International Journal of Biological Macromolecules 72 (2015) 855–861

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International Journal of Biological Macromolecules

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

Research Article

Effective dispersion and crosslinking in PVA/cellulose fiber

biocomposites via solid-state mechanochemistry
Yan Niu, Xiaofang Zhang, Xu He, Jiangqi Zhao, Wei Zhang ∗ , Canhui Lu ∗
State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute at Sichuan University, Chengdu 610065, China

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

Article history: A mechanochemical approach to improve the dispersion and the degree of crosslinking between cel-
Received 17 June 2014 lulose fiber and polymer matrix is presented herein to create high performance poly(vinyl alcohol)
Received in revised form 30 August 2014 (PVA)/cellulose biocomposites in a solvent-free and catalyst-free system. During a pan-milling process,
Accepted 22 September 2014
the hydrogen bonds in both cellulose and PVA were effectively broken up, and the released hydroxyl
Available online 7 October 2014
groups could react with succinic anhydride (SA) to form covalent bonds between the two components.
This stress-induced chemical reaction was verified by fourier transform infrared spectroscopy. The reac-
Keywords:
tion kinetics was discussed according to the conversion rate of SA during the pan-milling process. Soxhlet
Biocomposites
Fiber-reinforced composites
extraction with hot water showed that the crosslinked PVA/cellulose retained more PVA in the composites
Mechanical properties due to the homogeneous and heterogeneous crosslinking. Scanning electron microscope images indicated
Thermal properties the dispersion and interfacial interactions between PVA and cellulose were largely improved. The result-
Interface/interphase ing composites exhibited remarkably enhanced mechanical properties. The tensile strength increased
from 8.8 MPa (without mechanochemical treatment) to 18.2 MPa, and elongation at break increased from
76.8 to 361.7% after the treatment. Their thermal stability was also significantly improved.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
Over the past decade, fiber-reinforced polymer composites
are experiencing increased demand in various applications such
as aerospace, vehicles, sport equipment, etc. due to their sig-
nificantly improved strength and toughness over neat polymers.
Several important factors should be addressed to fully realize the
reinforcing potential of the final materials. First, homogeneous fiber
dispersion in a polymer matrix is desirable to reduce unreinforced
region and therefore distribute the load evenly in the composite.
Second, to achieve efficient stress transfer, the interfacial adhesion
between polymer matrix and fiber must be strong enough to pre-
vent the fiber from being pulled out. The covalent bond formation
between polymer matrix and fiber has been a common method to
improve the composite strength [1–3].
In recent years, the use of natural fibers as reinforcements in
polymers has attracted much attention due to the environmen-
tal concern. Cellulose fibers exhibit high mechanical properties
with the maximum macroscopic Young’s modulus (up to 138 GPa)
even higher than those of aluminum (69 GPa) and glass fiber
∗ Corresponding authors. Tel.: +86 28 85460607; fax: +86 28 85402465.
E-mail addresses: weizhang@scu.edu.cn (W. Zhang), canhuilu@263.net (C. Lu).
(69 GPa) [4]. Besides, they also offer a number of other advan-
tages over conventional reinforcing materials, such as low cost,
worldwide availability, biodegradability, and thermal recyclabil-
ity by combustion. Particular attraction is its low density which
leads to high specific mechanical properties [4,5]. These unique
properties have made cellulose an ideal candidate for high per-
formance biocomposites. Various biodegradable polymers, such
as chitosan [6], starch [7], polycaprolactone (PCL) [8,9], poly(3-
hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) [10,11], polylactic
acid (PLA) [12], poly(furfuryl alcohol) (PFA) [13], and polyvinyl alco-
hol (PVA) [14–16] have been explored as potential matrices for
this kind of composites. PVA is the most widely produced water-
soluble synthetic polymer in the world. It is also a versatile polymer
with broad applications due to its biodegradability, biocompatibil-
ity, high tensile strength, excellent adhesive properties, chemical
resistance and gas barrier properties.
Although both cellulose and PVA have plenty of hydroxyl groups
along their molecular chains, direct incorporation of pristine cel-
lulose fibers into PVA matrix cannot produce composites with
good mechanical properties [17]. This is due to the fact that most
hydroxyl groups in cellulose and PVA molecules have already
formed either intra- or inter-molecular hydrogen bonds. There-
fore, it is difficult to form new hydrogen bonds between the
two components by simple mixing, leading to poor interfacial

http://dx.doi.org/10.1016/j.ijbiomac.2014.09.042
0141-8130/© 2014 Elsevier B.V. All rights reserved.
856 Y. Niu et al. / International Journal of Biological Macromolecules 72 (2015) 855–861
adhesion, and deteriorated mechanical performance of the com-
posites. Moreover, the long pristine cellulose fibers can hardly
disperse well within a polymer matrix during conventional com-
posite fabrication processes. This situation is even worse for
the melt processing as the high viscosity of polymers will sup-
press free movement of fibers. As a result, the entangled and
agglomerated cellulose fibers may generate stress-concentrated
points in the composites and further deteriorate their perfor-
mance. Chemical crosslinking in composites is an efficient way
to achieve desired compatibility [18]. Chabba et al. crosslinked
soy flour/flax yarns composites using glutaraldehyde (GA) as the
crosslinking agent to improve the tensile and thermal properties
[19]. Li et al. also used GA to prepare crosslinked chitosan/PVA
blend beads with high mechanical strength [20]. Teramoto et al.
reported that the miscibility and mechanical properties of pul-
lulan/PVA composites were significantly improved after being
crosslinked with glyoxal [21]. More recently, the crosslinking
among cellulose, poly(methyl vinyl ether-co-maleic acid), and
poly(ethylene glycol) was reported [22]. However, all these reac-
tions are solvent based. When organic solvents are used, the
emission of toxic solvents may cause serious pollutions to the envi-
ronment.
Stress-induced reaction, which is also well-known as
mechanochemistry, is an interdisciplinary science based on
mechanics and chemistry. The pulverization of polymers is a
typical process of mechanochemistry [23]. Compared to the con-
ventional solvent-based chemical reactions, this approach appears
to be an energy intensive and environmentally benign technique.
As a heterogeneous solid-phase reaction, several processes may
occur during the mechanochemical synthesis: dispersion of the
components, generation of the contacts between them, the mass
transfer at the contact zones, and chemical reaction. All these pro-
cesses are induced only by the mechanical impact on the mixture of
solid reagents. In fact, mechanochemistry has been widely applied
in metal alloying and for production of inorganic salts. However,
very few organic reactions have been performed via this process,
especially in chemical modification of polymers. Furthermore,
the existing research on polymer pulverization was concentrated
either on improving the dispersion of particles in polymer matrix
[24–27], or solely on the synthetic aspects [28–30]. As far as we
know, taking advantages of the multi-functional mechanochem-
istry to simultaneously realize effective dispersion and sufficient
chemical crosslinking for fabricating high performance composites
has rarely been reported before.
The objective of this investigation is to achieve good disper-
sion of cellulose fibers in PVA matrix while having their interface
covalently crosslinked via solid-state mechanochemistry. A self-
designed pan-mill was used in the present study. The details of
the pan-mill equipment can be found in our previous publica-
tion [31]. Early studies showed that this equipment was much
more efficient for mechano-activation of cellulose compared to
conventional ball-mill, and acetylated cellulose was successfully
synthesized by co-milling of cellulose and acetic anhydride in
solvent- and catalyst-free conditions [31–33]. Succinic anhydride
(SA), a non-toxic solid reactant which is quite stable at room tem-
perature, was utilized as a crosslinking agent to form covalent
bonds between PVA and cellulose through ring-opening esterifi-
cation. After that, the obtained powders were ethanol extracted to
eliminate the residue SA, followed by melt mixing and compression
molding with plasticizers. The crosslinking was verified by fourier
transform infrared spectra (FTIR) and weight loss against water
extraction. The dispersion of cellulose fibers in polymer matrix was
detected using scanning electron microscope (SEM). The mechan-
ical properties and thermal stability of these biocomposites were
investigated and compared with those without mechanochemical
treatment.
2. Material and Methods
2.1. Materials
Polyvinyl alcohol 1799, with a degree of polymerization
1750 ± 50 and a degree of alcoholysis of 99%, was provided by
SINOPEC Sichuan Vinylon Works, China. Analytical grade suc-
cinic anhydride (SA) was purchased from Tianjin Dibo Chemical
Plant, China. Formamide and ethanol were obtained from Chengdu
Kelong Chemical Plant, China. Cellulose fibers were hardwood
pulp fibers with 90% cellulose content. Deionized water was used
throughout this experiment.
2.2. Mechanochemical crosslinking between PVA and cellulose
fibers
The crosslinking between PVA and cellulose was achieved using
SA as a crosslinker through co-milling in the pan-mill. The strong
compressive and shear forces generated by the pan-mill can induce
mechanochemical esterification reaction among the three ingredi-
ents. PVA, cellulose, and SA with a composition of 100:30:13 by
weight were blended using in a high speed laboratory mixer (FW-
100, Beijing, China) at 26,000 rpm for 5 min. The blend was then fed
into a hopper set at the middle of the moving pan. Milled powder
was discharged from the brim of the pans. The discharged powder
was then collected for the next milling cycle. At predetermined
milling cycles (0, 5, 10, 15, 20 cycles, respectively), part of the
milled power was collected for analysis. The milling process was
maintained at ambient temperature with a water cooling system.
The rotating speed of pan-mill was set at 30 rpm under a specific
pressure.
2.3. Melt processing of crosslinked PVA/cellulose fibers composites
The obtained pan-milled powder was ethanol extracted to
remove residual SA prior to being blended with plasticizers.
The plasticizers were prepared by mixing formamide and water
in equal weight. All ingredients (composite powders: plasticiz-
ers = 1:1, by weight) were blended in a laboratory mixer (FW-100,
Beijing, China) at 26,000 rpm for 3 min and sealed for one week
before thermal compounding. The blend was then melt mixed
using a Brabender Plasticorder PL2000 mixing machine (Duisburg,
Germany) at 150 ◦ C and 30 rpm for 10 min. The obtained paste was
kept at ambient condition for 24 h. After that, the paste was filled in
a metal mold (150 mm in diameter and 1 mm in thickness) under
a pressure of 10 MPa at 175 ◦ C for 15 min. For comparison, samples
without mechanochemical treatment were prepared in parallel fol-
lowing the same processing procedures.
2.4. Fourier transform infrared spectroscopy (FTIR) analysis
FTIR spectra were studied with a Nicolet 560 spectrometer
(Nicolet Co., USA), taking 32 scans for each sample with a resolu-
tion of 2 cm−1 , ranging from 400 to 4000 cm−1 . Approximately 2 mg
of pristine cellulose powder (obtained by milling cellulose fibers
with a mortar), neat PVA and crosslinked PVA/cellulose composite
powder (Soxhlet extracted with ethanol for 48 h) were mixed with
200–300 mg KBr, respectively. Pellets of 1 cm in diameter were then
obtained in a standard mold under a pressure of 4 MPa. Both test-
ing samples and KBr were dried before pellet preparation and were
subjected to FTIR analysis immediately.
2.5. Evaluation of reaction degree of SA during pan-milling
The degree of mechanochemical reaction was evaluated by SA
conversion after pan-milling. Unreacted SA can be removed easily
 Y. Niu et al. / International Journal of Biological Macromolecules 72 (2015) 855–861
during Soxhlet extraction with ethanol. Therefore, the SA conver-
sion is expressed in Eq. (1):
 (Wa − Wb )

Conversion rate (%) = 1 − × 100%,
˛Wa
where Wa and Wb represent the dried weight of powder samples
before and after Soxhlet extraction, respectively. ␣ stands for the
SA fraction in the composition.
2.6. Weight loss against water extraction
PVA can be easily dissolved in hot water, whereas crosslinked
PVA only swells under the same condition. Water extraction exper-
iment on samples (after removal of residue SA) was performed to
verify the crosslinking structure in the composite. The weight loss
was calculated by Eq. (2):
 (W − W ) 
c d
Weight loss (%) = × 100%,
Wc
where Wc and Wd represent the dried weight of the powder
samples before and after Soxhlet extraction, respectively.
2.7. Tensile tests
The compression molded sheets were equilibrated in ambi-
ent environment for one week at a relative humidity of 75%. The
dumbbell-shaped specimens were then punched out from the
sheets by a tensile specimen cutter according to ASTM D 15–54 T.
The stress-strain properties were measured by an Instron 5567 Uni-
versal Testing Machine (Instron Co., USA) at a crosshead speed of
50 mm/min. At least five measurements for each composite were
performed.
2.8. Morphology observation
Scanning electron microscope (SEM, model JEOL JSM-5600,
Japan) was used to observe the liquid nitrogen fractured surface
of composites. Prior to SEM evaluation, the samples were sputter-
coated with gold to avoid charging during tests.
2.9. Thermogravimetric analysis
Thermal gravimetric analysis (TGA) was conducted on TA-2000
analyzer (TA Instruments, USA) from room temperature to 600 ◦ C
at a heating rate of 20 ◦ C/min. The measurements were operated
under a nitrogen purge (25 mL/min). All samples were dried in a
vacuum oven at 100 ◦ C for 2 h before the testing. About 5 mg sam-
ples were used in each test.
3. Results and Discussion
3.1. FTIR analysis
It has been reported that acetic anhydride itself is difficult to
react with cellulose before activation which weakens the inter-
and intra-molecular hydrogen bonds [34]. Traditional ways for the
esterification reactions between cellulose and anhydride always
require the use of a large amount of solvents in the presence of cata-
lysts at elevated temperature [35,36]. In this study, the crosslinking
among PVA, cellulose and SA was realized at ambient temperature
via solvent- and catalyst-free mechanochemical reaction. FTIR was
used to verify this chemical reaction. Fig. 1 compares FTIR spectra of
cellulose, PVA and co-milled PVA/cellulose/SA samples. The spec-
trum of PVA/cellulose/SA sample exhibits a less intensive hydroxyl
stretching adsorption peak at 3400 cm−1 . In addition, a new peak
appears at 1725 cm−1 assigned to C O stretching vibration. These
857
(1)
(2)
Fig. 1. FTIR analysis of cellulose, PVA and PVA/cellulose/SA co-milled for 20 cycles.
findings indicate mechanochemical esterification reaction among
PVA, cellulose and SA indeed happened during the pan-milling
process. The absence of peaks at 1850 and 1780 cm−1 of this spec-
trum confirms that the products were free of unreacted SA after
purification. Similar to those multi-component crosslinking reac-
tions in solvent [17,21], the homogeneous chemical crosslinking
between two hydroxyl groups from either PVA or cellulose may also
take place during the solid-state mechanochemical process (see
Fig. 2). It is important to note that the C O absorption peak may not
be responsible merely for ester linkage. As illustrated in Fig. 2, the
monoester derivative with the formed succinyl groups contributes
a portion of the peak. This is because that the monoester derivative
is produced at first when SA reacts with hydroxyl-bearing materi-
als. The resultant carboxyl groups are less reactive as compared to
the corresponding acid anhydride. It is difficult for those carboxyl
groups to be completely converted into ester bonds. This claim was
also supported by Yoshimura et al. who had studied the cotton
cellulose/SA crosslinking system [37].
3.2. Weight loss against water extraction
PVA is a water-soluble polymer, and its solubility depends on
the degree of polymerization (DP) as well as the degree of alcohol-
ysis (DA). The PVA 1799 used in this work is hard to be dissolved in
water except for under heating over 80 ◦ C, owing to its high DP and
DA. During the Soxhlet extraction process, the temperature of sol-
vent water was higher than 90 ◦ C. Therefore, it was easy to dissolve
and remove the uncrosslinked PVA from the composite, leaving
the crosslinked portion swelled. Fig. 3 shows the weight loss of the
samples during the Soxhlet extraction with water. The control sam-
ple without mechanochemical treatment exhibits an almost linear
weight loss as a function of extraction time. This trend is signifi-
cantly reduced for the PVA/cellulose/SA samples. The weight loss
of control sample is 65.2% after 300 min extraction, which means
84.8% of total PVA has been extracted into water, considering PVA
fraction in the composite. On the contrast, the co-milled sample
with SA shows 30.1% weight loss, thereby only 43.1% of total PVA
was extracted. These results strongly confirmed the crosslinking
structure of the material which has prevented extraction of PVA
into water.
3.3. Reaction kinetics
PVA and cellulose cannot be dissolved in ethanol which is a
good solvent for SA. The unreacted SA can be thoroughly removed
from the composite by Soxhlet extraction using ethanol as a solvent
858 Y. Niu et al. / International Journal of Biological Macromolecules 72 (2015) 855–861
Fig. 2. Scheme of the mechanism of the mechanochemical esterification between PVA, cellulose and SA.
while retaining the PVA, cellulose and reacted SA in the composi-
tion. Therefore, it is possible to evaluate the conversion rate of SA
from a comparison of the weight loss after Soxhlet extraction with
initial SA weight. Fig. 4 illustrates the conversion rate of SA dur-
ing the pan-milling process. The conversion rate increased quickly
at the early milling stage, followed by a relatively slow increase.
The conversion rate of SA reached 61.6% after 20 cycles of co-
milling.
The solid-state esterification among PVA, cellulose, and SA
is based on the mechanism of mechanochemical activation of
hydroxyl groups of cellulose and PVA. When cellulose and PVA are
subjected to mechanical forces, their massive hydrogen bond net-
work can be destroyed, releasing highly reactive hydroxyl groups
on the fresh particle surface which are capable to react with SA
even in solvent- and catalyst-free conditions. Moreover, because all
the reactants are in solid form, the esterification thus mainly hap-
pens at the particle surface. In this study, PVA and cellulose after
pan-milling are several to several tens of microns in size [31]. There-
fore, the crosslinking is considered to take place at a macroscopic
phase.
Fig. 3. Weight loss of powder samples of (A) PVA/cellulose (B) Crosslinked
PVA/cellulose during Soxhlet extraction using water as the solvent.
3.4. Mechanical properties of melt processed composites.
A multi-component plasticizer comprised of formamide and
water was adopted for the melt processing of PVA composites [38].
It is well-known that highly crosslinked polymer cannot be melt
processed. However, as indicated above, the crosslinking density
of PVA was not too high since 43.1% PVA could be removed from
the composites after 300 min of water extraction. Therefore, this
composite was still thermoplastically processable in the presence
of plasticizers.
All samples, including PVA, PVA/cellulose, and crosslinked
PVA/cellulose composites were fabricated by melt mixing followed
by compression molding. Their tensile strength (TS), elongation at
break (EL), and modulus were recorded from tensile testing and
summarized in Table 1. It is evident that the direct incorporation
of cellulose fibers into PVA cannot yield high strength composites.
Their TS and EL were significantly lower as compared to those of
PVA, indicating a weak load transfer from the matrix to fibers. How-
ever, their moduli were the highest due to the hardening effect
when the high modulus cellulose fibers were added into soft chain
Fig. 4. Conversion rate of SA as a function of pan-milling cycles.
 Y. Niu et al. / International Journal of Biological Macromolecules 72 (2015) 855–861 859

Table 1
Mechanical properties of PVA and PVA/cellulose composites.

Sample Strength Elongation at Modulus

(MPa) break (%) (MPa)

PVA 14.0 ± 0.5 339.3 ± 10.0 44.7 ± 3.3

PVA/cellulose 8.8 ± 0.6 76.8 ± 7.2 96.3 ± 9.6
Crosslinked PVA/cellulose 18.2 ± 0.8 361.7 ± 22.1 65.7 ± 6.0

polymers such as PVA. The mechanical properties of the compos-

ites were drastically improved after mechanochemical treatment.
The resultant crosslinked PVA/cellulose biocomposites exhibited
TS, EL, and modulus of 18.2 MPa, 361.7% and 65.7 MPa, respec-
tively, demonstrating a remarkably improved performance. It is
interesting to notice the crosslinked composites showed a slightly
increased EL as compared to PVA. This phenomenon seems to be
contradictive to other composites with strengthened interfacial
adhesion as they generally exhibit decreased EL. A possible rea-
son lies on the fact that the mechaochemical reaction also brings
some highly hydrophilic carboxyl groups into the system, retain-
ing more water in the composite. Consequently, a more plasticizing
effect was exhibited, leading to a longer strain. However, this effect
may also reduce the materials’ moduli. Furthermore, the shortened
and less entangled fibers after pan-milling may be responsible for
the decreased moduli as well.

3.5. Morphological observation on the fractured surface of

composites

Fig. 5 gives SEM images of liquid nitrogen fractured surface of

PVA composites. The PVA component exhibited relatively smooth
texture. This was because part of PVA, which had not been
crosslinked, could be melted during compression molding. How-
ever, those regions containing cellulose fibers (identified using
red circles on the images) were much rougher because cellulose
could not be melted. The fiber dispersion and interfacial adhesion
between PVA and cellulose were largely improved by mecha-
nochemical treatment. As shown in Fig. 5(A) for PVA/cellulose
composite made by simple blending, the coarse fractured sur-
face with twisted fiber agglomerates was observed, suggesting
the inferior fibers dispersion and poor adhesion between two
phases. On the contrast, no fiber agglomeration was seen for the
mechanochemically crosslinked composite owing to the excel-
lent mixing and dispersion from pan-milling. The fine cellulose
particles were evenly dispersed in the matrix from the global
view in Fig. 5(B). The cellulose fibers were firmly embed-
Fig. 5. SEM images of liquid nitrogen fractured surface of (A) PVA/cellulose com-
ded in PVA matrix. As indicated in Fig. 5(C), the broken fiber posite by simple blending (B, C) mechanochemically crosslinked PVA/cellulose
cross-section (white dot) together with quite a few PVA fibrils stuck composite.
to fiber surface in response to external forces strongly demonstrate
the favorable interfacial adhesion between PVA and cellulose due to
the covalent crosslinking. The imposed load can be efficiently trans- 3.6. Thermal stability measurements
ferred from matrix to the reinforcing cellulose fibers, and therefore
improved performance could be achieved. The thermal stability of pristine PVA, PVA/cellulose and
For fiber-reinforced composite materials, it is generally crosslinked PVA/cellulose composite were compared through
accepted that fibers with a relatively high aspect ratio are beneficial thermogravimetric analysis (TGA). Both TGA and derivative ther-
for the composites’ physical properties. However, the dispersion of mogravimetric (DTG) curves are provided in Fig. 6. As shown in
fibers in matrix and the adhesion between them are also crucial fac- the figure, PVA experiences two major weight losses in the tem-
tors for an efficient stress transfer. During the mechanochemical perature range of 200-500 ◦ C. The first one begins at 241 ◦ C with
process, the aspect ratio of cellulose fibers is reduced due to the a major degradation peak at 263 ◦ C according DTG curves, which
strong shearing forces [31]. Besides, the molecular weight of the mainly involves dehydration and formation of some volatile prod-
milled matter can be degraded, which worsens its mechanical prop- ucts. The other one starts at 418 ◦ C, which involves the degradation
erties [39,40]. However, our results did reveal positive effects of of polyene residue to yield carbon and hydrocarbon [41]. Both
mechanochemical treatment. The excellent fiber dispersion and PVA/cellulose and crosslinked PVA/cellulose composites show a
the crosslinking structure could compensate the negative influence relatively slow weight loss before the major degradation, owing to
from milling and yield products with improved performance. the evaporation of plasticizer in the composite. A higher weight loss
860 Y. Niu et al. / International Journal of Biological Macromolecules 72 (2015) 855–861
Fig. 6. TGA and DTG curves for pristine PVA, PVA/cellulose and crosslinked
PVA/cellulose.
is recorded for the crosslinked sample in this stage. As discussed
above, the presence of carboxyl groups can retain more water in
composition, which corresponds to the greater weight loss. The
onset temperature for major degradation of PVA/cellulose is 291 ◦ C
with the major degradation peak at 329 ◦ C, whereas these values
are 307 and 340 ◦ C for the crosslinked PVA/cellulose composite,
respectively. The results indicate that the incorporation of cellu-
lose into PVA could remarkably enhance the thermal stability of
final composites. This is in accordance with previous report on cel-
lulose/PVA composite films [41]. In addition, the results also show
that chemical crosslinking in PVA/cellulose composites can further
improve their thermal stability. Such phenomena have been discov-
ered in crosslinked PVA/TiO2 composites too [42]. It is worth noting
that the crosslinked composite yielded significantly higher amount
of carbon residues after testing. Previously, other crosslinked PVA
composites were also reported to have more carbon residues than
the uncrosslinked ones [42,43].
4. Conclusions
The potential property improvement of any composites depends
on the degree of dispersion and the bonding ability between
matrix and reinforcing phase. To realize good dispersion and
strong bonding, the mechanochemical crosslinking treatment of
PVA/cellulose/SA under solvent-free and catalyst-free conditions
was reported herein. As expected, the chemical crosslinking with
SA happened when the hydroxyl groups in cellulose and PVA
were mechanochemically activated by the compressive and shear
forces. Meanwhile, the pulverization process could distribute cel-
lulose fibers homogeneously in the polymer matrix. The cutting
of cellulose fibers during milling eliminated entanglement and
agglomeration of long fibers. In addition, it produced a large spe-
cific surface area which was favorable for a stronger interfacial
interaction. The obtained biocomposites exhibited highly enhanced
mechanical properties together with significantly improved ther-
mal stability.
Acknowledgements
The authors would like to thank National Natural Science Foun-
dation of China (51303112, 51473100 and 51433006) and Young
Scholar Foundation of Sichuan University (2012SCU11074) for
financial support of this work.
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