Co., Ltd., Thailand, for providing STR-5L.
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LIST OF FIGURE CAPTIONS

Fig. 1. Mooney viscosity and gel content of rubber samples at various storage hardening

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times

Fig. 2. Gel content of rubber samples at various times of mastication

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Fig. 3. Schematic representation of branching and gel of NR after deproteinization and

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subsequently by transesterification

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Fig. 4. Logarithmic plots of G' as a function of % strain of the rubber sample after mastication
for 15 min (gel content of all samples: ~0% w/w) and DPTE-NR measured at a frequency of
1 rad/s
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Fig. 5. Schematic representation of gel fraction of NR at low gel content and high gel content
after mastication
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Fig. 6. Cure characteristics and crosslink density of unfilled vulcanizates prepared from NR
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containing various amounts of gel: Scorch time and cure time (a) and Crosslink density (b)

Fig. 7. Stress-strain curves of unfilled vulcanizates prepared from NR containing various

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amounts of gel
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Fig. 8. Cure characteristics and crosslink density of carbon black filled vulcanizates prepared
from NR containing various amounts of gel: Scorch time and cure time (a) and Crosslink
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density (b)

Fig. 9. Bound rubber content of rubber compounds prepared from NR containing various
amounts of gel

Fig. 10. ∆G' as Payne effect of rubber compounds prepared from NR containing various
amounts of gel
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Fig. 11. SEM micrographs of the cryogenic fracture surfaces of vulcanizates prepared from
NR containing various amounts of gel

Fig. 12. Stress-strain curves of carbon black filled vulcanizates prepared from NR containing

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various amounts of gel

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LIST OF TABLES

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Table 1 Compound formulation of rubber samples
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Table 2 Gel content, Mooney viscosity, and M w of rubber samples before and after
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mastication for 15 min and DPTE-NR

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Table 1 Compound formulation of rubber samples

Ingredient Quantity (phr)

Unfilled compound Carbon black filled compound

NR 100 100

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ZnO 6 6

Stearic acid 0.5 0.5

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Sulfur 3.5 3.5

CBS1 0.5 0.5

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Carbon black (N330) - 50

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N-cyclohexylbenzothiazole-2-sulfenamide

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Table 2 Gel content, Mooney viscosity, and Mw of rubber samples before and after mastication for
15 min and DPTE-NR
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Before mastication After mastication
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Sample Gel content Mooney Gel content Mooney

(%w/w) viscosity M w × 105 (%w/w) viscosity M w ×105
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(ML 1+4) (ML 1+4)

1 ~0.5 72.2 8.49 ~0 22.4 2.49

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2 ~4 74.4 8.37 ~0 22.6 2.52

3 ~6 77.6 8.47 ~0 23.5 2.48

4 ~12 78.3 8.34 ~0 22.9 2.59

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5 ~17 78.5 8.45 ~0 22.5 2.47

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DPTE-NR ~0 53.2 7.50 - - -

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