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polymers

Article
The Dispersion of Pulp-Fiber in High-Density
Polyethylene via Different Fabrication Processes
Xiaohui Yang 1 , Guangzhao Wang 1 , Menghe Miao 2 , Jinquan Yue 1 , Jianxiu Hao 1
and Weihong Wang 1, *
1 Key Lab of Bio-based Material Science Technology of Education Ministry, Northeast Forestry University,
Harbin 150040, China; xiaohuiyang90@163.com (X.Y.); guangzhaowang1@163.com (G.W.);
yuejinq@163.com (J.Y.); jianxiuhao2016@163.com (J.H.)
2 CSIRO Manufacturing, 75 Pigdons Road, Waurn Ponds, VIC 3216, Australia; Menghe.Miao@csiro.au
* Correspondence: weihongwang2001@nefu.edu.cn; Tel.: +86-451-8219-2145

Received: 13 December 2017; Accepted: 24 January 2018; Published: 26 January 2018

Abstract: In this study, a pulp beating machine was used to premix the pulp fibers with high density
polyethylene (HDPE) particles in water. The wet or pre-dried pulp fiber/HDPE mixture was then
melt-compounded by a twin screw extruder. For further improving the dispersion of pulp fiber,
some mixture was forced to pass through the twin-screw extruder twice. The resulting mixture was
compression molded to the composite. The fiber distribution was observed by the aid of an optic
and scanning electron microscope. The mechanical and rheological properties and creep resistance of
the composites were characterized. Test results demonstrate that when the wet pulp fiber/HDPE
mixture was subjected to pre-pressing and oven drying prior to extrusion compounding, the resulting
composites exhibited homogeneous fiber distribution, superior flexural property, creep-resistance,
and high storage modulus. Particularly, its flexural strength and modulus were 57% and 222% higher,
respectively, than that of the neat HDPE, while the composites prepared without pre-dried were 19%
and 100% higher, respectively. Drying the wet mixture in advance is more effective than re-passing
through the extruder for improving the fiber dispersion and composite performance.

Keywords: pulp fiber; polyethylene; composites; fiber dispersion; drying

1. Introduction
Natural fibers—Such as hemp, wood, or bamboo—Possess great potential to replace conventional
synthetic fibers (i.e., glass fiber, carbon fiber, etc.) for petroleum-based polymer composites due to their
renewability, biodegradability, low density, as well as the high specific mechanical properties [1–3].
As a product of natural fibers, pulp fibers have an average elastic modulus of 40 GPa, which is higher
than bulk natural fibers (10 GPa) [4]. Pulp fibers are typically finer and more uniform than natural
fibers, so it is possible that there are fewer defects in the composites and it has potentially better
performance [5]. In addition, the discarded polyolefin and paper have become an important part
of the waste stream. Reinforcing polyolefin with paper fibers would be a good choice to recycle
these materials.
Commonly, pulp/thermoplastic composites are prepared by a process consisting of mixing,
melt-compounding, and extrusion or injection. Several options are available for the melt-compounding
of pulp/thermoplastic, including using a twin-screw extruder [6,7], internal mixer [8,9], or multi-kinetic
mixer [10]. In most cases, the pulp fibers were dried before mixing and melt-compounding [11–13].
However, the dried natural fibers in general present low bulk density. A large difference in bulk
densities between pulp fibers and polymer matrix may cause problems in the mixing, such as poor
feeding, bridging, surging, and finally non-uniform dispersion [14,15]. Valente et al. [16] also reported
that it is difficult to mix fluffy paper fibers with polymers that have high viscosity. Owing to the fact

Polymers 2018, 10, 122; doi:10.3390/polym10020122 www.mdpi.com/journal/polymers


Polymers 2018, 10, 122 2 of 13

that fibers agglomerate at 5.5 wt %, a high weight percentage of paper fibers cannot be introduced into
an extruder. The dispersion of pulp fibers in polymer matrix is a difficult task for pulp/thermoplastic
composite fabrication.
Since pulp fibers can be easily separated in water attributable to the polarity of cellulose and are
usually obtained as an aqueous suspension, mixing pulp with thermoplastics component in water
is expected to be an effective approach [17]. However, the liquid medium in pulp/polymer mixture
still needs to be removed before melt-compounding. During the drying process, the contraction of
the fibrils pulls the fibers closer together, promoting the formation of hydrogen bonds between the
pulp fibers [18,19], and leading to fiber re-agglomeration. Some methods have been investigated to
solve this problem. For example, Suzuki et al. [20,21] kneaded refiner-treated never-dried kraft pulp
with powdered polypropylene by a twin-screw extruder at 0 ◦ C. The wet pulp/polymer mixture was
then directly melt-extruded. By the aid of coupling agents, the mechanical properties of the resulting
composites were improved. Other research shifted to compression molding. Du [5] and Thumm
et al. [22] prepared a pulp/polymer mixture in the form of mats after dewatering and followed by
oven-drying. The mats were thermoformed into composites in a match mold.
Another critical factor determining the mechanical properties of composites is the interphase
between reinforcing element and matrix. However, the compatibility between the hydrophilic cellulose
fibers and the hydrophobic matrix—Especially hydrocarbon matrixes such as polypropylene (PP) and
polyethylene (PE)—is poor [23]. The design of an appropriate interphase for efficient stress-transfer
from the matrix to the reinforcements is required [24]. Adding a coupling agent is an effective method.
Maleated polyolefins (MAPP, MAPE, and so on) are the most common coupling agents used to improve
the natural fiber–matrix interface via the chemical interactions of –OH/maleic [25]. Meanwhile, surface
treatment with carbon nanotubes (CNTs) [26], surfactants [27], or chemical modification [28] can also
help disperse the natural fibers within the matrix.
In the present study, MAPE was used to improve the compatibility between the pulp fiber and
high density polyethylene (HDPE) matrix. New methods of dispersing pulp fiber in HDPE matrix
were developed for the preparation of pulp fiber/HDPE composites. The pulp fibers and HDPE
powder were premixed in water. After dewatering, the wet, oven-dried, or prepressed oven-dried
pulp fiber/HDPE mixtures were melt-compounded by a twin-screw extruder. To further improve the
dispersion of pulp fiber in HDPE matrix, part of the pulp fiber/HDPE mixtures was forced to pass
through the twin-screw extruder twice. The effects of these methods on the dispersion of pulp fiber in
HDPE and the properties of the resulted composites are discussed.

2. Materials and Methods

2.1. Materials
Bleached hardwood pulp board was supplied by Mudanjiang Hengfeng Paper Co., Ltd.
(Mudanjiang, China). The length, width and aspect ratio of pulp fiber were 1.0 mm, 20.3 µm, and
49.3, respectively. HDPE (grade: 5000 s; melt flow index: 0.8–1.1 g/10 min at 190 ◦ C; density:
0.949–0.953 g/cm3 ) was purchased from Petro China Daqing Petrochemical Company (Daqing, China).
MAPE (grafting percentage: 0.9%) was obtained from Shanghai Sunny New Technology Development
Co., Ltd. (Shanghai, China). Prior to mixing with pulp fibers, HDPE and MAPE granules were milled
into a powder (80–120 mesh) by using a mill (FZ102, TAISITE, Tianjin, China).

2.2. Dispersion of Pulp Fiber and Preparation of Composites


The pulp board was immersed in water for 24 h and then transferred to a pulping beater (ZQS2-23,
Shanxi University of Science and Technology Machinery Factory, Xian, China). HDPE and MAPE
powders were added in the beater. The mixture was disintegrated until the fibers were fully dispersed
and uniformly mixed with the plastic powders. Following, the pulp fiber/HDPE slurry was dewatered
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wasusing
by dewatered by using
a spin-dryer a spin-dryerLittleswan,
(TT75-S189C, (TT75-S189C,Wuxi,Littleswan,
China) untilWuxi,
theChina)
water until theof
content water content
the mixture
of the mixture
decreased decreased to ~50%.
to ~50%.
To remove
To remove thethe residual
residual water,
water,the
thewet
wetpulp
pulpfiber/HDPE
fiber/HDPE mixture experienced oven drying (O),
twin-screw extruding (TS), or prepressing and oven drying (PO). The mixture was forced to re-pass
through the twin-screw extruder to further improve the dispersion of the pulp fiber in the the HDPE
HDPE
matrix melt-compounding in the twin-screw was conducted at the speed of
melt-compounding in the twin-screw was conducted at the speed of 40 rpm at 145–165 40 rpm at 145–165 °C. ◦As
C.
shown
As shownin Figure 1, different
in Figure fabrication
1, different routes
fabrication prepared
routes pulp
prepared fiber/HDPE
pulp fiber/HDPE compound mixtures.
compound The
mixtures.
weight
The ratioratio
weight of pulp fiber/
of pulp HDPE
fiber/ /MAPE
HDPE was 50/47/3.
/MAPE was 50/47/3.
fiber/HDPE mixture
Method (a): the wet pulp fiber/HDPE mixture waswas dried
dried out ◦ C in an oven. After drying,
out at 80 °C
the separated
the separatedfibers
fiberswere
weretightly
tightlyregrouped
regroupedinto
intoblocks.
blocks. The
The dry
dry blocks
blocks were
were scattered
scattered intointo particles
particles by
by using a pulverizer (HNEB-115K, TAISITE, Tianjin, China). These particles were
using a pulverizer (HNEB-115K, TAISITE, Tianjin, China). These particles were manually forced into a manually forced
into a twin-screw
twin-screw extruderextruder
(Nanjing (Nanjing
Rubber andRubber and
Plastics Plastics Plant,
Machinery Machinery Plant,
Nanjing, Nanjing,
China) China) for
for compounding.
compounding.
The The resulting
resulting mixture was namedmixture
O. was named O.

Figure 1.1.Fabrication
Figure Fabrication processes
processes of pulp
of pulp fiber/HDPE
fiber/HDPE mixture.
mixture. MixtureMixture
O: wet O: wet
pulp pulp fiber/HDPE
fiber/HDPE mixture
mixture
was driedwasby dried
oven. by oven. TS1:
Mixture Mixture
wet TS1:
pulp wet pulp fiber/HDPE
fiber/HDPE mixture
mixture was driedwas dried by twin-screw
by twin-screw extruder.
extruder.TS2:
Mixture Mixture TS2:
TS1 was TS1 was melt-extruded
melt-extruded again.
again. Mixture PO1:Mixture
wet pulpPO1: wet pulpmixture
fiber/HDPE fiber/HDPE mixture
was dried by
was dried by prepressing and oven. Mixture PO2: PO1 was
prepressing and oven. Mixture PO2: PO1 was melt-extruded again. melt-extruded again.

Method (b): without prior drying, the wet pulp fiber/HDPE mixture was manually forced into
Method (b): without prior drying, the wet pulp fiber/HDPE mixture was manually forced into
the twin-screw extruder, and then melt-compounded. Water in the mixture was expected to
the twin-screw extruder, and then melt-compounded. Water in the mixture was expected to evaporate
evaporate during compounding. The resulting mixture was named TS1.
during compounding. The resulting mixture was named TS1.
Method (c): part of mixture TS1 was pulverized into small particles by using the
Method (c): part of mixture TS1 was pulverized into small particles by using the above-mentioned
above-mentioned pulverizer and fed into the twin-screw extruder again. The resulting mixture was
pulverizer and fed into the twin-screw extruder again. The resulting mixture was named TS2.
named TS2.
Method (d): the wet pulp fiber/HDPE mixture was manually torn into small pieces (diameter:
Method (d): the wet pulp fiber/HDPE mixture was manually torn into small pieces (diameter:
~8 mm). These pieces were pressed into slices with a thickness of 3 mm under 10 MPa at 105 ◦ C
~8 mm). These pieces were pressed into slices with a◦ thickness of 3 mm under 10 MPa at 105 °C for 5
for 5 min. The slices were then oven-dried at 80 C. The dried mixture slices were fed into the
min. The slices were then oven-dried at 80 °C. The dried mixture slices were fed into the extruder. By
extruder. By this method, the dried mixture can be smoothly fed into the twin-screw extruder without
this method, the dried mixture can be smoothly fed into the twin-screw extruder without
enforcement. The resulting mixture was named PO1.
enforcement. The resulting mixture was named PO1.
Method (e): part of mixture PO1 was pulverized into small particles and fed into the twin-screw
Method (e): part of mixture PO1 was pulverized into small particles and fed into the twin-screw
extruder again. The resulting mixture was named PO2.
extruder again. The resulting mixture was named PO2.
The five pulp fiber/HDPE mixtures from the above routes were reduced to small particles by
The five pulp fiber/HDPE mixtures from the above routes were reduced to small particles by
using the pulverizer mentioned above. These particles were compression molded at 165 ◦ C and 15 MPa
using the pulverizer mentioned above. These particles were compression molded at 165 °C and 15
for 10 min to obtain 4 mm thick composite sheets. The composites were named O, TS1, TS2, PO1,
MPa for 10 min to obtain 4 mm thick composite sheets. The composites were named O, TS1, TS2,
and PO2, respectively corresponding to the mixtures. For comparison, the pure HDPE sheet was also
PO1, and PO2, respectively corresponding to the mixtures. For comparison, the pure HDPE sheet
prepared at the same compression molding conditions.
was also prepared at the same compression molding conditions.
Polymers 2018, 10, 122 4 of 13

2.3. Mechanical Property Test


Samples were stored at 50% RH at room temperature for 48 h before being tested. Mechanical
property measurements were performed on specimens at room temperature (relative humidity: ~50%).
At least six specimens were tested from each sample.
Flexural tests were performed in accordance with ASTM D 790-03, “Standard Test Methods
for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials”,
on 80 × 13 × 4 mm (span length: 64 mm) specimens. A loading speed of 2 mm/min was used
during testing.
The unnotched impact strength was determined in accordance with a Chinese standard GB/T
1043.1-2008 (Plastics, Determination of Charpy Impact Properties, Part 1: Non-instrumented Impact
Test). A striking velocity of 2.9 m/s and pendulum energy of 2 J were employed to test the specimens,
which had dimensions of 80 × 10 × 4 mm (span length: 60 mm).

2.4. Morphological Analysis


The quantification of the pulp fiber macro-dispersion in the HDPE matrix was performed by
optical image. The thickness of sample was 0.5 mm. The state of dispersion was determined by
analyzing the remaining, white appearing fiber agglomerates in the recorded image. The agglomerate
area ratio was calculated by the Image J software (NIH, Bethesda, MD, USA). At least five individual
recorded images were used for the calculations.
The fiber length distributions and damage assessments of fibers in composite samples were
determined after extraction with xylene. The images of the fibers were captured by a light optical
microscopy and the fiber length was measured by the Image J software. At least 500 individual
recorded fibers were measured for one sample.
A scanning electron microscope (SEM, FEI Quanta 200, Hillsboro, OR, USA) was used to
characterize the morphology of paper pulp/HDPE composite. The cross sections of the samples
were sputter-coated with gold and subsequently observed in SEM.

2.5. Dynamic Rheological Properties


An AR2000ex rheometer (TA Instruments, New Castle, DE, USA) was used to determine the
rheological properties of the pulp fiber/HDPE composite. A 25 × 3 mm (diameter × thickness) sample
was clamped using a pair of parallel stainless plates (diameter: 25 mm), separated by a target working
distance of 3 mm. The test was run at 180 ◦ C and a frequency sweep pattern of 1–600 rad/s.

2.6. Short-Time Creep-Recovery Test


The short-time creep-recovery test of rectangular 52 × 10 × 3 mm composite samples was
performed in torsion mode using the rheometer mentioned above. The samples were mounted on the
sample holder (span: 40 mm), and the chamber temperature was maintained at 30 ◦ C during testing.
An isothermal creep test was run under 0.5 MPa for 30 min. The sample was then unloaded, and the
strain (of the sample) was continuously recorded for 30 min.

2.7. Statistics
Significant differences (α = 0.05) between the different methodologies were determined via
analysis of the variance.

3. Results and Discussion

3.1. Morphology of the Composites


As shown in Figure 2, the composite TS1 showed significant agglomeration of fibers.
The agglomerate area ratio (abbreviated as AA ) of composite TS1 was 69.6%. After dewatering,
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theextruding
wet pulpatfibers highformed a looseinblock
temperature wrapped with
the twin-screw, HDPE
water powders.
in pulp fibers When
quicklytheevaporated.
wet mixture The
experienced extruding at high temperature in the twin-screw, water in pulp
water evaporation promoted the formation of direct hydrogen bonds between the fibers, which fibers quickly evaporated.
The water evaporation
resulted promoted the
in fiber agglomeration. In formation of direct
addition, water hydrogenmight
evaporation bondsform
between the fibers,
a water vapor which
layer on
resulted in fiber
the surface of agglomeration.
pulp fiber, serving In addition, water evaporation
as a protection from shear mighteffect form
during a water vapor layer[29].
melt compound on theThis
surface of pulp fiber, serving as a protection from shear effect during melt
water vapor layer also slowed down HDPE melting and penetrating into pulp fibers during the compound [29]. This water
vapor
entire layer also slowed
extrusion process.down HDPEthe
Therefore, melting and TS1
composite penetrating
exhibitedinto pulp fibers
extremely poor during the entire
fiber distribution.
extrusion process. Therefore, the composite TS1 exhibited extremely poor fiber
When the wet pulp fiber/HDPE mixture was oven dried prior to the extrusion of compound, distribution.
most WhenHDPE the particles
wet pulpwere fiber/HDPE
embedded mixture
in pulpwas ovenThis
fibers. driedis prior to thetoextrusion
beneficial prevent the of compound,
formation of
most HDPE particles
hydrogen bond between were embedded in pulp
the pulp fibers. Onfibers.
the otherThishand,
is beneficial
the driedto pulp
prevent theare
fibers formation of
more brittle
hydrogen bond between the pulp fibers. On the other hand, the dried pulp fibers
than wet fibers, which is advantageous for the dispersion of fibers in matrix. Thus, the resulting are more brittle than
wet fibers, which
composite (i.e.,isO)
advantageous for the
exhibits a better dispersionof
distribution of fibers
fibers than
in matrix. Thus, the
TS1 (Figure 2).resulting
The AA of composite
composite
(i.e., O) exhibits
decreased from a better
69.6%distribution of fibers than
to 11.7%. However, TS1oven
during (Figure 2). The
drying, someAA HDPE
of composite
powders decreased
detached from
from
69.6% to
the fibers.11.7%. However, during oven drying, some HDPE powders detached from the fibers.

Figure 2. (a) Optic photos of neat HDPE and pulp fiber/HDPE composites. The thickness of sample
Figure
is 0.5 mm.2. (a) Optic
Scale barphotos
was 5 of neat(b)
mm. HDPE and pulp fiber/HDPE
Agglomerate composites. as
area ratio (abbreviated TheAthickness ofsample.
A ) of each sample is
0.5 mm. O:
Composite Scale bar was
wet pulp 5 mm. (b)
fiber/HDPE Agglomerate
mixture was dried area ratioComposite
by oven. (abbreviated
TS1: as A) offiber/HDPE
wetApulp each sample.
Composite
mixture O: wet
was dried pulp fiber/HDPE
by twin-screw extruder.mixture was TS2:
Composite dried by oven.
mixture Composite
TS1 was TS1: wet
melt-extruded pulp
again.
Composite PO1:mixture
fiber/HDPE wet pulpwas
fiber/HDPE
dried bymixture was dried
twin-screw by prepressing
extruder. and TS2:
Composite oven. mixture
Composite PO2:
TS1 was
mixture PO1 was again.
melt-extruded melt-extruded again.
Composite PO1: wet pulp fiber/HDPE mixture was dried by prepressing and
oven. Composite PO2: mixture PO1 was melt-extruded again.
For composite PO1, the wet pulp fiber/HDPE mixture was reduced into small pieces and then
For composite
experienced PO1, the and
hot pre-pressing wet oven
pulp fiber/HDPE mixture was
drying. Pre-pressing reduced into
embedded HDPE small pieces and
powders then
tightly
experienced hot pre-pressing and oven drying. Pre-pressing embedded HDPE powders
between the pulp fibers, and few HDPE powders detached from the mixture during the subsequent tightly
between
oven dryingthe pulp fibers,
process. Thus, and
pulpfew HDPE
fibers werepowders detached
effectively from
separated bythe mixture
HDPE during
particles. theshould
This subsequent
be
oven drying process. Thus, pulp fibers were effectively separated by HDPE particles. This should
be the main reason for composite PO1 showing better fiber distribution than composite O. The AA
of composite decreased from 11.7% to 4.7%.
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the main reason for composite PO1 showing better fiber distribution than composite O. The AA of
composite decreased from
The composites TS2 (A11.7% to 4.7%.
A = 13.3%) and PO2 (AA = 0.7%) present less fiber agglomeration than
The
TS1 (A composites TS2 (A (A=A 13.3%)
A = 69.6%) and PO1 A = 4.7%),and PO2 (AA =(Figure
respectively 0.7%) present
2). Thisless fiber agglomeration
indicates than TS1
that the dispersion of
(A
pulp = 69.6%) and PO1
A fiber in HDPE could (A A be further improved if the mixture passed through the twin-screwfiber
= 4.7%), respectively (Figure 2). This indicates that the dispersion of pulp and
in HDPE could
pulverizer be further
twice. improved
However, even ifthough
the mixture passed through
the composite TS2 the
weretwin-screw
blendedand pulverizer
twice through twice.
the
However, even though the composite TS2 were blended twice through the twin-screw,
twin-screw, the composite TS2 exhibited a poorer fiber distribution than composite PO1. This the composite TS2
exhibited
indicates athat
poorer fiber distribution
pre-drying than composite
is more effective PO1. This
than repeated indicates that
pulverization pre-drying
and extrusion is compounding
more effective
than repeated
for fiber pulverization and extrusion compounding for fiber dispersion.
dispersion.
The
The SEM images
SEM images inin Figure
Figure 33 show
show that
that HDPE
HDPE does
does not
not penetrate
penetrate intointo agglomerate
agglomerate fibers
fibersininTS1.
TS1.
Most fibers inside lack adhesion or separation, only fibers on the agglomeration contact
Most fibers inside lack adhesion or separation, only fibers on the agglomeration contact the matrix. the matrix.
These
These locations
locations weaken
weaken thethe stress
stress transmission.
transmission. InIn contrast,
contrast, evenly
evenly dispersed
dispersed fibers
fibers inin matrix
matrix inin
composite
composite PO1 possess larger interaction area in matrix than those of agglomerated fibers, which
PO1 possess larger interaction area in matrix than those of agglomerated fibers, which isis
more
more effective
effective for
forstress
stresstransfer
transferfrom
fromthethematrix
matrixtotothe
thereinforcing
reinforcingelements.
elements.

Figure3.3.SEM
Figure SEM images
images of cross
of the the section
cross section
of pulp of pulp fiber/HDPE
fiber/HDPE composites.
composites. The corresponds
The right image right image
to the circled region of left image. Composite TS1: wet pulp fiber/HDPE mixture was driedwas
corresponds to the circled region of left image. Composite TS1: wet pulp fiber/HDPE mixture by
dried by twin-screw
twin-screw extruder. Composite
extruder. Composite PO1: fiber/HDPE
PO1: wet pulp wet pulp fiber/HDPE
mixture wasmixture was
dried by dried by
prepressing
prepressing
and oven. and oven.

3.2. Fiber
3.2. Fiber Damage
Damage
The effect
The effect of
of composite
composite fabrication
fabrication methods
methods on on fiber
fiber damage
damagewaswasexamined.
examined. The The length
length
distribution of fibers extracted from pulp fiber/HDPE composites fabricated by
distribution of fibers extracted from pulp fiber/HDPE composites fabricated by different methodsdifferent methods is
significantly
is significantly changed
changed(Figure
(Figure4).4).ItItreveals
revealsthat
thatcomposite
compositeTS1
TS1 contains
contains more
more fibers above 0.5
fibers above 0.5 mm
mm
(46.7%) compared to O (34.0%) and PO1 (24.1%). This suggests that the wet
(46.7%) compared to O (34.0%) and PO1 (24.1%). This suggests that the wet pulp fiber/HDPE mixture
pulp fiber/HDPE
mixture reduced fiber broken during twin-screw extrusion due to better plasticity, while dry fibers
reduced fiber broken during twin-screw extrusion due to better plasticity, while dry fibers are fragile
are fragile and are easily sheared. Fibers less than 0.175 mm accounted for 58.2% of PO2, which is
and are easily sheared. Fibers less than 0.175 mm accounted for 58.2% of PO2, which is most among
most among these tested methods. This result is closely related with the fiber distribution. The good
these tested methods. This result is closely related with the fiber distribution. The good fiber dispersion
fiber dispersion implies serious fiber damage.
implies serious fiber damage.
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10, xx FOR
FOR PEER
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Figure
Figure4. Fiber length distribution of fibers extracted from pulp fiber/HDPE composites. Composite O:
Figure 4.
4. Fiber
Fiber length
length distribution
distribution of
of fibers
fibers extracted
extracted from
from pulp
pulp fiber/HDPE
fiber/HDPE composites.
composites. Composite
Composite
wetO:
pulp
wet fiber/HDPE
pulp mixture
fiber/HDPE was
mixture dried
was by
dried oven.
by Composite
oven. TS1:
Composite wet
TS1: pulp
wet fiber/HDPE
pulp fiber/HDPE
O: wet pulp fiber/HDPE mixture was dried by oven. Composite TS1: wet pulp fiber/HDPE mixture mixture was
mixture
dried
wasby
was twin-screw
dried
dried by extruder.
by twin-screw
twin-screw Composite
extruder.
extruder. TS2: mixture
Composite
Composite TS2: TS1 was
TS2: mixture
mixture TS1 melt-extruded
TS1 was
was again.
melt-extruded
melt-extruded Composite
again.
again. PO1:
Composite
Composite
wetPO1:
pulp wet pulp
fiber/HDPEfiber/HDPE
mixture mixture
was was
dried bydried by prepressing
prepressing and and
oven. oven. Composite
Composite PO2:
PO1: wet pulp fiber/HDPE mixture was dried by prepressing and oven. Composite PO2: mixture PO2:
mixturemixture
PO1 was
PO1 was
melt-extruded melt-extruded
again.
PO1 was melt-extruded again.
again.

3.3.3.3.
3.3. Mechanical
Mechanical
Mechanical Properties
Propertiesofof
Properties the
ofthe Composites
theComposites
Composites
Figure 55 and Table 11 show
Figure
Figure 5 and and Table
Table 1 show thatthat
show the the
that the flexural
flexural
flexural property
property
property of
of HDPE
of HDPE was was
HDPE was significantly
significantly
significantly improved
improved
improved when
when
when HDPE
HDPE was
was filled
filled with
with pulp
pulp fibers.
fibers. The
The flexural
flexural strength
strength and
and modulus
modulus of
of composites
composites
HDPE was filled with pulp fibers. The flexural strength and modulus of composites manufactured via
manufactured
manufactured via
via different
different drying
drying methods were in
in the following order: PO1
PO1 >is
>O >> TS1,
TS1, which is
different drying methods were in themethods
following were
order: the following
PO1 order:
> O > TS1, which O
consistent which
withisthe
consistent with
with the
consistenthomogeneity the dispersion
dispersion homogeneity
homogeneity of
of the
the fiber
fiber in
in the composite
the 2).
composite (Figure
(Figure 2).
2). The
The composite
compositethe
dispersion of the fiber in the composite (Figure The composite PO1 displayed
PO1 displayed the highest flexural strength and modulus, 57% and 222% higher, respectively, than
highest flexural strength and modulus, 57% and 222% higher, respectively, than that of the neat than
PO1 displayed the highest flexural strength and modulus, 57% and 222% higher, respectively, HDPE,
that
that of the neat HDPE, while TS1 exhibited 19% and 100% higher, respectively. Theoretically, the
of the neat HDPE, while TS1 exhibited 19% and 100% higher, respectively. Theoretically, the
while
fiber TS1 exhibited 19% and 100% higher, respectively. Theoretically, the fiber damage reduces the
fiber damage
damage reduces
reduces thethe reinforcement
reinforcement effect
effect of
of the
the fibers.
fibers. Nevertheless,
Nevertheless, it it has
has also
also been
been reported
reported
reinforcement
that effect of the fibers. Nevertheless, it has alsomechanical
been reported that good dispersion of the
that good
good dispersion
dispersion of of the
the fibers
fibers could
could improve
improve the the mechanical properties
properties of of the
the composite,
composite,
fibers
thoughcould improve the mechanical properties of the composite, though simultaneously reducing
though simultaneously
simultaneously reducing
reducing the the fiber
fiber length
length [30,31].
[30,31]. As
As shown
shown in in Figures
Figures 33 and
and 4,4, the
the pulp
pulp
thefibers
fiberinlength
PO1 [30,31].
were As shown
damaged more in Figures
severely 3 and
than in O 4,and
theTS1,
pulp fibersthey
though in PO1
were were
evenly damaged more
distributed
fibers in PO1 were damaged more severely than in O and TS1, though they were evenly distributed
severely than in OHDPE
throughout and TS1, though they were evenly distributedassisting
throughoutthe the HDPE transfer
matrix with
throughout the the HDPE matrix
matrix withwith good
good fiber/polymer
fiber/polymer adhesion,
adhesion, assisting in in the efficient
efficient transfer ofof
good
forcefiber/polymer
from the adhesion,
matrix to the
force from the matrix to the fiber. assisting
fiber. in the efficient transfer of force from the matrix to the fiber.

Figure
Figure 5. 5.
Figure 5. Flexural
Flexural
Flexural strength
strength and
strengthand modulus
andmodulus
modulusof of pulp
ofpulp fiber/HDPE
fiber/HDPE composites.
pulpfiber/HDPE composites.Composite
composites. Composite
Composite O: wet
O:O:
wet pulp
wet pulp
pulp
fiber/HDPE
fiber/HDPE mixture
fiber/HDPEmixture
mixturewaswas dried
was dried by
dried by oven. Composite
oven. Composite
by oven. TS1:
CompositeTS1: wet
TS1: pulp
wet
wet fiber/HDPE
pulp
pulp fiber/HDPE
fiber/HDPE mixture was
mixture
mixture dried by
was dried
was dried by
bytwin-screw
twin-screwextruder.
twin-screw extruder.Composite
extruder. CompositeTS2:
Composite TS2:mixture
TS2: mixtureTS1
mixture TS1was
TS1 wasmelt-extruded
was melt-extrudedagain.
melt-extruded again. Composite
again. Composite
Composite PO1:
PO1:
PO1: wet
wet
wet
pulp
pulp
pulp fiber/HDPE
fiber/HDPE mixture
fiber/HDPEmixture was
mixturewas dried
wasdried by
dried by prepressing
prepressing and
by prepressing and oven.
and oven. Composite
oven. CompositePO2:
Composite PO2:mixture
PO2: mixture
mixture PO1
PO1
PO1 was
was
was
melt-extruded
melt-extruded
melt-extruded again.
again.
again.
Polymers 2018, 10, 122 8 of 13

Table Results
Polymers1.2018, of the
10, x FOR analysis
PEER REVIEW of variance for mechanical properties of pulp fiber/HDPE composites.
8 of 12

Table 1. Results of
Composites the analysis
Flexural of variance
strength (MPa)for mechanical
Flexuralproperties
modulus of (GPa)
pulp fiber/HDPE strength (kJ/m2 )
Impactcomposites.
Composites
O Flexural
37.2 ± 0.5 a,b
strength (MPa) Flexural modulus
2.3 ± 0.09 a,b
(GPa) Impact strength 6.8(kJ/m
± 1.02) a,b

TS1 O 37.2 ±
33.0 ± 0.5
0.5 a,b,c
a,b 2.31.8
± 0.09 a,b
± 0.05 a,b,c 11.4 ± 1.4 a,b,c
6.8 ± 1.0 a,b

a,b,ca,c a,c
TS2 TS1 33.0 ± 0.5
41.8 ± 1.3 1.8 ± 0.05 a,b,c
2.3 ± 0.06 11.4 ± 1.4 a,b,c
8.6 ± 1.0 a,c
PO1 TS2 41.8 ± 1.3
43.4 ± 1.3 a,b,d
a,c 2.3 ± 0.06
2.9 ± 0.14a,c a,b,e 8.6 ± 7.0 ± 0.5 a,b,d
1.0 a,c

PO2 PO1 43.4 ± 1.3 2.9 ± 0.14 7.0 ± 0.5


a,b,d
a,d a,b,e a,e a,b,d
39.9 ± 0.7 2.9 ± 0.06 6.0 ± 1.1 a,d
PO2 39.9 ± 0.7 a,d 2.9 ± 0.06 a,e 6.0 ± 1.1 a,d
a Significant for varying fabrication methods; b Significant for varying drying methods; c Significant for the number
a Significant for varying fabrication methods; b Significant for varying drying methods; c Significant
of times passed through the twin-screw extruder for TS; d Significant for the number of times passed through the
for theextruder
twin-screw number for
of times
PO; epassed through the
Not significant twin-screw
for the number extruder
of times for TS; dthrough
passed Significant
the for the number
twin-screw extruder
for PO.
of times passed through the twin-screw extruder for PO; Not significant for the number of times
e

passed through the twin-screw extruder for PO.

The flexural strength and modulus of TS2 were significantly higher than those of TS1 (Figure 5).
The flexural strength and modulus of TS2 were significantly higher than those of TS1 (Figure 5).
Though both of them were prepared from the un-dried pulp fiber/HDPE mixture before extrusion,
Though both of them were prepared from the un-dried pulp fiber/HDPE mixture before extrusion,
the former
the formerwaswas subjected
subjected to to
extrusion
extrusioncompounding
compounding twice, twice,resulting
resulting in in
thethe improvement
improvement of fiber
of fiber
distribution andand
distribution adhesion
adhesion to to
thethematrix.
matrix.However,
However, the theflexural
flexuralstrength
strength of PO2
of PO2 (39.9
(39.9 MPa) MPa) was lower
was lower
than than
that that
of PO1 (43.4
of PO1 MPa).
(43.4 MPa).The Theprocess
processofof pre-pressing,
pre-pressing, oven ovendrying,
drying, plusplus twin-screw
twin-screw extruding
extruding
(PO1) has dispersed fibers suitably in HDPE. Owing to the shear forces
(PO1) has dispersed fibers suitably in HDPE. Owing to the shear forces acting on the materials, these acting on the materials,
fibersthese
werefibers weredamaged
further further damaged
after two after two rounds
rounds of extrusion
of extrusion and pulverization.
and pulverization.
Fiber drying, mixing, and compounding
Fiber drying, mixing, and compounding with HDPE occurred with HDPE occurred simultaneously
simultaneously during extrusion
during extrusion
for TS, which significantly increased the production efficiency of composite preparation. Compared
for TS, which significantly increased the production efficiency of composite preparation. Compared to
to composite O (37.2 MPa), TS2 displayed higher flexural strength (41.8 MPa), suggesting that the
composite O (37.2 MPa), TS2 displayed higher flexural strength (41.8 MPa), suggesting that the screw
screw drying can be used to replace the time-consuming oven drying for pulp/HDPE composite
drying can be used to replace the time-consuming oven drying for pulp/HDPE composite fabrication.
fabrication.
Compared
Compared to neat HDPE,
to neat HDPE,all pulp
all fiber
pulp reinforced HDPEHDPE
fiber reinforced decreased in impact
decreased strength
in impact (Figure 6),
strength
which (Figure 6), which is adverse to flexural properties. In other words, pulping fiber reinforcement the
is adverse to flexural properties. In other words, pulping fiber reinforcement stiffens
HDPE matrix,
stiffens thebut decreases
HDPE matrix,its buttoughness.
decreases This is in accordance
its toughness. This is in with the results
accordance reported
with in other
the results
reported
research in other
[32,33]. research
The impact [32,33]. of
strength The
TS1impact
was the strength
highest of among
TS1 was the composites
these highest among these6 and
(Figure
Tablecomposites
1). This may (Figure
be due6 and Table
to its poor 1).distribution
This may be of due to itsfibers
pulp poor and
distribution of pulp fibers
weak bonding betweenandpulp
weakfibers
bonding between pulp fibers and HDPE matrix, as shown in Figure 3.
and HDPE matrix, as shown in Figure 3. Voids existed in aggregated fiber bundles. However, these Voids existed in aggregated
fiber bundles. However, these defects could absorb impact energy. The impact strength of TS2 and
defects could absorb impact energy. The impact strength of TS2 and PO2 was lower than that of TS1
PO2 was lower than that of TS1 and PO1, respectively. This is in accordance with the fiber damage.
and PO1, respectively. This is in accordance with the fiber damage. The number of stress concentration
The number of stress concentration points increases with the fiber damage, which leads to a
points increases
decrease with
in the the fiberimpact
unnotched damage, which leads to a decrease in the unnotched impact strength.
strength.

Figure
Figure 6. Impact
6. Impact strength
strength of of pulp
pulp fiber/HDPE composites.
fiber/HDPE composites.The
Theneat
neatHDPE
HDPEwaswas
unbroken. Composite
unbroken. Composite
O: wet pulp fiber/HDPE mixture was dried by oven. Composite TS1: wet pulp
O: wet pulp fiber/HDPE mixture was dried by oven. Composite TS1: wet pulp fiber/HDPEfiber/HDPE mixture
mixture
was dried
was dried by twin-screw
by twin-screw extruder.
extruder. CompositeTS2:
Composite TS2: mixture
mixtureTS1
TS1was
wasmelt-extruded again.
melt-extruded Composite
again. Composite
PO1: wet pulp fiber/HDPE mixture was dried by prepressing and oven. Composite PO2: mixture
PO1: wet pulp fiber/HDPE mixture was dried by prepressing and oven. Composite PO2: mixture PO1
PO1 was melt-extruded again.
was melt-extruded again.
Polymers 2018, 10,
Polymers 2018, 10, 122
x FOR PEER REVIEW 9 of 13
12

3.4. Dynamic Rheological Properties of the Composites


3.4. Dynamic Rheological Properties of the Composites
The storage modulus of all samples increased linearly with the angular frequency. Changing
The storage
the frequency hadmodulus
a greaterofeffect
all samples
on the neatincreased
HDPElinearly
than onwith the the angular frequency.
composites. The storageChanging
modulus
the frequency had a greater effect on the neat HDPE than
of the pulp fiber/HDPE composites was considerably higher than that of the neat HDPEon the composites. The storage(Figure
modulus 7).
of the pulp fiber/HDPE composites was considerably higher than that
The increase of storage modulus means the system changed from viscous to more elastic. This effect of the neat HDPE (Figure 7).
The increase of storage modulus means the system changed from
may be attributed to the mechanical reinforcement of the percolated filler network in the blendviscous to more elastic. This effect
may be attributed
systems. to the mechanical
The micro-scale filler had reinforcement
an impact similar of thetopercolated
the nano-scalefiller network
filler theinmelt-rheology
the blend systems.on a
The micro-scale filler had an impact similar to the nano-scale filler
polymer thermoplastic matrix. As shown in the study done by Liebscher et al. [34], the addition ofthe melt-rheology on a polymer
thermoplastic
CNTs to the blend matrix. As shown
system caused inathe study done
noticeable by Liebscher
increase of storage et al. [34], the
modulus ataddition of CNTs to the
lower frequencies.
blendThesystem caused a noticeable increase of storage modulus at lower
complex viscosity of both neat HDPE and pulp fiber/HDPE composites decreased with the frequencies.
The complex
increase of angular viscosity
frequency, of both neat HDPE
signifying that aand
shearpulp fiber/HDPE
thinning process composites
occurred decreased
[35]. Changing with the
the
increase
frequency had a greater effect on the composites than on the neat HDPE (Figure 7). This maythe
of angular frequency, signifying that a shear thinning process occurred [35]. Changing be
frequency had a greater effect on the composites than on the
attributed to the more significant non-Newtonian pseudoplastic fluid characteristics of the neat HDPE (Figure 7). This may be
attributed
composites. to Owing
the more tosignificant
interactionnon-Newtonian
between the rigid pseudoplastic
fibers, the fluid characteristics
movement of the composites.
of the polymer matrix in
Owing to interaction between the rigid fibers, the
the fiber network is more difficult than in neat polymer [36,37]. movement of the polymer matrix in the fiber network
is moreThedifficult
storagethan modulusin neatandpolymer
complex [36,37].
viscosity of PO1 were higher than that of composites O and
The storage modulus and
TS1; this is possibly owing to the relativelycomplex viscosity
evenofdispersion
PO1 were and higher thancompounding.
better that of composites O and
The evenly
TS1; this is possibly owing to the relatively even dispersion and better
dispersed fibers possessed a larger interaction area in matrix than the agglomerated fibers, and the compounding. The evenly
dispersed fibers possessed
evenly dispersed fibers formed a larger interaction
a more effectivearea in matrix
adhesion withthanHDPEthe agglomerated
matrix. Therefore, fibers,
it and the
is more
evenly dispersed fibers formed a more effective adhesion with HDPE
difficult for the melt polymer to move between the evenly dispersed fibers, resulting in higher matrix. Therefore, it is more
difficult
modulus. for the melt polymer to move between the evenly dispersed fibers, resulting in higher modulus.
Reprocessing
Reprocessing also also played
playedan animportant
importantrole rolein in
thethe rheological
rheological property
property of composite.
of the the composite. The
The storage modulus and complex viscosities of PO1 were higher
storage modulus and complex viscosities of PO1 were higher than that of PO2, respectively. than that of PO2, respectively.
The
The
fibersfibers
in PO2 in PO2 underwent
underwent more more severedamage
severe damagecaused causedbyby the the twice
twice pulverization
pulverization and and
melt-extruding
melt-extruding than those in PO1. Furthermore, the longer fibers in PO1 may form more
than those in PO1. Furthermore, the longer fibers in PO1 may form more stable
stable and
and
complex
complex entanglements,
entanglements,potentiallypotentially hindering
hindering the motion
the motion of theofHDPE chain. The
the HDPE interaction
chain. between
The interaction
shorter fibers (PO2) was more easily disrupted than that between longer
between shorter fibers (PO2) was more easily disrupted than that between longer fibers (PO1), thus fibers (PO1), thus allowing
relatively free motion
allowing relatively of the
free motionpolymer
of the chain and leading
polymer chain and the former
leadingtothe a lower
former storage modulus
to a lower and
storage
smaller
modulus complex
and smallerviscosity.
complex viscosity.

Figure 7. Storage modulus of (a) pulp fiber/HDPE composites and (b) neat HDPE; Complex viscosity
Figure 7. Storage modulus of (a) pulp fiber/HDPE composites and (b) neat HDPE; Complex viscosity
of (c) pulp fiber/HDPE composites and (d) neat HDPE. Composite O: wet pulp fiber/HDPE mixture
of (c) pulp fiber/HDPE composites and (d) neat HDPE. Composite O: wet pulp fiber/HDPE mixture
was dried by oven. Composite TS1: wet pulp fiber/HDPE mixture was dried by twin-screw extruder.
was dried by oven. Composite TS1: wet pulp fiber/HDPE mixture was dried by twin-screw extruder.
Composite TS2: mixture TS1 was melt-extruded again. Composite PO1: wet pulp fiber/HDPE mixture
Composite TS2: mixture TS1 was melt-extruded again. Composite PO1: wet pulp fiber/HDPE
was dried by prepressing and oven. Composite PO2: mixture PO1 was melt-extruded again.
mixture was dried by prepressing and oven. Composite PO2: mixture PO1 was melt-extruded again.
Polymers
Polymers 2018,
2018, 10,
10, x122
FOR PEER REVIEW 10
10 of
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13

On the contrary, the storage modulus and complex viscosity of TS2 were higher than that of
TS1. OnThethe contrary,
mixture of the
TS2storage modulus
experienced twoandpasses
complex of viscosity
extrusionofwith
TS2 were higher than
significantly that offiber
reduced TS1.
The mixture of TS2 experienced two passes of extrusion with significantly
agglomerates. Though the pulp fibers were also damaged when subjected to the second extrusion, reduced fiber agglomerates.
Though
the the pulp
uniform fiberfibers were also
distribution damagedcontributed
positively when subjected moretothan
the second extrusion,
fiber damage the properties
to the uniform fiber of
distribution positively contributed more than fiber damage to the properties
TS2. Similar to PO1, the uniformly dispersed fibers in TS2 had larger contacting surface area with of TS2. Similar to PO1,
the matrix,
uniformly dispersed
resulting fibers shear
in higher in TS2viscosity
had larger andcontacting surface area with the matrix, resulting in
storage modulus.
higher shear viscosity and storage modulus.
3.5. Creep-Recovery Test of the Composites
3.5. Creep-Recovery Test of the Composites
Creep is the continuous accumulation of deflection over time when the material is subjected to
Creepload
a constant is the[38].
continuous
The creep accumulation
resistance isof andeflection
importantover time when
property the material
of material. is subjected
The large creep and to
a constant load [38]. The creep resistance is an important property of material.
residual deformation of material indicate poor creep resistance. The neat HDPE exhibits larger The large creep and
residualand
creep deformation
residual ofdeformation
material indicatethanpoor thecreeppulpresistance. The neat
fiber/HDPE HDPE exhibits
composites (Figurelarger
8). creep
The
and residual deformation than the pulp fiber/HDPE composites (Figure
creep-recovery of pulp fiber/HDPE composites varied between the fabrication methods and was 8). The creep-recovery of
pulp fiber/HDPE composites varied between the fabrication methods and
consistent with their flexural property. The composites with higher flexural modulus presented was consistent with their
flexural
better property.toThe
resistance composites
creep. The creep with higher
and flexural
residual modulusof
deformation presented
compositebetter
PO resistance to creep.
were significantly
The creep
lower thanand residual
that deformation
of composites of composite
O and TS. This is POowing
were significantly lower
to the fact that theythanhadthattight
of composites
adhesion
O and TS. This is owing to the fact that they had tight adhesion between
between pulp fibers and HDPE matrix and exhibited uniform fiber dispersion, limiting pulp fibers and HDPE matrix
the motion
andmatrix
of exhibited uniformand
molecules fiberreduced
dispersion, limiting
defect points thecaused
motion byof matrix
the lack molecules
of matrix andpenetration.
reduced defect In
un-reinforced locations, the matrix behaved like pure HDPE. Thus, the composite TS1behaved
points caused by the lack of matrix penetration. In un-reinforced locations, the matrix showed like the
pure HDPE.
highest strainThus,
and thethe lowest
composite TS1 showed
recovery among the the highest strain andwhich
five composites, the lowest recovery among
is attributable the
to its poor
five composites,
fiber dispersion. which is attributable to its poor fiber dispersion.

Figure 8.
Figure Creep-recovery curves
8. Creep-recovery curvesof
of(a)
(a)pulp
pulpfiber/HDPE
fiber/HDPEcomposites
compositesand
and(b)
(b)neat HDPE.
neat HDPE.Composite O:
Composite
wet pulp fiber/HDPE mixture was dried by oven. Composite TS1: wet pulp fiber/HDPE
O: wet pulp fiber/HDPE mixture was dried by oven. Composite TS1: wet pulp fiber/HDPE mixturemixture was
drieddried
was by twin-screw extruder.
by twin-screw Composite
extruder. TS2: TS2:
Composite mixture TS1 was
mixture TS1 melt-extruded again.
was melt-extruded Composite
again. PO1:
Composite
wet pulp fiber/HDPE mixture was dried by prepressing and oven. Composite PO2: mixture
PO1: wet pulp fiber/HDPE mixture was dried by prepressing and oven. Composite PO2: mixture PO1 was
melt-extruded again.
PO1 was melt-extruded again.

4. Conclusions
4. Conclusions
In this
In this study,
study, several
severalmethods
methodsfor fordispersing
dispersingpulp
pulpfibers
fibersinin HDPE
HDPE matrix
matrix were
were investigated.
investigated. It
It was
was found
found that
that when
when thewet
the wetpulp
pulpfiber/HDPE
fiber/HDPE mixturewas
mixture wasdirectly
directlyfed
fedinto
intoaatwin-screw
twin-screwextruder,
extruder,
the resulting
the resulting composite
composite hadhad significantly
significantly improved
improved flexural
flexural properties,
properties, storage
storage modulus,
modulus, andand the
the
resistance to creep over neat HDPE. A second pass through the extruder and
resistance to creep over neat HDPE. A second pass through the extruder and pulverizer furtherpulverizer further
improved the
improved the fiber
fiber dispersion
dispersion and
and flexural
flexural properties.
properties. Moreover,
Moreover, drying
drying before
before extrusion
extrusion was
was more
more
effective than repassing through the extruder. The best drying method was pre-pressing
repassing through the extruder. The best drying method was pre-pressing followed followed by
oven drying, which resulted in composites with the most uniform fiber dispersion, the
by oven drying, which resulted in composites with the most uniform fiber dispersion, the highest highest flexural
flexural property and storage modulus, and the best resistance to creep. Using this method, the
compound can be fed into the extruder without enforcement.
Polymers 2018, 10, 122 11 of 13

property and storage modulus, and the best resistance to creep. Using this method, the compound can
be fed into the extruder without enforcement.

Acknowledgments: This study was supported by the Fundamental Research Funds for the Central Universities
(2572015AB22 and 2572017ET05), the National Natural Science Foundation of China (31670573) and China
Scholarship Council.
Author Contributions: Xiaohui Yang and Weihong Wang conceived and designed the experiments; Xiaohui Yang
performed the experiments; Guangzhao Wang, Jinquan Yue, and Jianxiu Hao significantly contributed
reagents/materials/analysis tools; Xiaohui Yang wrote the manuscript, with revisions made by Weihong Wang
and Menghe Miao.
Conflicts of Interest: The authors declare no conflict of interest.

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