Carbohydrate Polymers 169 (2017) 324–331

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

The fabrication of microcrystalline cellulose-nanoZnO hybrid

composites and their application in rubber compounds
Yunhao Liang a , Xiaoling Liu a , Lili Wang a , Jutao Sun a,b,∗
a
Key Laboratory of Rubber-Plastics, Ministry of Education, Shandong Provincial Key Laboratory of Rubber-plastics, Qingdao University of Science &
Technology, P.O. Box 73, Qingdao 266042, People’s Republic of China
b
Key Laboratory of Wood Science and Technology, Zhejiang Province, Lin’an 311300, People’s Republic of China

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

Article history: Microcrystalline cellulose (MCC) was first swollen and then hybridized with nano-ZnO to prepare MCC-
Received 1 December 2016 ZnO hybrid composites using a microreactor technique. The microstructure of the ZnO particles was
Received in revised form 11 April 2017 controlled and characterized. The results showed that the nano-ZnO particles had a Wurtzite structure
Accepted 11 April 2017
and were successfully loaded on the surface of the MCC, and the ZnO morphologies could be shaped as
Available online 14 April 2017
spheres, rods or tubes by controlling the size of microreactor. The hybrid ratio of ZnO was approximately
20%. The MCC-ZnO hybrids were used in SSBR2557A/SiO2 compounds to replace portions of the silica. The
Keywords:
results showed that MCC-ZnO compounds had improved processing and mechanical properties compared
Microcrystalline cellulose
Nano-ZnO
to the pure MCC sample. The dynamic mechanical analysis (DMA) indicated that MCC-ZnO compounds
Hybrid composites had higher wet-skid resistance and lower rolling resistance than the control samples. The interfacial
Microreactor bonding between the hybrids and rubber was also improved; the sizes of the hybrid composites decreased
Rubber compounds in situ during the rubber processing.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Rubber is a kind of essential and irreplaceable material for the
national economy and people’s daily lives. The currently used rein-
forcing fillers for the rubber industry include carbon black and
silica (Karásek & Sumita, 1996; Kaewsakul, Sahakaro, Dierkes, &
Noordermeer, 2014). Both of them are derived from non-renewable
resources, and their production requires tremendous amount of
energy. Furthermore, they have difficulty decomposing in the wild,
and the disposal of their rubber composites by combustion causes
environment pollution because a large amount of ash is generated
(Luo, Xu, Gu, & Jia, 2012; Dong et al., 2016). Therefore, developing
new reinforcing filler that are inexpensive, readily available, light
in weight and renewable is a very important task for the rubber
industry.
Biomass fillers, including starch (Wu, Ji, Qi, Wang, & Zhang,
2004; Rouilly, Rigal, & Gilbert, 2004), cellulose (Haghighat,
Khorasani, & Zadhoush, 2007; Deng et al., 2016), lignin (Wang,
Easteal, & Edmonds, 2008; Botros, Eid, & Nageeb, 2010) and protein
∗ Corresponding author at: School of Polymer Science and Engineering, Qing-
dao University of Science and Technology, P.O. Box 73, Qingdao 266042, People’s
Republic of China.
E-mail address: sjt-hit@163.com (J. Sun).
(Tian, Zhang, Wu, Wang, & Chen, 2010), have the advantages being
biodegradable and renewable and have attracted much attention
for use in the rubber industry. Among them, cellulose is the most
attractive filler due to its high strength, low cost and wide avail-
ability. Cellulose contains both amorphous and crystalline regions.
Microcrystalline cellulose (MCC), prepared from natural cellulose
using a simple treatment to remove most of the amorphous regions,
is much stronger and stiffer than cellulose itself, and has the poten-
tial to be used as reinforcing filler (Bai & Li, 2009). Compared
with silica and carbon black, MCC particles have the advantages
of being abundant, low cost, renewable, degradable and low den-
sity and are supposed to be a superior filler for use in “green
tires”. However, MCC forms large particle sizes (20–90 ␮m) and
highly polar, which deteriorates its reinforcing efficiency in non-
polar polymer matrixes. Many methods have been developed to
decrease the size of MCC particles, including mechanical shearing
(Chinga-Carrasco & Syverud, 2009; Iyer, Flores, & Torkelson, 2015),
acidolysis (Ma, Hu, & Wang, 2016; Nascimento et al., 2016), and
enzymolysis (Jiang, Chen, & Zong-Ren, 2008; Vancov & Mcintosh,
2012). MCC particles less than 20 ␮m and even nanocrystalline cel-
lulose (NCC) (Iyer, Schueneman, & Torkelson, 2015) can be obtained
using these methods. However, the polarity of MCC remains high
and its aggregation is significant, which weakens its reinforcing
efficiency. Other approaches have been explored to improve the
interfacial interactions and compatibility of MCC-rubber reacting

http://dx.doi.org/10.1016/j.carbpol.2017.04.022
0144-8617/© 2017 Elsevier Ltd. All rights reserved.
 Y. Liang et al. / Carbohydrate Polymers 169 (2017) 324–331
Table 1
Recipes of the experiment.
Ingredients Silica (control) MCC MCC-ZnO
(phr) (phr) (phr)
SSBR2557A 100 100 100
Silica 50 45 45
MCC/MCC-ZnO 0 5 5 room temperature and then leached and vacuum dried respectively
ZnO 3 2 2
SA 1 1 1
TBBS (NS) 1.5 1.5 1.5
DPG 1 1 1 actor for the following sol-gel reaction. The swollen MCC (partially
Si-69 4 4 4 dried for different durations) was dispersed in ethanol, added drop-
Sulfur 1.76 1.76 1.76
the hydroxyl groups of MCC with modifiers, such as esterifica-
tion (Pratheep Kumar & Pal Singh, 2007; Ma, Liu, Anderson, &
Chang, 2016), etherification (Dankovich & Hsieh, 2007), grafting
(Deng et al., 2016; Deng, Ge, Zhang, Li, & Cho, 2015) and silaniza-
tion (Spoljaric, Genovese, & Shanks, 2009; Paopattra, Sarintorn, &
Kawee, 2012) reactions. These chemical methods can improve the
interfacial bonding of MCC-rubber significantly; however, they are
not suitable for large-scale applications due to the extreme reaction
conditions and high costs.
Fillers with a three-dimensional heterostructure have been of
particular interest in recent years, and it has been reported that
3-D heterostructures play a key role as strong reinforcing agents
in polymer matrixes (Kim et al., 2012; Perotti, Barud, Messaddeq,
Ribeiro, & Constantino, 2011). NCC is a rod-like particle and is capa-
ble of serving as a template to generate inorganic particles on its
surface to prepare hybrid composites (Gebauer et al., 2011; Qiao-
Mei, Chen, Huang, & Chen, 2014). MCC has a similar structure as
NCC; however, its use as a template for preparing hybrid com-
posites has been seldom reported. A hybrid filler, MCC-ZnO, was
prepared in this study by using a microreactor technology (a thin
layer of NaOH solution) on the surface and interspaces of MCC. In
addition, this hybrid filler was then used in SSBR/silica compounds
to replace a portion of the silica. One objective of this study was to
prepare MCC-ZnO hybrid fillers with different three-dimensional
heterostructures by controlling the size of the microreactor. The
other objective was to study the reinforcing efficiency of the MCC-
ZnO hybrid filler and discuss the possibility of using it in tire tread
compounds.
2. Experimental
2.1. Materials
Microcrystalline cellulose (20–90 ␮m), made by mechanical
shearing, was purchased from Shandong Liaocheng Luxi Medici-
nal Materials Co.,Ltd., China; Zinc acetate (Zn(Ac)2 ·2H2 O), sodium
hydroxide and alcohol, analytically pure, were received from Tian-
jin Yongda Chemical Reagent Co.,Ltd., China; Table 1 gives the
compositions of the rubber compounds studied. The elastomer
was a solution-polymerized styrene butadiene rubber (SSBR2557A,
the styrene content was approximately 25% and the butadiene
content was approximately 75%) received from Sinopec Dushanzi
Co.,Ltd., China. Silica (1165 MP, with a specific surface area of
165 m2 /g) was obtained from Solvay Fine Chemical Additives Qing-
dao Co.,Ltd., China. [3-(Triethoxysilyl)propyl]tetrasulfide (Si-69),
industrial grade, was purchased from Qingdao Degussa Chemi-
cal Co.,Ltd., China. The other materials, such as zinc oxide, stearic
acid, sulfur, diphenylguanidine (DPG) and N-tertiarybutyl-2-
benzothiazole sulfonamide (TBBS), industrial grade, were received
from Sentury Tires Co.,Ltd., China.
325
2.2. The fabrication of the MCC-ZnO hybrids
The preparation of the MCC-ZnO hybrids included swelling
the MCC, followed by sol-gel process with Zn(Ac)2 . The MCC was
swollen with an 8 wt% NaOH solution (this concentration was
determined from our large number of pre-experiments) for 4 h at
for 6, 22, 44 or 96 h at room temperature to control the thickness of
the absorbed NaOH solution layer. This layer was used as a microre-
wise to an ethanol solution of Zn(Ac)2 using a separating funnel,
and then reacted at 80 ◦ C for 1 h. The MCC-ZnO hybrids (MCC-ZnO-
1, MCC-ZnO-2, MCC-ZnO-3 and MCC-ZnO-4) were obtained after
washing them with distilled water 3 times and drying at 80 ◦ C in a
vacuum oven for 6 h. The swollen MCC used for MCC-ZnO-1, MCC-
ZnO-2, MCC-ZnO-3 and MCC-ZnO-4 corresponded to partial drying
times of 6, 22, 44 and 96 h respectively.
2.3. Preparation of the rubber compounds
The rubber and other ingredients were weighed, as reported in
Table 1, and then mixed in a torque rheometer (Rheomix3000OS,
Haake, Germany) according to the standard procedure (ASTM
D3182-07). The feeding order was as follow: rubber, a half of the
total silica (with Si-69), the other half of the silica (with Si-69) and
MCC, and the rest of the components (ZnO, SA, NS and DPG).
The sulfur was added onto an open mill, and sheets with an
approximate thickness of 2 mm were obtained. The curing time
(t90 ) was measured using a rheometer vulcanization machine
(MDR-2000, Alpha, USA) at 160 ◦ C. The oscillating frequency was
1.7 ± 0.1 Hz with an amplitude of ±3.0◦ . The volume of the test
specimens were approximately 5 cm3 , and the total test time was
1 h. The vulcanization was carried out at t90 in a hydraulic press
(HS100T-RTMO, Shenzhen Jiaxin Co. Ltd., China) at 160 ◦ C and
10 MPa, and then, the vulcanizates were obtained.
2.4. Characterization of MCC and its hybrids
2.4.1. Fourier transform infrared spectroscopy (FT-IR)
MCC and MCC-ZnO samples tableted with KBr powder were
tested using a Fourier infrared transform spectrometer (VERTEX70,
Bruker Corporation, Germany) with scanning wavenumbers rang-
ing from 400 to 4000 cm−1 .
2.4.2. X-ray diffraction (XRD)
The X-ray diffraction spectra of the MCC, swollen MCC and MCC-
ZnO hybrids were obtained using an XRD (Ultima IV, Rigaku, Japan)
with a Cu K␣ source at 40 kV and 40 mA.
2.4.3. Field-emission scanning electron microscope (SEM)
analysis
A field-emission scanning electron microscope (JSM-7500F,
Japan Electron Optics Laboratory Co., Ltd., Japan) was used to obtain
micrographs of the MCC and its hybrids. The samples were sputter-
coated with a thin layer of gold before the measurements.
2.4.4. Thermogravimetric analysis (TGA)
A thermogravimetric analysis (TGA) was performed using a NET-
ZSCH thermogravimetric analyser (209F1, NETZSCH, Germany).
The samples were heated from 30 to 800 ◦ C in a nitrogen atmo-
sphere with a heating rate of 20 ◦ C/min.
326 Y. Liang et al. / Carbohydrate Polymers 169 (2017) 324–331
Fig. 1. IR spectra of the MCC and MCC-ZnO hybrids.
22.4 MCC
Swollen MCC
MCC-ZnO-1
MCC-ZnO-4
Intensity[a.u.]
15.7
10 20 30 40
2?[°]
Fig. 2. The XRD spectra of the MCC, swollen MCC and MCC-ZnO hybrids.
2.5. Characterization of the rubber compounds
2.5.1. The physio-mechanical properties of the vulcanizates
The physio-mechanical properties of the vulcanizates, such as
the tensile properties including the tensile strength and modulus
at 100% and 300% elongation (ASTM D412), tear strength (ASTM
D624), Shore hardness (ASTM D2240) and resilience (ASTM D2632),
were determined following their respective ASTM standard.
2.5.2. DIN abrasion
The abrasion tests were carried out using a DIN abrader (GT-
7012-D, Gotech Testing Machines Co., Ltd., Taiwan) according to
ASTM D5963. A cylindrical rubber test specimen, 16 mm in diam-
eter and 10 mm high, was abraded against an abrasive surface
mounted on a rotating cylindrical drum. The specimen was gripped
in a steel collet chuck and was clamped tightly into the specimen
holder with a portion of it protruding 2 mm from the clamping
aperture with a gauge. The drum, 150 mm in diameter, rotated at
approximately 40 revs/min, and the chuck moved parallel to the
axis of the drum at approximately 3 mm/s, simultaneously. Dur-
ing the whole experiment, the sample slid for approximately 120 s,
which was equivalent to approximately 84 revolutions. The mass
loss of the test specimen and its density were measured, and its
volume loss was calculated.
Fig. 3. TGA curves of the MCC and MCC-ZnO hybrids.
2.5.3. Dynamic mechanical analysis (DMA)
The dynamic mechanical properties of the samples were mea-
sured using a dynamic mechanical analyser (DMTS EPLEXOR 500N,
GABO, Germany) in tensile mode at a constant frequency of 10 Hz.
The specimens were 20 mm in length, 4 mm in width and 2 mm in
thickness. The temperature ranged from −80 to 80 ◦ C at a heating
rate of 3 ◦ C/min. The loss angle tangent (tan␦) was measured as a
function of temperature under identical conditions.
2.5.4. SEM analysis
The vulcanizates were stretched to failure, and the fractographs
were observed using SEM to study the microstructure of the MCC
and MCC-ZnO hybrids in the matrix. The fracture surfaces were
sputter-coated with a thin layer of gold to prevent electrical charg-
ing during the examination.
3. Results and discussion
3.1. Characterization of the MCC-ZnO hybrids
3.1.1. FT-IR analysis
The IR spectra of the MCC and MCC-ZnO hybrids are shown in
Fig. 1.
A peak at 475 cm−1 in Fig. 1 appeared in the IR spectrum of the
MCC-ZnO hybrid, which was the characteristic absorption band of
the Zn-O bonds (Ko, Mun, Min, Kim, & Kim, 2014). In addition, the
peak at 2900–3000 cm−1 belonging to the stretching vibration of
the C H bonds was weaker for the hybrids than that of the pure
MCC because the methyl and methylene groups of the hybrid MCC
were covered with loaded ZnO particles. The characteristic band
for the C C groups within the benzene rings at 1649 cm−1 was
attributed to the cellulose (Ko et al., 2014), which weakened in the
MCC-ZnO curves due to the ZnO particle coverage on the cellulose.
These results indicated that ZnO had been loaded successfully on
the surface of the MCC. The peaks at 1576 cm−1 for the stretching
vibration of C O belonged to Zn(Ac)2 , showing that Zn(Ac)2 had
not reacted completely (Song, Yong, Yang, Liu, & Bingshe, 2012).
3.1.2. XRD analysis
The XRD spectra of the MCC and MCC-ZnO hybrids are shown
in Fig. 2.
Fig. 2 shows the XRD patterns of the MCC, swollen MCC and
MCC-ZnO hybrids (MCC-ZnO-1 and MCC-ZnO-4). Characteristic
peaks of the MCC appeared at 2␪ = 15.7◦ and 22.4◦ and indicated
that these samples had the structure of cellulose I (Lee et al., 2013).
The swelling process did not change the crystal form of MCC but
 Y. Liang et al. / Carbohydrate Polymers 169 (2017) 324–331 327

Fig. 4. The morphologies of the MCC and MCC-ZnO hybrids.

decreased its crystallinity significantly. The crystallinity was 87.9%
for MCC, 61.9% for swollen MCC, 87.2% for the MCC-ZnO-1 and 84.9%
for MCC-ZnO-4, as calculated according to the “Segal Equation”:
C␥ I = (I002 − Iam )/I002 *100%, where C␥ I, I002 and Iam respectively,
represent the percentage of relative crystallinity, the maximum
intensity of the lattice diffractive angle and the scattering inten-
sity of the amorphous background diffraction. The crystallinity of
swollen MCC decreased obviously due to the NaOH destroyed the
crystalline of cellulose I at high temperature (Nakano, Tanimoto, &
Hashimoto, 2013) in the drying process. The NaOH was reacted in
the sol-gel process for MCC-ZnO-1 and MCC-ZnO-4, and therefore
their crystallinity hadn’t decreased sharply than that of MCC.
Compared with MCC, the peaks at 31.6◦ , 34.2◦ and 36.2◦ in the
MCC-ZnO-1 and MCC-ZnO-4 curves were assigned to (100), (002)
328 Y. Liang et al. / Carbohydrate Polymers 169 (2017) 324–331

Table 2
Effects of the MCC-ZnO hybrids on the curing properties of the compounds.

Samples control MCC MCC-ZnO-1 MCC-ZnO-2 MCC-ZnO-3 MCC-ZnO-4

t10/ min 1.38 2.41 2.21 2.52 2.13 2.27

t90 /min 26.47 26.60 25.61 26.21 24.62 24.61
ML /dN.m 4.12 3.13 2.98 3.30 3.36 3.39
MH /dN.m 31.42 27.89 27.21 27.82 28.17 28.25
MH -ML /dN.m 27.30 24.76 24.23 24.52 24.81 24.86
Mooney viscosity/MU 102 89 90 90 91 90

and (101), respectively, which confirmed the Wurtzite structure of
the loaded ZnO particles (Ko et al., 2014). The crystallinity size of
ZnO in MCC-ZnO-4 was slightly higher than that in the MCC-ZnO-1
according to the “Scherrer equation”: Dc = K␭/Bcos , where Dc is
the diameter of the crystalline phase, and B, ␭ and ␪ are the full
width at half maximum intensity, the wavelength of the X-ray and
incident angle, respectively.
3.1.3. Thermogravimetric analysis
The TGA curves of the MCC-ZnO hybrids prepared under differ-
ent conditions were compared with the pure MCC to determine the
amount of loaded ZnO particles, as shown in Fig. 3.
As observed from the TGA curve of MCC, the thermal-
decomposition temperature of MCC was 350 ◦ C and the residue
tended to be 5% at 800 ◦ C, which indicated the amount of resid-
ual carbon after 400 ◦ C. The thermal-decomposition temperature
of MCC-ZnO was approximately 300 ◦ C, lower than that of the pure
MCC due to the alkali catalysis (Niemela, 1987). In addition, the
residue of the hybrids was approximately 25% at 800 ◦ C, indicating
that the amount of loaded ZnO on the MCC was approximately 20%.
3.1.4. The microstructure of the MCC-ZnO hybrids
The morphology, structure and size of the ZnO particles in the
MCC-ZnO hybrids were observed using a scanning electron micro-
scope (SEM). Fig. 4(a)–(j) shows the SEM images of the pure MCC
and samples MCC-ZnO-1 through MCC-ZnO-4, respectively.
From Fig. 4, it was observed that the surface of the MCC hybrids
was loaded with ZnO particles or tubes. The ZnO morphologies
varied from MCC-ZnO-1 to MCC-ZnO-4. For MCC-ZnO-1, the mor-
phology of the loaded ZnO was mainly spherical particles with size
of 50–100 nm and a few aggregates. For MCC-ZnO-2, some larger
spherical ZnO particles were formed on the surface of the smaller
ZnO particles. Meanwhile, for MCC-ZnO-3 and MCC-ZnO-4, rod-
like and tubular ZnO particles with diameters of 10–20 nm were
formed. The different patterns of ZnO have been caused by the
thickness of the lye layer absorbed on the surface of the swollen
MCC, which acted as a microreactor during the sol-gel reaction.
When the thickness of the lye layer decreased due to vacuum
drying, the dimensions of the microreactor decreased and the con-
centration of NaOH increased, and then more ZnO particles could
form into tubes or rods by self-assembly (Wang, Qian, Yin, & Zhu,
2004). These results indicated that different ZnO structures and
morphologies could be prepared by controlling the thickness of
the lye layer on the swollen MCC. The different structures and
morphologies of the loaded ZnO particles could result in different
reinforcing efficiencies in rubber matrix.
3.2. The application of MCC-ZnO hybrids in silica/SSBR
compounds
The effects of the MCC (used as received) and MCC-ZnO hybrid
fillers on the processing, physio-mechanical and dynamic mechan-
ical properties of the vulcanizates were studied by using 5phr MCC
or 5phr MCC-ZnO hybrids to replace the same amount of silica in
the compounds described in Table 1. Due to the loading of nano-
ZnO particles in the MCC was approximately 20%, the 1phr activator
ZnO in the formula was also replaced.
3.2.1. The curing characteristics
The effects of the MCC and MCC-ZnO hybrids on the curing prop-
erties of the compounds are shown in Table 2.
Compared to the control specimen, the scorch time of MCC-ZnO
was extended, and the curing time was also shortened slightly.
Longer scorch times ensured higher processing safety, and shorter
curing time endowed the compounds with higher production effi-
ciency. The ZnO loaded on the surface of the MCC was able to
activate the curing system by reacting with stearic acid (SA), which
enhanced not only the curing efficiency but also the interactions
between the rubber and MCC-ZnO hybrids. Table 2 also showed the
Mooney viscosity decreased when portions of silica were replaced
by MCC-ZnO hybrids, which meant that a better processing fluidity
could be achieved.
3.2.2. The physio-mechanical properties
The effects of the MCC and MCC-ZnO hybrids on the physical and
mechanical properties of the SSBR/SiO2 vulcanizates are shown in
Table 3.
The Table 3 shows that the physio-mechanical properties of
the MCC specimens were lower than those of the control, indicat-
ing the poor reinforcing efficiency of MCC as compared to silica.
MCC has large particle size (20–90 ␮m) and high polarity, there-
fore its interaction and compatibility with rubber matrix is poor,
resulting in the poor reinforcing efficiency. However the tensile and
tear performances of the MCC-ZnO-2 and MCC-ZnO-3 vulcanizates
were comparable to those the control vulcanizates and were higher
than those of the pure MCC sample, indicating that MCC-ZnO-2
and MCC-ZnO-3 improved the reinforcing efficiency compared to
MCC. However, compared to the MCC, the reinforcing efficiencies
of MCC-ZnO-1 and MCC-ZnO-4 were not improved.

Table 3
Effects of the MCC-ZnO hybrids on the mechanical properties of the vulcanizates.

Properties control MCC MCC-ZnO-1 MCC-ZnO-2 MCC-ZnO-3 MCC-ZnO-4

Tensile strength/MPa 15.7 14.4 14.3 15.4 15.5 14.1

Elongation at break/% 347 326 347 342 334 346
Tear strength/kN.m−1 48.8 46.8 47.1 47.6 48.0 41.9
100% modulus/MPa 3.12 3.16 3.16 3.13 3.12 2.71
300% modulus/MPa 7.81 7.72 7.65 7.69 7.81 6.54
Resilience/% 18.0 23.0 25.0 25.0 24.0 25.0
Hardness/shore A 73.0 74.0 71.0 71.0 71.0 71.0
 Y. Liang et al. / Carbohydrate Polymers 169 (2017) 324–331 329

From Fig. 5, the abrasion loss of the MCC sample was much
0.10 higher than that of the control, meaning that the addition of MCC
deteriorated the abrasion resistance. However, the abrasion loss
decreased significantly for the MCC-ZnO samples, especially for
DIN abrasion loss(cm )
3

0.08
MCC-ZnO-2 and MCC-ZnO-3, indicating the improved abrasion
resistance.
0.06

0.04 3.2.4. The dynamic mechanical properties

The rolling resistance and wet-skid resistance of tires are two
0.02 important features of an automotive. These two properties are
related to the viscoelastic properties of the rubber compounds and
can be characterized from curves of the loss angle tangent (tan␦) vs.
0.00 the temperature (T). These curves can be obtained by conducting
control MCC MCC-ZnO-1MCC-ZnO-2MCC-ZnO-3MCC-ZnO-4
DMA tests. Tire tread compounds, especially for high-performance
Samples
tires, should have a low tan␦ at 60 ◦ C to ensure a low rolling resis-
Fig. 5. Effect of the MCC-ZnO hybrids on the abrasion loss of the vulcanizates.
tance and a high tan␦ at 0 ◦ C to ensure a high wet-skid resistance.
The effects of using 5phr MCC and MCC-ZnO-3 (replacing 5phr sil-
ica of the total 50phr) on the tan␦-T curves were compared with
those using only silica compounds. The curves are shown in Fig. 6.
It is shown in Fig. 6(b) and (c) that, compared with the control,
3.2.3. The DIN abrasion resistance the tan␦ values of the MCC and MCC-ZnO-3 samples at 0 ◦ C were
Abrasion or wear resistance is an important property for many significantly improved while they were reduced at 60 ◦ C, especially
products, such as belts, shoe soles, and, especially, tires. The effects for the MCC-ZnO-3 vulcanizates. These results indicated that if MCC
of the MCC-ZnO hybrids on the DIN abrasion resistance are shown or MCC-ZnO hybrids were used in tire tread compounds, a higher
in Fig. 5. wet-skid resistance would be achieved, accompanied by a lower

Control Control
1.1
1.0 MCC MCC
MCC-ZnO-3
MCC-ZnO-3
0.8
1.0
Tand

Tand

0.6

0.9
0.4

0.2
0.8

0.0
-80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80 -10 0 10
Temp.[°C] Temp.[°C]
(a) Full spectrum (b) Magnification of one segment
0.16
Control
MCC
0.14 MCC-ZnO-3
Tand

0.12

0.10

0.08

40 50 60 70
Temp.[°C]

(c) Magnification of one segment

Fig. 6. Curves of tan␦ vs. temperature.
330 Y. Liang et al. / Carbohydrate Polymers 169 (2017) 324–331

Fig. 7. The tensile fracture morphologies of the vulcanizates.

rolling resistance. In addition, compared to MCC, MCC-ZnO-3 per-
formed better.
3.3. The morphology of the MCC-ZnO hybrids in the rubber matrix
The tensile samples were stretched to failure and then the failure
sample surfaces were sputter-coated with a thin layer of gold. The
morphology of the MCC and MCC-ZnO hybrids in the rubber matrix
was analysed from SEM photographs, as shown in Fig. 7.
The sizes of the MCC particles in the rubber matrix were very
large, aapproximately 20–90 ␮m, as observed in Fig. 7(a), which
was the main reason for the poor reinforcing efficiency. However,
compared with the MCC vulcanizates, the sizes of the MCC-ZnO
hybrid particles in rubber matrix were decreased to some extent,
 Y. Liang et al. / Carbohydrate Polymers 169 (2017) 324–331
as observed from Fig. 7(b). The decrease in the size of the MCC-
ZnO particles was attributed to the loose structure of the swollen
MCC and strong force field produced during the rubber processing.
The modulus values of the MCC and ZnO loaded on the hybrids were
quite different, so MCC might have disintegrated under the pressure
or shear force during the rubber processing, causing micronization.
Fig. 7(a) and (c) showed that a large portion of the MCC had
been pulled out from the rubber matrix, and the MCC was almost
completely separated from the rubber matrix, which indicated
that the interfacial bonding between the MCC and rubber was
very poor. For the MCC-ZnO samples, the pull-out phenomenon
was decreased (Fig. 7(b)), and the interfacial separation was not
apparent (Fig. 7(d)). Even at the location of the interfacial separa-
tion, adherence phenomenon still existed between the hybrids and
rubber, as shown in Fig. 7(e) and (f). These results demonstrated
that the MCC-ZnO hybrids increased the interfacial interactions
between the MCC and rubber, thereby improving the reinforcing
efficiency.
4. Conclusions
MCC-ZnO hybrid composites were prepared by loading nano-
ZnO onto the surface of MCC using a microreactor technology.
The sizes and morphologies of the loaded ZnO can be sphere-like,
rod-like and tube-like by controlling the thickness of microreactor.
The MCC-ZnO hybrid composites exhibited higher reinforcing effi-
ciency than the pure MCC, and their vulcanziates had improved
wet-skid and rolling resistance performance when used in tires
tread compounds, indicating that the MCC-ZnO hybrids had the
potential to be used in green tire tread compounds. SEM pho-
tographs showed that MCC-ZnO hybrid composites were in situ
micronized during the rubber processing and had improved inter-
facial bonding with rubber matrix.
Acknowledgments
The authors acknowledge financial support through the
National Natural Science Foundation of China (Grant 51372128),
the Zhejiang Key Level 1 Discipline of Forestry Engineering
(2014lygcy014), and the Anhui Province Key Laboratory of
Environment-friendly Polymer Materials.
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