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Effect of acetone extract from natural rubber on

Cite this: RSC Adv., 2017, 7, 26458
the structure and interface interaction in NR/CB
composites
Open Access Article. Published on 17 May 2017. Downloaded on 06/06/2018 01:57:16.

Tiwen Xu,a Zhixin Jia, *a Lianghui Wu,a Yongjun Chen,a Yuanfang Luo,a Demin Jiaa
and Zheng Pengb

The influences of acetone extract (AE) from natural rubber on the interface structure of NR/CB composites
were investigated through rubber process analyzer (RPA), scanning electron microscopy (SEM), Raman
spectroscopy, X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The results
demonstrated that the crystallite size of CB was increased by AE, leading to the decrease of dispersive
free energy (gds) on the CB surface, which results in a reduction of CB–NR interaction. Oppositely, AE
also increased the number of physical entanglement points in NR/CB matrix for its polarity interaction
Received 22nd March 2017
Accepted 3rd May 2017
with CB, which could promote the CB–NR interaction. Consequently, the optimized value of AE in NR/
CB matrix is 2 phr, where the optimal mechanical and dynamical properties were obtained.
DOI: 10.1039/c7ra03354k
Simultaneously, AE had a negative effect on the strain-induced crystallization behaviors of NR/CB
rsc.li/rsc-advances composites. This research may draw attention to the evaluation of quality standards of NR.

a common ller, is widely used in natural rubber composites. W.

Introduction Thongruang14 explored the correlations of electrical and
Natural rubber is collected from Hevea brasiliensis and is widely mechanical properties of NR/CB composites, focusing on differ-
used in the industry. For its natural distinction, NR is actually ences in mixing methods, curing ingredients or sample thick-
a mixture of compounds, consisting of cis-1,4-polyisoprene (95% w/ ness. Xu15 investigated the inuence of CB graed with degraded
w) and non-isoprene compounds as proteins (1–2% w/w), acetone natural rubber on the mechanical and dynamical properties of
extract (1–2% w/w), carbohydrates (0.4% w/w) and minerals (0.3– NR/CB composites, which performed well on tensile stress and
0.7% w/w).1 All of these are affected by climate, territory, breed or tear strength. Others reports about the inuence of ller types16
process conditions. These non-isoprene compounds are important or hybrid ller17 on the properties of NR/CB composites were also
to the stability of natural rubber latex, rubber processability, and done. Above all, researchers payed close attention to the modi-
even the mechanical properties2–6 of the vulcanizate. Unfortu- cation of CB particles, and preparation methods that could
nately, the critical components of non-isoprene compounds are signicantly improve the performance of NR/CB composites. No
still unclear, let alone the effect of these factors on the natural reports were published about the effects of AE on the dynamical
rubber network structure and application performance. In fact, NR and mechanical properties or structure variation of NR/CB
is oen applied with inorganic particles, such as carbon black, composites, which are valuable to the application of NR in tyres.
silica,7 MMT,8 and HNTs,9 which is more valuable to practice. In this study, NR/CB composites with different AE were
However, few researchers were concerned about the inuence of prepared on double rolls open mill. The structural variations of CB
non-isoprene compounds on the mechanical and dynamical and composites caused by AE were investigated through Raman
properties or interface structure of lled NR composites. spectroscopy, XRD, DSC and stress–strain behaviors. Simulta-
Acetone extract (AE), as one of the non-isoprene compounds, neously, the mechanical and dynamic properties of composites and
is important to the quality of NR. It consists of oleic acid, linoleic CB–rubber interaction were also illustrated. The results claried the
acid, stearic acid, and sterol ester, as reported.10 Researchers re- impact of AE on the structure and dynamic properties of NR/CB
ported that some accelerants and sterol antioxidant contained in composites, which could offer valuable information on Hevea bra-
AE could positively affect the curing rate and anti-aging resis- siliensis cultivation and on the application of NR/CB composites.
tance to ozone11–13 of unlled natural rubber. Carbon black, as
Experimental
a
College of Materials Science and Engineering, South China University of Technology, Materials
Guangzhou 510640, China. E-mail: 18620901980m@sina.cn; Tel: +86 20 87114857
b
Agricultural Product Processing Research Institute, Chinese Academy of Tropical Natural rubber (NR), with trade name SCR-WF, was supplied by
Agriculture Sciences, Zhanjiang 524001, China Hainan Sinochem Rubber Company, Ltd (Hainan, China).

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Carbon black (CB N330) was purchased from Guangzhou 3000 cm1 at a wavelength of 523 nm. XRD spectrum was
Institute of Rubber Industry Products Co., Ltd (Guangdong, recorded on a X' Pert PRO (PANalytical, Holland) wide angle X-
China). DBP was determined to be 103
105 m3 kg1. Other ray diffraction system, using Cu Ka radiation (l ¼ 0.154 nm)
ingredients are commercially industrial products and used as with a diffraction angle of 5–90 at a step order of 0.017 per
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received. 16.24 s.
The glass transition behaviors of NR/CB composites were
Preparation of NR/CB composites modied by AE examined on a NETZSCH DSC 204 F machine. The temperature
First, natural rubber was extracted by acetone for 48 h through program involved a 5 min isothermal hold at 80  C, followed
the Soxhlet extraction method and the residual solution was by heating at 3  C min1 to 10  C under nitrogen. The heat
concentrated using a rotary evaporator to obtain the acetone capacity step, DCpn, and weight fraction of immobilized poly-
extract (AE). The dried natural rubber NR was mixed with other mer layer, cim,18,19 were calculated as follows:
Open Access Article. Published on 17 May 2017. Downloaded on 06/06/2018 01:57:16.

ingredients on a X(S)K-160 open-mill (Dongguan, China) at

DCpn ¼ DCp/(1  w) (1)
room temperature. Basic formulation (mass parts): NR 100, CB
(0 or 30), AE (0–5), zinc oxide 5, stearic acid 2, sulfur 1.5, N- cim ¼ (DCp0  DCpn)/DCp0 (2)
cyclohexyl-2-benzothiazolesulfenamide (accelerator CZ) 1.5,
benzothiazole disulde (accelerator DM) 0.5. The optimum where DCp is the heat capacity jump at Tg. DCpn is normalized to
curing time (T90) was determined at 143  C by a UR-2030 the polymer weight fraction. w is the weight fraction of ller.
oscillating disk rheometer (U-CAN Technology Company, Ltd, DCp0 refers to the heat capacity jump at Tg of the unlled
Taiwan). The compounds were vulcanized on a KSH R100 at polymer matrix. cim is the weight fraction of immobilized
vulcanizing machine (Kesheng Machinery Co., Ltd, Dongguan, polymer layer. Tg was determined according to ASTM E1356-08,
China) aer their accommodation at room temperature for 4 h. and DCp was calculated using the NETZSCH Thermal Analysis
soware.
Preparation of NR/CB/AE model compound
NR/CB/AE and NR/CB model compounds with the mass ratios Results and discussion
of 100/30/5 and 100/30, respectively, were made on a X(S)K-160
Effect of AE on the dispersion of CB in NR/CB composites
open-mill at room temperature for 10 min. No additives were
used in this experiment. Then, the compounds were extracted Fig. 1 depicts the RPA strain sweep plots of unvulcanized NR/CB
in a Soxhlet extractor using acetone for 72 h, to eliminate the composites with different AE. It can be seen that shear modulus
free-moving components of AE, and then extracted by toluene (G0 ) is increased by increasing AE until it obtains a threshold
for 72 h continuously, to remove the weakly adsorbed NR value at 4 phr AE. The result illustrates that the Payne effect of
molecules from CB. The residuum aer extraction was analyzed NR/CB composites was enhanced via adding AE. Normally, G0
through Raman spectroscopy and XRD to investigate the decreases along with an increase in strain, which is called the
interaction. Payne effect; a high value of G0 at low strain presents a great
degree of aggregation of ller network that would deduce a poor
Analysis and characterization mechanical performance of composites. To further investigate
the dispersion of CB in NR matrix, SEM images of NR/CB
Strain sweeps of unvulcanized NR/CB composites were con-
composites were obtained, which are displayed in Fig. 2. It
ducted by Rubber Processing Analyzer (RPA) (RPA 2000, Alpha,
can be seen that there are no CB aggregates in NR matrix except
USA) from 0.7% to 200% at 100  C, 1 Hz. The morphology of
those shown in Fig. 2(f). Therefore, the enhancement of the
fractured surfaces of vulcanized NR/CB composites (15 mm
6
mm
1 mm) was observed using a ZEISS Merlin SEM (EVO18
German) machine at an acceleration voltage of 10.0 kV. Tensile
properties and tear strength of vulcanizates were determined
according to ISO 37-2005 standard (dumbbell A shape) and ISO
34-1:2004 (nicked angle), respectively, at 25  C using a U-CAN
UT-2060 instrument. Shore A hardness was performed
following ISO 7619-1:2004 using a XY-1 durometer (Shanghai).
Rolling resistance of composites was obtained via a RSS-II
rolling resistance testing machine (Beijing Wan Hui Tech-
nology Development Co., Ltd, China). Compression fatigue heat
production of composites was determined by a RH-2000N
(GOTECH Testing Machines Inc.) compression fatigue tester
according to ISO4666/3-1982. Abrasion resistance of vulcanized
composites was determined using a rotating cylindrical drum
device (DIN) according to ISO 4649:2002. Raman spectrum was
implemented by a DXR (American Thermo Electron) Laser Co- Fig. 1 RPA strain sweep of unvulcanized NR/CB composites with
focal Microscopy Raman Spectrometer in the range of 100– different contents of AE.

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Fig. 2 SEM images of brittle fracture surfaces of vulcanized NR/CB composites with different AE contents: (a) 0 phr, (b) 1 phr, (c) 2 phr, (d) 3 phr,
(e) 4 phr, (f) 5 phr.

Payne effect could not have been caused by the aggregation of length scale of segmental motion and the relaxation is inde-
CB. This phenomenon could be interpreted through chain pendent of the composition.23 The other is the plasticization
entanglement theory. Aer extraction treatment by acetone, effect24 caused by AE that might promote the mobility of the
physical entanglement points of natural rubber were destroyed molecular chain. The normalized heat capacity (DCpn) is
and then replaced by CB particles when preparing NR/CB proportional to the number of internal degrees of freedom of
composites. Due to the alkyl and oxygen-containing groups molecular motion and could represent the change of polymer
structure10 of AE components, CB could migrate more easily in chain mobility in the composites directly.20,25 The greater value
the NR/CB/AE system than that of unmodied composites to of DCpn at the glass transition region indicates a better chain
form a large number of new entanglement points, leading to the mobility. In Fig. 3, DCpn is increased via increasing AE in NR/CB
enhancement of G0 of composites at low strain. Simultaneously,
the decrease of G0 on 5 phr loading should be attributed to the
plasticizing effects of small molecular substances of AE.

Analysis of constrained regions of composites by DSC

It is well known that glass transition behavior is a typical feature
of polymer molecules that can offer structural variation infor-
mation of polymers. Normally, Tg and normalized change of
heat capacity (DCp) of a polymer at the glass transition region
are used to evaluate the mobility of polymer molecules that are
sensitive to the local environment.20 Fig. 3 shows the glass
transition behaviors of unlled NR and NR/CB composites with
different AE.
As can be seen, Tg parameters of all samples exhibit no
systematic variation upon changing the composition, which is
in line with other reports.21,22 One reason for this is that the Fig. 3 Glass transition behaviors of NR/CB composites with different
average size of immobilized polymer region is greater than the contents of AE.

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Fig. 4 Raman spectra peak fitting of pure CB, residual CB from extracted NR/CB and NR/CB/AE model compounds.

composites, which indicates improved mobility of the rubber lineshape and band intensity, mixed Gaussian–Lorentzian
chain. Thus, a reduction of constrained regions is achieved curve tting26,29 was carried out for each spectrum. Good ts are
through the decline of weight fraction of immobilized polymer obtained in Fig. 4, and the data are shown in Table 1. The
layer (cim) directly. Synthetically, AE might give a negative effect degree of disorder of D1 is lower than D2 or D3. The denition
on ller–rubber interaction in NR/CB matrix, particularly with in article is in line with other report.28 Compared with the
a high loading content. parameters of pure CB, the D1 band of CB shis from 1345
cm1 to 1355 cm1 in the NR/CB system, in contrast with 1339
cm1 in the NR/CB/AE system. G band of CB appears to have
Raman spectrum
a larger variation for the NR/CB system than that of the NR/CB/
Raman spectroscopy is sensitive to short range disorder and it AE system. Simultaneously, the bandwidth of D1 mode is
can reveal the microstructure of CB for its activity toward C–C signicantly narrower than that of pure CB, conrming that the
single bond.26 A previous report27 indicated the importance of degree of ordering of CB in the NR/CB/AE system is greater than
Raman spectrum on surface characterization of partially that of pure CB.26 Contrasting with the D1 bandwidth of CB in
ordered carbon materials. As we know, CB consists of
agglomerated spherical primary particles and exists in a wide
range of ordered and disordered regions, also called graphite Table 1 Raman spectroscopic parameters of CB, residual CB from
crystalline regions and amorphous areas.28 To further inves- extracted NR/CB and NR/CB/AE model compounds obtained after
tigate the inuence of AE on the microstructure of CB, Raman curve fitting the experimental spectra by using two Lorentzian bands
(D1 and G) and two Gaussian bands (D2 and D3)
spectrum was employed and the spectral information of pure
CB and residual CB from extracted NR/CB and NR/CB/AE Peak position Bandwidth Intensity La
model compounds is presented in Fig. 4. It can be seen that Sample n (cm1) u1/2 (cm1) (peak area%) (nm)
two relatively broad bands appear in the range of 1000–1800
cm1: the former at 1350 cm1 is D band is typical of the CB D1 1345 147 31 1.1
D2 1228 273 25
structural disorder and defects, and the latter at 1580 cm1 is
D3 1540 204 36
G band for the typical graphitic order.27 Generally, the varia- G 1586 60 8
tion information of CB microstructure is much more signi- NR/CB D1 1355 146 24 1.8
cant in NR matrix without AE for its larger Raman shi D2 1263 304 32
compared with pure CB spectrum. This might be evidence of D3 1540 211 34
G 1602 76 10
the weakened interaction between CB and the rubber phase
NR/CB/ D1 1339 122 11 5.2
caused by AE. AE D2 1268 306 34
In order to improve the accuracy in the determination of D3 1506 291 42
spectroscopic parameters, such as peak position, bandwidth, G 1585 79 13

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the NR/CB system, it indicates that AE could increase the degree 110 peak appear around 25 and 44 , respectively,35,37 which
of ordering of CB. Normally, G mode is related to the crystalline are assigned according to the standard XRD spectrum of
component in carbons, and an increase of order in carbona- graphite. In contrast to the spectrum of pure CB, the shapes
ceous materials is reected by a decrease of its bandwidth. and positions of diffraction peaks of residual CB from
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However, the comparative study of the bandwidth of G mode extracted NR/CB and NR/CB/AE systems signicantly
does not allow conclusive remarks mentioned above. This changed. This indicates that a signicant variation in the
might be due to the fact that D3 mode, which usually appears at microstructure of CB appears via mixing of CB and NR, or
1620 cm1 as a shoulder, is not observed in these four spectra adding AE into NR/CB compound.
and interferes with the G mode, thus complicating the To further study the variation of crystallites structure of CB
interpretation.26,30 in three different conditions, a Gaussian peak tting program
The nanoscale crystal on the CB surface, proven by High was employed; the results are shown in Fig. 5(b) and the data
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Resolution Transmission Electron Microscopy (HRTEM),31 is parameters are listed in Table 2. According to the theory of J.
important and its size, called microcrystalline planar crystal Biscoe,32,34,35 crystallite plane size Ha (110 band) and crystallite
size (La), has a negative relationship to the dispersive free energy axial size Hc (002 band) can be calculated by eqn (3) and (4):
(gds)32 of the CB surface. It is well known that gds is the nonpolar 1:84l
part of CB surface free energy, and it presents a positive effect Ha ¼ (3)
B cos q
on the ability of CB to absorb the rubber macromolecule. Thus,
La could be a direct evidence reecting the adsorbability of CB 0:89l
Hc ¼ (4)
on the rubber macromolecule. The larger its value, the weaker is B cos q
its adsorption capacity on the rubber phase, as well as a weak- where l is the wavelength of the incident X-ray. B is the width of
ened interaction between CB and rubber phase. La could be half maximum intensity. q is the Bragg angle (half of the scat-
calculated from the following empirical formula: La ¼ 4.4 IG/ tering angle). B and q must be converted into radians during
ID,26,28,32 where IG and ID are the integrated intensities of the G calculation. As is illustrated, Ha is increased from 1.87 nm of
and D1 bands, respectively. It can be seen that La is increased pure CB to 2.39 nm of the NR/CB system, and it further
from 1.1 nm of pure CB to 5.2 nm of the NR/CB/AE system,
compared with 1.8 nm of the NR/CB system. This means that AE
causes a signicant decline in gds of CB that induces the
Table 2 XRD parameters of CB, residual CB from extracted NR/CB
reduction of CB–NR interaction. The increase of La would lead
and NR/CB/AE model compounds obtained after curve fitting by
to the diminution of quality and total area of grain boundary, Gaussian bands
both of which could cause the decrease of high-energy parts on
the CB surface. Sample Peak B ( ) 2q ( ) Ha (nm) Hc (nm)

CB 002 6.72 24.27 – 1.20

XRD spectrum 110 9.64 44.22 1.87 –
NR/CB – 7.65 19.22 – –
It was reported that carbon black is a heterogeneous mixture 002 1.14 22.55 – 6.99
of particles that range from single graphite lavers up to – 5.40 24.79 – –
graphite crystals several layers thick.33 The effective method to 110 7.52 44.38 2.39 –
NR/CB/AE – 12.77 21.82 – –
investigate the microstructure of CB particles is X-ray
002 4.87 25.08 – 1.65
diffraction (XRD).34–36 Fig. 5 demonstrates the XRD spectra 110 5.41 43.15 3.31 –
of CB, residual CB from extracted NR/CB and NR/CB/AE model – 17.45 47.09 – –
compounds. It can be seen in Fig. 5(a) that the 002 peak and – 8.37 79.88 – –

Fig. 5 XRD spectra of CB, residual CB from extracted NR/CB and NR/CB/AE model compounds: (a) original curves, (b) peak fitting through
Gaussian curves.

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increases to 3.31 nm when AE is added. Simultaneously, Hc is In order to reveal the structural variation of NR/CB
also increased in the NR/CB or the NR/CB/AE system compared composites clearly, a peak tting program was employed
with that of pure CB, and the largest value is obtained without using Origin soware and Gaussian bands of XRD curves in the
AE. Experimentally, Ha plays a negative role on the dispersive range of 10–30 are described in Fig. 7. All the samples with
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free energy (gds) of the CB surface, where a large value of Ha different AE display four Gaussian bands at l ¼ 3, and a new
implies a small value of gds. In addition, there is no remarkable peak around 28 shows up when l is 5. This implies a signicant
relationship between Hc and gds.32 Therefore, the increase of Ha change in the structures of the composites with large strain. The
by AE indicates a decline of gds, which induces the formation of crystallinity index CI and the average crystallite size L120 (taking
weakened CB–rubber interaction. The result agrees with those 120 plane as an example) were calculated according to the data
of Raman spectra analysis and the bound rubber test. Generally, in Fig. 7 using eqn (5) and (6);42–45 then the results are found in
the critical parts that inuence gds are the small crystallites or Fig. 8.
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faulty crystallites that result in numerous high energy parts Ic

where crystal boundary and defects exist, leading to the increase CI ¼
100% (5)
Ic þ Ia
of gds.38–40
kl
L120 ¼ (6)
Effects of AE on strain-induced crystallization behaviors of b1=2

cos q
NR/CB composites 57:3

It is well known that NR is amorphous under the quiescent where Ic is the total integrated intensity of crystals (200 120
condition, but highly crystallizable upon stretching. XRD reections were taken) and Ia is the total integrated intensity of
spectra of NR/CB composites at constant strain ratios (l) are amorphous peaks. K is a constant value of 0.89.43 l is the
presented in Fig. 6. The 200 band and 120 band both reect the wavelength 0.154 nm. b1/2 is the width at half-height of the 120
change of crystallinity on the lateral direction,41 which is reection, and q is the Bragg angle (half of the scattering
perpendicular to the stretching orientation. It can be seen angle).
that crystallization behaviors show up at l ¼ 3 for all specimens In Fig. 8(a), it can be seen that CI increases with increasing
and these could be enhanced while increasing the strain strain but decreases aer adding AE into the composites, which
sequentially. However, there is no signicant difference can be noticed apparently at l ¼ 3, in contrast to the system with
observed in the curves with different AE. no AE. This means that AE has a negative effect on the

Fig. 6 XRD spectra of NR/CB composites under constant strains: (a) 0 phr AE, (b) 3 phr AE, (c) 5 phr AE (strain ratio, l ¼ constant length/initial
length).

Fig. 7 XRD crystallization peak fitting of NR/CB composites without AE at different strain.

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Fig. 8 Crystallization index (CI) (a) and lateral crystallite size, L120, (b) of NR/CB composites with different AE.

crystallization behavior of NR/CB composites. However, in at low strain should be related to the unrestricted rubber
light of the difference in slopes, it can be seen that the chains. The new generated crystallites can be compressed44
composites with AE have large values of crystallization rate, easily while stretching for the weakened ller–rubber
CR, with increasing strain, and CR becomes higher when AE is interaction, due to which the stress is focused on the rubber
added at 5 phr compared with that of 3 phr. Generally, strain- chain. Then, lateral size of composites L120 is decreased
induced crystallization SIC of natural rubber is inuenced by sharply.
stretching velocity,46 ller,43,45 additives,44,47 temperature,45
ller–rubber interaction and so on. In the composites, AE
and ller–rubber interaction might be the dominant reasons Effects of AE on mechanical properties of NR/CB composites
for the variation of SIC behaviors. The increase in CR due to AE Table 3 compares the impact of different AE on the mechanical
in composites should be because of the enhanced slipping properties of NR/CB composites. It can be seen that 100%
effect of NR molecular chains that induce a growth of lattice modulus is increased by adding AE, and the maximum value is
size along the stretching direction; moreover, the weakened obtained when loading AE at 1 phr. 300% modulus of
ller–rubber interaction improves the mobility of NR molec- composites appears to be a decreasing tendency when AE
ular chains, which is benecial for crystallization. On the exceeds 1 phr and the values are lower than that of blank
other hand, the slipping effect of NR molecular chains by AE sample without AE. The increase of 100% modulus should be
might also collapse the chain-folded lamellae or sheaike caused by the augment of physical entanglement points that
(fringed micelle) crystallites43,45,48 and decrease the CI. made a positive effect on CB–NR interaction. On the other hand,
According to the experimental results that CI decreased via the decrease of dispersive free energy on the CB surface caused
adding AE at the same strain ratio, the later one might be by AE would take a dominant position compared with the
primary. Another fact to interpret the decline of CI is the entanglement effect at large strain, such as 300% elongation,
decrease of L120 with increasing strain in NR/CB composites where entanglement points could be destroyed, resulting in the
(Fig. 8(b)), which is in agreement with previous reports.42,43,49 It reduction of CB–NR interaction. This is the reason for the
can be observed that L120 appears to slightly uctuate in decline of 300% modulus. Simultaneously, tear strength is
composites without AE with increasing strain, which indicates increased with the increase of AE until it reaches a threshold
that the increase in crystallinity is because of the increased value at 2 phr AE, and a degressive trend shows up for the value
number of crystallites.41 However, L120 is increased with the of elongation at break. However, there is no signicantly
increase of AE at l ¼ 3 and it decreases signicantly on disciplinary change on tensile strength on increasing AE.
increasing the strain. The greater the content of AE, the larger Generally, the optimal content of AE for NR/CB composites is 2
is the value of the slope of the curve. The increase of L120 by AE phr.

Table 3 Mechanical properties of NR/CB composites modified by AE

Modulus (Mpa)

Properties 100% 300% Tensile strength (Mpa) Elongation at break (%) Tear strength (KN m1)

AE (phr) 0 2.12  0.05 12.51  0.22 32.12  0.83 505  11 39.90  1.47
1 2.50  0.04 12.75  0.14 30.20  1.33 486  16 46.35  1.17
2 2.33  0.03 12.00  0.16 31.13  0.95 502  8 49.32  0.80
3 2.32  0.03 11.61  0.04 30.77  0.78 507  8 43.76  0.69
4 2.27  0.08 10.97  0.28 32.55  0.72 537  7 43.56  0.95
5 2.16  0.07 10.38  0.17 31.88  0.38 542  9 36.67  1.29

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Effects of AE on dynamical properties of NR/CB composites

Rolling power loss, L, and temperature raise of NR/CB
composites were investigated and the results are shown in
Fig. 9. It can be seen that L is decreased rstly while increasing
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AE until it gets the minimum value at AE of 2 phr. With the

increase of AE, temperature raise also decreases slightly until it
obtains a threshold value at AE is 2 phr. Therefore, the opti-
mized ratio for AE in NR/CB composites is 2 phr. The increase of
L and the temperature raise should be caused by the weakened
CB–rubber interaction. The increase of entanglement points
might be responsible for the slight decrease of L and tempera-
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ture raise, which has a positive effect on CB–rubber interaction

and a negative inuence on CB–CB interaction.
Compression fatigue heat production and DIN abrasion
Fig. 9 Influence of AE on rolling power loss and temperature raise of volume were characterized, and the results are shown in
NR/CB composites. Fig. 10. It is observed that heat production decreases slightly
with the increase of AE until it achieves a threshold value at
AE of 2 phr. This is correlated well with the results in Fig. 9.
DIN abrasion volume is signicantly decreased on increasing
AE and it obtains its minimum value when AE is 4 phr.
Although a decline in DIN abrasion volume is seen, the
difference is not signicant. Generally, the optimized ratio of
AE is 2 phr.
Above all, two ambivalent aspects inuenced the CB–
rubber interaction. One is the positive effect of AE on the
formation of entanglement points, which improved the CB–
rubber interaction. The other is the decrease of dispersive free
energy (gds) on the CB surface via adding AE that reduced the
CB–rubber interaction. The latter should be the dominant
factor when the content of AE exceeded 2 phr where the
optimal dynamic properties of NR/CB composites were ob-
tained. The mechanism of CB–rubber interactions are shown
Fig. 10 Influence of AE on compression heat production and abrasion in Fig. 11.
resistance of NR/CB composites.

Fig. 11 Mechanism of CB–rubber interaction influenced by AE.

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9 B. Zhong, Z. Jia, Y. Luo, B. Guo and D. Jia, Composites, Part A,

Conclusions
2015, 73, 63–71.
In summary, the inuence of acetone extract (AE) from natural 10 H. Yingpin, Natural Rubber Processing, Hainan press,
rubber on the interface structure and mechanical properties of Haikou, 2007.
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

NR/CB composites were investigated. Raman spectrum and 11 B. Wang, The effects of the Properties of Nature Rubber aer
XRD representation illustrated that crystallite size of CB was Ozone Aging under different Production Processes and
increased in NR matrix, and it became a larger value when AE Components, Hainan University, 2015.
was added. The result induced a decrease of the dispersive free 12 L. Ma, Extraction and Analysis of Acetone Extract from Natural
energy (gds) on CB surface, which led to the reduction of CB–NR Latex and its Effects on Properties of Rubber, Hainan
interaction. These phenomena were also proven by the decrease University, 2011.
of constrained regions of NR/CB composites. Simultaneously, 13 L. Fan, Extraction and Analysis of Water-soluble Substance in
Open Access Article. Published on 17 May 2017. Downloaded on 06/06/2018 01:57:16.

AE could improve the contact between CB and NR that Natural Rubber Latex and its Effects on Properties of Natural
increased the number of entanglement points and resulted in Rubber, Hainan University, 2013.
the promotion of CB–NR interaction. The two contradictory 14 W. Thongruang, B. Nooklay, P. Bunnaul, R. J. Spontak,
aspects affected the application properties of NR/CB compos- P. Smithmaitrie and K. Chetpattananondh, Adv. Mater.
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ites is 2 phr where the optimal mechanical and dynamical 15 H. Xu, J. Han, F. Liang, X. Zhang and C. Wu, Acta Polym. Sin.,
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by decreasing the crystallization index (CI). Our study clearly Mater. Res., 2011, 264–265, 646–651.
disclosed the relationship between AE and structural variation 17 H. Ismail, S. Z. Salleh and Z. Ahmad, J. Elastomers Plast.,
or application performance of NR/CB composites rstly, which 2013, 45, 445–455.
is useful to the improvement of theoretical research for NR. It 18 D. Fragiadakis and P. Pissis, J. Non-Cryst. Solids, 2007, 353,
might also make sense to the cultivation of Hevea brasiliensis 4344–4352.
concerning the content of AE, or how to control an appropriate 19 A. Sargsyan, A. Tonoyan, S. Davtyan and C. Schick, Eur.
content of AE to meet the needs of the market. Simultaneously, Polym. J., 2007, 43, 3113–3127.
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