Composites Science and Technology 69 (2009) 1797–1803

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Composites Science and Technology

journal homepage: www.elsevier.com/locate/compscitech

Review

The impact of esterification on the properties of starch/natural rubber composite

Zhi-Fen Wang a, Zheng Peng b, Si-Dong Li a,c,*, Hua Lin a, Ke-Xi Zhang a, Xiao-Dong She a, Xin Fu a,*
a
Material and Chemistry Engineering College, Hainan University, Danzhou 571737, PR China
b
Chinese Agricultural Ministry Key Laboratory of Tropical Crop Products Processing, Agricultural Product Processing Research Institute,
Chinese Academy of Tropical Agriculture Sciences, Zhanjiang 524001, PR China
c
College of Science, Guangdong Ocean University, Zhanjiang 524088, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The starch was modified by esterification, and the starch/natural rubber composite was prepared by
Received 14 June 2008 blending the modified starch with natural rubber latex. The morphology, thermal stability and mechan-
Received in revised form 20 April 2009 ical properties of the composite were investigated. The results show that the crystal structure of starch in
Accepted 24 April 2009
the composite disappears after modification with esterification, and the starch particles with an average
Available online 5 May 2009
size around 200 nm homogenously disperse throughout the natural rubber (NR) matrix. The thermal sta-
bility of composite is improved significantly after the modification with starch. The mechanical proper-
Keywords:
ties of composite are enhanced with the increase of starch loading. The composite possesses the best
A.Natural rubber
A.Starch
properties at the starch xanthate content of 20 parts per hundred rubber (phr). The enhanced thermal
A.Composites stability and mechanical properties of modified starch/NR composite are mainly due to the improved
A.Starch xanthate phase interface interactions between rubber and starch.
Esterification Crown Copyright Ó 2009 Published by Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1797
2. Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1798
2.1. Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1798
2.2. Modification of starch [34] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1799
2.3. Preparation of starch/NR composite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1799
2.4. Characterizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1799
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1800
3.1. Characterization of starch/NR composite by XRD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1800
3.2. FTIR analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1800
3.3. Morphology of starch/NR composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1801
3.4. The effect of xanthates on the thermal stability of starch/NR composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1801
3.5. The effect of xanthates on the mechanical properties of starch/NR composite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1802
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1802
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1802

1. Introduction process-ability. However, as an unsaturated polymer, NR will

gradually degrade at a high temperature or when exposed to oxy-
Natural rubber (NR) containing 93–95% cis-1,4-polyisoprene is gen, ozone or ultraviolet, which has a significant negative effect on
an elastomer produced from the latex of rubber tree. NR, as a its especial applications [1,2]. To overcome these limitations of NR
renewable natural resource, has many excellent comprehensive and expand its application, the modification of NR is crucial. Vari-
properties, such as outstanding resilience, high strength and good ous methods can be employed to modify NR. One of the ways is
chemical modification, in which other groups or atoms are intro-
duced onto the NR molecular chains, and thus derives epoxidized
* Corresponding authors. Tel.: +86 759 2210491; fax: +86 759 2383636.
E-mail addresses: [email protected] (S.-D. Li), [email protected] NR [3,4], chloridized NR [5,6], grafted NR [7,8], hydrogenated NR,
(X. Fu). cyclized NR and so forth [9,10]. Another simple and economical

0266-3538/$ - see front matter Crown Copyright Ó 2009 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2009.04.018
1798 Z.-F. Wang et al. / Composites Science and Technology 69 (2009) 1797–1803

way is to blend intensifiers or fillers including black carbon, white to partially replace carbon black in a premium tread [31,32]. Good-
carbon, clay and calcium carbonate with NR [11–15]. With the year Company employed modified cornstarch which was called fil-
gradual drying up of petroleum and the higher demand of environ- ler of biological polymer to partly replace traditional fillers like
mental protection, starch, as a natural, cheap, abundant and bio- black carbon or white carbon to improve the properties of tyres.
degradable resource, has been identified to modify NR [16–30]. Those tyres reinforced with cornstarch possess many advantages,
The mechanical properties of NR filled with starch are domi- such as light quality, low rolling resistance, low noise and low
nated by many factors, such as the dispersing ability, the interfacial emission of carbon dioxide [33]. Carvalho et al. [24] prepared
combination and the type of starches. As the particle size of starch starch/NR composite by blending NR latex and starch paste. Wu
is very big (1000–5000 nm), and the starches contain many hydro- et al. [27,28] prepared composite with rubber latex and starch
xy groups with strong polarity, its compatibility with NR is poor. paste by co-coagulation method. It was found that co-coagulation
Hence, the mechanical properties (elasticity and tear) of composite method can decrease the particle size of starch in NR to less than
filled by direct loading of starch will deteriorate. A large amount of 1000 nm, and the mechanical properties of the composite is much
work has been contributed to improve the mechanical properties better than the composite made by direct blending. Rouilly et al.
of starch/NR composites. In the 1970s, Buchanan et al. prepared [23] prepared the composite by blending dimethylaminoethyl
crosslinked starch xanthide–styrene butadiene rubber (SBR) mas- methacrylate grafted latex and starch. Nakason et al. [30] synthe-
ter batches. It was demonstrated that crosslinked starch xanthide sized grafted copolymer by grafting NR with methyl methacrylate,
could improve the fatigue life and abrasion resistance, when used and then blending the copolymer with NR and cassava starch. The
results showed that the induction period of cure of the composite
decreased with the increase of cassava starch loading.
Due to the strong interaction between hydroxy groups, the
starch particles have a strong self-aggregation nature and therefore
exhibit a poor dispersion within NR matrix. In the present paper,
starch was modified by esterification, and the starch/NR composite
was produced by blending the modified starch with NR latex.
Starch particles with an average size around 200 nm are uniformly
dispersed in NR matrix. The relationship between microstructure,
thermal stability and mechanical properties of starch/NR compos-
ite were investigated.

2. Experimental

2.1. Materials

Natural rubber latex, 30% (w/w), was kindly provided by the

rubber processing factory of experimental farm which belongs to
Fig. 1. XRD patterns of starch and composites: (a) unmodified starch; (b) Chinese Tropical Agriculture Academy (Hainan, PR China). Cassava
unmodified starch (15 phr)/NR composite; (c) modified starch and (d) modified starch was purchased from starch factory of Qiongzhong, Hainan
starch (15 phr)/NR composite. province (Hainan, PR China).

Fig. 2. FTIR spectra of starch: (a) unmodified starch and (b) modified starch.
 Z.-F. Wang et al. / Composites Science and Technology 69 (2009) 1797–1803 1799

2.2. Modification of starch [34] 2.3. Preparation of starch/NR composite

One hundred and sixty two gram starch was blended with Modified starch and NR latex were mixed, and the contents of
2400 ml distilled water to form a paste, 100 ml 5 mol/L sodium starch were 0, 5, 10, 15, 20 and 25 parts per hundred rubber
hydroxide was then added into the paste and the mixture was kept (phr), respectively. The acetic acid was added to co-coagulate the
under stirring for 30 min. After that, 12 ml carbon bisulfide was rubber latex and starch xanthate. After being washing for several
added into the mixture under strong stirring for 1 h until 17 ml times by water, the coagulum was dried in an oven at 75 °C to ob-
0.5 mol/L hydrogen peroxide solution was added. The product tain modified starch/NR blends. The composites were vulcanized
was finally dried to obtain starch xanthate. with the following formula: stearic acid 2.0 phr; zinc oxide
5.0 phr; diben zothiazole disulfide 1.5 phr; diphenyl guanidine
0.5 phr and sulphur 2.0 phr. The temperature of vulcanization is
145 °C, and the times of curing are 8.63, 6.33, 6.23, 6.18, 5.65
and 5.55 min, respectively.

2.4. Characterizations

X-ray diffraction (XRD) analyses were conducted on a D/max

Vpc under a Cu target, with 40 kv, 30 mA and 5.0° at 2h/min. Fou-
rier transform infrared spectroscopy (FTIR) was preformed on a
Perkin–Elmer spectrum one FTIR spectroscopy in horizontal atten-
uated total refraction (HATR). Scanning Electron Microscopy (SEM)
Scheme 1. The formation of S–C bond. morphologies were taken from the tensile fracture surface of com-

Fig. 3. FTIR spectra of NR, starch and composite: (a) NR; (b) modified starch and (c) modified starch (15 phr)/NR composite.
1800 Z.-F. Wang et al. / Composites Science and Technology 69 (2009) 1797–1803

posites using a JSM-T300 SEM. Transmission Electron Microscopy starch was xanthated, S–C bond is formed in the starch molecular
(TEM) observations were performed with a CM300 TEM. A TA chains. The equation is as follow (Scheme 1).
Q600 thermogravimetric analyzer (TGA) was used for the thermal The FTIR spectra of NR, modified starch and modified starch/
degradation measurement. In nitrogen, the measurement of the NR composite are shown in Fig. 3. As presented in Fig. 3a, the
sample (ca. 10 mg) was carried out from 100 °C to 600 °C at a heat- absorptions at 2960 cm 1, 2917 cm 1 and 2851 cm 1 are attrib-
ing rate of 10 °C/min. uted to the stretching vibrations of the methyl and methene in
The Shore A hardness (H) was determined according to ISO 7619- NR [36]. Absorptions at 1662 cm 1 and 1547 cm 1 are vibrations
1986. The stress at 500% (S), tensile strength (TS), elongation at break of acidamide I and acidamide II of a few proteins in NR [35]. The
and permanent set (Sb) were determined according to ISO 37-1994. absorptions at 1447 cm 1 and 1375 cm 1 are attributed to the
The tear strength (Ts) was determined according to ISO 34-1-1994. bending vibrations of methene and the vibrations of methyl in
NR. The absorptions at 1036 cm 1 and 839 cm 1 are attributed
3. Results and discussion to –NH of protein in NR and bending vibrations of C–H bond
in the double bond. Fig. 3b shows there is a absorption at
3.1. Characterization of starch/NR composite by XRD 3340 cm 1 which is attributed to the stretching vibrations of hy-
droxyl group of modified starch. Absorption at 1638 cm 1 is C–O
XRD patterns of unmodified starch, unmodified starch/NR com- vibrations in the chelate aldehyde group. The vibrations of
posite, starch xanthate and starch xanthate/NR composites are pre- unsymmetry C–O–C bond and C–O bond of primary alcohol are
sented in Fig. 1. Fig. 1a shows the diffraction peaks of starch at 1154 cm 1 and 1045 cm 1. Absorption at 879 cm 1 is of meth-
appearing at 15.1°, 17.1°, 18.2° and 22.8°, which present the crys- ene vibration in modified starch. As presented in Fig. 3c, in addi-
talline structure of starch. NR is an amorphous elastomer in room tion to the characterization absorptions of NR (Fig. 3a), those of
temperature, but it will make crystalline until in lower tempera- modified starch (Fig. 3b) are also presented in the spectra of
ture ( 25 °C) or under strain. Although starch was blended with modified starch/NR composite. From the spectra of composite,
NR, the crystalline structures can be clearly observed (Fig. 1b). it can be seen there is the broader and stronger absorption at
After modification, crystalline structure of starch is ruptured as 1659 cm 1, which contains both absorptions of acidamide I of
the crystalline diffraction peaks disappeared (Fig. 1c). The crystal- NR (1662 cm 1) and that of C–O bond of chelate aldehyde group
line peaks cannot be found in Fig. 1d, which demonstrates that the of starch (1638 cm 1). The reason is the formation intra-hydro-
starch dispersed in the NR matrix is in an amorphous state. gen bonding between NR and starch, which leads to chemical
bond polarization for attending intra-hydrogen bonding. The
3.2. FTIR analyses absorption at 1023 cm 1 is attributed to absorption both –NH
(1036 cm 1) in NR and primary alcohol C–O (1045 cm 1) in
The FTIR spectra of starch are shown in Fig. 2. Comparing with starch. The formation of intra-hydrogen bonding between NR
unmodified starch (Fig. 2a), it is found that the absorbent band of and starch results in the reducing of the vibrations frequency
hydroxyl group (3340 cm 1) of modified starch (Fig. 2b) becomes of –NH and polar bond C–O, which attends the formation hydro-
narrower, and there is a new absorption at 1084 cm 1 which is gen bonding [37]. From absorptions at 1659 cm 1 becoming
attributed to the stretching vibration of S–C [35]. It indicates after broad and strong, vibrations frequency at 1023 cm 1 reducing,

Fig. 4. SEM micrographs of starch and composite: (a) unmodified starch; (b) unmodified starch (15 phr)/NR composites; (c) modified starch (5 phr)/NR composite and (d)
modified starch (15 phr)/NR composite.
 Z.-F. Wang et al. / Composites Science and Technology 69 (2009) 1797–1803 1801

Fig. 5. TEM micrographs of starch and composite: (a) unmodified starch (15 phr)/NR composites and (b) modified starch (15 phr)/NR composite.

it can be concluded that the hydrogen bonding has been formed

between starch and NR. The formation of hydrogen bonding be-
tween the acidamide group of a few proteins in NR [35] and the
hydroxyl group in starch enhances the interface interaction be-
tween starch and NR.

3.3. Morphology of starch/NR composite

SEM micrographs of starch and the tensile-fractured surface

of starch/NR composite are shown in Fig. 4. Fig. 4a shows the
size of the starch granules is around 1000–5000 nm, and the
shape of the starch granules is circular or polygonal. The surface
of starch is compact and smooth. In Fig. 4b, it can be seen that
the size and shape of the starch granules in unmodified starch/
NR composite remains almost the same as that of the original
starch. There are some apparent holes on the fracture surface
Fig. 6. TG curves of NR and composites: (a) NR; (b) unmodified starch (15 phr)/NR
of the composites, which suggests that the interfacial interaction
composite and (c) modified starch (15 phr)/NR composite.
between the starch and rubber is weak. After the starch is mod-
ified, the size of the starch granules in composite strongly re-
duces to be smaller than 200 nm (Fig. 4c and d). The fracture
surface of the composite becomes coarser with increasing the
dosage of starch xanthate, indicating that the resistance of com-
posite to external force is the bigger, and NR is strengthened
with starch obviously.
TEM micrographs provide other evidences to support the
improvement of the dispersion of starch particles in NR when they
are modified (Fig. 5). The light phase in the TEM micrograph repre-
sents the NR matrix and the dark phase corresponds to the starch
particles. The size of the unmodified starch granules is about
1000 nm (Fig. 5a). After modification, the size of the starch parti-
cles in the composites is smaller than 200 nm (Fig. 5b). It is found
that almost all the modified starch particles are homogenously dis-
persed within NR matrix.
SEM and TEM characterizations demonstrate that after modifi-
cation, the size of starch particles in NR matrix significantly de-
creases, the dispersion of starch is greatly improved and the
phase interface interaction between rubber and starch is markedly Fig. 7. DTG curves of NR and composites: (a) NR; (b) unmodified starch (15 phr)/NR
enhanced. composite and (c) modified starch (15 phr)/NR composite.

3.4. The effect of xanthates on the thermal stability of starch/NR

composite

The thermal degradation process of NR and composites are

Table 1
very similar, and there is only one turn in the TG curve Thermal degradation temperatures of NR and composites.
(Fig. 6) and a single peak in the DTG curves (Fig. 7), indicating
Samples T0 (°C) Tp (°C) Tf (°C)
that the thermal degradation of NR and composites is a one-step
reaction. The thermal degradation curve of unmodified starch/NR NR 333 372 428
composite, compared to the pure NR, shifts towards low temper- Unmodified starch (15 phr)/NR composite 312 367 413
Modified starch (15 phr)/NR composite 346 376 442
atures, while that of the modified starch/NR composite moves to
1802 Z.-F. Wang et al. / Composites Science and Technology 69 (2009) 1797–1803

Table 2
Mechanical properties of composites prepared with different starch.

Starch content (phr) Hardness (Shore A) Stress at 500% (MPa) Tensile strength (MPa) Elongation at break (%) Permanent set (%) Tear strength (kN/m)
0 41 6.3 18.8 650 20 32.9
10 (unmodified) 45 7.7 19.8 620 17 32.4
10 (modified) 49 10.8 20.8 585 30 36.6

Table 3
Mechanical properties of composites prepared with different modified starch loadings.

Modified starch content Hardness (Shore Stress at 500% (MPa) Tensile strength Elongation at break Permanent set (%) Tear strength
(phr) A) (MPa) (%) (kN/m)
0 41 6.3 18.8 650 20 32.9
5 43 7.9 19.6 580 28 35.4
10 49 10.8 20.8 585 30 36.6
15 52 14.6 22.9 580 36 36.7
20 51 17.6 24.9 580 33 36.9
25 52 16.3 24.7 575 40 40.3

high temperatures. The initial temperature (T0) and the final 4. Conclusions
temperature (Tf) of NR and composites are obtained with a bi-
tangent method, and Tp is the temperature at maximum weight In the resulting composite, the crystal structure of starch parti-
loss rate which can be obtained from the peak of the DTG curves cle is translated into amorphism after being esterified. The modi-
(Table 1). The T0, Tp and Tf of unmodified starch/NR composite fied starch can be homogenously dispersed in the natural rubber
are lower (21 °C, 5 °C and 15 °C, respectively) than those of NR, matrix with an average particle size around 200 nm. The loading
while the T0, Tp and Tf of modified starch/NR composite increase of esterified starch leads to a significant improvement of thermal
13 °C, 4 °C, 14 °C, respectively, compared to NR (Table 1). The stability. When the esterified starch content is less than 20 phr,
interfacial combination between NR and starch is weak when the mechanical properties of the composites receive a linear
the starch is not modified, which leads to the deterioration of increase.
thermal stability. However, when the starch is esterified, the
interfacial combination between NR and starch is improved, Acknowledgement
and the thermal stability of composite is therefore enhanced.
The authors would like to acknowledge the financial support
3.5. The effect of xanthates on the mechanical properties of starch/NR from National Natural Science Foundation of China (No.
composite 50773013).

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