J Polym Eng 2017; aop
Chin-San Wu* and Hsin-Tzu Liao
Fabrication, characterization, and application of
polyester/wood flour composites
DOI 10.1515/polyeng-2016-0284
Received August 1, 2016; accepted November 4, 2016
Abstract: The mechanical properties, thermal properties,
antibacterial activity, and fabrication of three-dimensional
(3D) printing strips of composite materials containing
polyhydroxyalkanoate (PHA) and wood flour (WF) were
evaluated. Maleic anhydride (MA)-grafted PHA (PHA-g-
MA) and WF were used to enhance the desired character-
istics of these composites. The PHA-g-MA/WF composites
had better mechanical properties than the PHA/WF com-
posites did. This effect was attributed to a greater compat-
ibility between the grafted polyester and WF. Additionally,
the PHA-g-MA/WF composites provided higher quality 3D
printing strips and were more easily processed because of
ester formation. The water resistance of the PHA-g-MA/
WF composite was greater than that of PHA/WF. Moreo-
ver, WF enhanced the antibacterial activity of the compos-
ites. Composites of PHA-g-MA or PHA containing WF had
better antibacterial activity.
Keywords: 3D printing strips; antibacterial activity; poly-
mer-matrix composites; wood flour.
1 Introduction
Three-dimensional (3D) printing technology arose in
the 1980s and has been gradually used in the field of
rapid prototyping to accelerate commercial product
research and development. It is free of expensive tools,
instruments, and waste materials; 3D printing has been
identified as a key aspect of a new Industrial Revolution
[1–3]. Fused deposition modeling is the most widely used
process for 3D printing strips; it uses acrylonitrile-buta-
diene-styrene, polycarbonate, polyamide, and mixtures
of thermoplastic materials [4–6]. However, most of these
*Corresponding author: Chin-San Wu, Department of Applied
Cosmetology, Kao Yuan University, Kaohsiung County, Taiwan 82101,
Republic of China, e-mail: t50008@cc.kyu.edu.tw
Hsin-Tzu Liao: Department of Applied Cosmetology, Kao Yuan
University, Kaohsiung County, Taiwan 82101, Republic of China
materials are not environmentally friendly. Furthermore,
toxic substances can be released during printing, which
can cause serious harm to the environment and the
human body [7, 8].
In response to the international trends of energy
savings, carbon reduction, and sustainable development,
more environmentally friendly aliphatic polyesters have
been developed; they can be decomposed by microorgan-
isms in the wild after being mixed with CO2, water, and
other harmless residues [9–11]. Among these polyesters,
polyhydroxyalkanoate (PHA) is one of the most promising
because microorganisms are polymerized by β-hydroxyl
eicosanoic acid into aliphatic polyester [12]. This provides
PHA with good biocompatibility, biodegradability, non-
toxicity, processability, and mechanical properties [13, 14].
However, PHA’s high production cost is the main bottle-
neck to its commercialization. Most PHA products cannot
compete with petrochemical plastics in the market, limit-
ing their commercial development and applications. The
linking of PHA with 3D printing technology is one way
to reduce PHA’s cost and increase its added-value. For
example, when PHA/wood flour (WF) composite is made
into 3D printing strips, the value and competitiveness of
the composite are enhanced.
This study used waste WF (Chamaecyparis formosen-
sis) as an additive. Chamaecyparis formosensis is hard,
contains wood alcohol, is moth-proof antibacterial and
deodorizing, and has anticancer properties. It is a valuable
crop for these reasons [15–17]. Chamaecyparis formosensis
is commonly used in buildings, furniture, woodcarvings,
tableware, and other commodities [18, 19], but the manu-
facturing process is accompanied by residues and chips
that cause environmental problems. To reduce the waste
and increase the reuse effectiveness, C. formosensis chips
were ground into WF and mixed with PHA; then, maleic
anhydride (MA) was used as a compatibilizing agent to
enhance the adhesion between PHA and the WF [20]. This
composite was formed into a 3D printing strip, which dif-
fuses the aroma of wood alcohol during the 3D printing
process, thus increasing the added-value of the product.
The waste from this composite strip after 3D printing can
be decomposed by microorganisms in soil by composting
and will not pollute the environment.
Brought to you by | Iowa State University
Authenticated
Download Date | 1/14/17 9:41 AM
2      C.-S. Wu and H.-T. Liao: Polyester/wood flour composites

2 Materials and methods layers of cheesecloth. The dichloromethane-insoluble

2.1 Materials
Commercial-grade PHA (EM 5400F) was obtained from
Shenzhen Ecomann Biotechnology Co., Ltd. (Shenzhen,
China). MA, obtained from Sigma (St. Louis, MO), was
purified before use by recrystallization from chloroform.
Dicumyl peroxide (DCP; Sigma) was used as an initiator
and was purified by dissolution in chloroform and repre-
cipitation in methanol. Other reagents were purified using
conventional methods. WF was obtained from Taiwan.
2.2 M
 A-grafted PHA copolymer
The reaction grafted MA onto PHA (PHA-g-MA). In a pre-
liminary test using dichloromethane as the solvent in
a round-bottomed flask, a mixture of MA and DCP was
added in four equal portions at 2-min intervals to PHA to
allow grafting to take place. The reaction was performed
in a nitrogen (N2) atmosphere at 50 ± 2°C. Preliminary
experiments showed that equilibrium was attained in less
than 12  h. Thus, reactions were allowed to progress for
12 h with stirring at 60 rpm. Samples of 4 g of the product
were dissolved in 200 ml of refluxing dichloromethane
at 50 ± 2°C and the solution was filtered through several
product remaining on the cheesecloth was washed with
acetone to remove the unreacted MA and was then dried
in a vacuum oven at 80°C for 24 h. The MA loading of the
dichloromethane-soluble polymer was determined by
titration and expressed as the grafting percentage [21]. The
grafting percentage was 0.96  wt%. The loadings of DCP
and MA were maintained at 0.3 and 10 wt%, respectively.
2.3 Preparation of WF and its composites
Chamaecyparis formosensis was purchased from the
Taiwan Forestry Bureau. After being cut at a timber mill,
the residual dark brown coarse wood chips were crushed
by a coarse crusher, resulting in 0.2–1.0-cm-long fine
wood chips. These chips were immersed in 1000 ml of dis-
tilled water for 1 day to remove any water-soluble compo-
nents. After filtering, the wood chips were further ground
six times in a high-speed rotary grinder (Yowlin Industrial
Co. Ltd., Taipei, Taiwan) for 10  min and vacuum-dried
at 50–60°C for 1 day. The resulting dry wood chips were
then ground again and sieved through 400- and 500-mesh
sieves and vacuum-dried for at least 12  h at 100–110°C
until the moisture content of the resulting dark brown
WF was 1.0 ± 0.3%. The entire WF processing procedure is
shown in Scheme 1.

WF
Drying at (Wood flour)
100~110°C
1 days
Crushed sieve
analysis

Wood chips

1 days
Wash
Water for
Drying at 1 days
50~60°C
Immerse
in distilled

Scheme 1: Modification of PHA with WF and the preparation of three-dimensional (3D) printing strips.

Brought to you by | Iowa State University

Authenticated
Download Date | 1/14/17 9:41 AM

The WF samples were washed with acetone and dried
in an oven at 100–110°C for 1 day prior to composite prepa-
ration. Composites were prepared in a Brabender (Dayton,
OH, USA) “Plastograph” W50EHT 200-Nm mixer equipped
with a rotor blade. The blends were mixed at 140–150°C for
15 min at a rotor speed of 50 rpm. The WF contents in the
hybrid materials, i.e. PHA/WF and PHA-g-MA/WF, were 0,
10, 20, 30, and 40 wt%. After mixing, the composites were
pressed into thin plates using a hot press and placed in a
dryer for cooling. These thin plates were cut into standard
sample dimensions for further characterization.
2.4 F abrication of 3D printing strips and
products
An extruder (Model TUS-194T; Atlas Electric Devices
Company, Chicago, IL) was used for making the 3D print-
ing strips at a fabrication temperature of 140–150°C and a
screw rotation rate of 50 rpm. A sample (PHA or PHA-g-MA
and their composites) was placed in the single extruder
and heated until it was molten. The sample was slowly
extruded and cooled by a cooling system. The coiler speed
was used to control the diameter of the 3D printing strip
to 1.75 ± 0.05  mm. Scheme 1 shows the fabrication of 3D
printing strips and products from the composite materials.
2.5 Characterization
Solid-state 13C nuclear magnetic resonance (NMR) spectra
were acquired using an AMX-400 NMR spectrometer (Bruker,
Billerica, MA) at 100  MHz under cross-polarization, while
spinning at the magic angle. Power decoupling conditions
were set with a 90° pulse and a 4-s cycle time. A contact time
of 2.0 ms was used. Samples were loaded into 4-mm fused
zirconia tubes and sealed with Kel-FTM caps. Spectra were
obtained at a spinning rate of ca. 4700 Hz. Infrared spectra of
the samples were obtained using an FTS-7PC Fourier-trans-
form infrared (FT-IR) spectrophotometer (Bio-Rad, Hercules,
CA). The spectra were acquired at 2 cm − 1 resolution between
400 and 4000 cm − 1 with collection times of ca. 1 min. X-ray
diffraction (XRD) data were recorded using a D/max 3-V
X-ray diffractometer (Rigaku, Tokyo, Japan) with a Cu target
and Kα radiation at a scanning rate of 2° min − 1.
2.6 Thermal properties
The phase compatibility in the composites was evaluated
using dynamic mechanical analysis (DMA) (Model 2080;
C.-S. Wu and H.-T. Liao: Polyester/wood flour composites      3
TA Instruments, New Castle, DE) operating in film tension
mode. Test specimens were rectangular thin films measuring
25 × 5 × 1 mm3. DMA tests were performed at a frequency of
1 Hz and a strain level of 0.075% under conditions in which
the temperature rose from − 60 to 70°C at a rate of 3°C min − 1.
The glass transition temperature (Tg), melting temperature
(Tm), and heat of fusion (∆Hf) were determined using a dif-
ferential scanning calorimeter (DSC) (Model 2010; TA Instru-
ments). The mass of the specimens ranged from 4–6  mg.
Melting curves were recorded from − 40 to 180°C at a heating
rate of 10°C min − 1. A mechanical tester (Model LR5K; Lloyd
Instruments, Bognor Regis, West Sussex, UK) was used to
measure the tensile strength at failure, in accordance with the
American Society for Testing and Materials (ASTM) Standard
D638. Test samples were prepared using a hydraulic press at
150°C and conditioned at a relative humidity of 50 ± 5% for
24 h prior to taking measurements. Testing was carried out at
a crosshead speed of 10 mm min − 1. Mean values were deter-
mined from the values of five specimens. A thin membrane
of each composite was prepared with a hydraulic press and
heated in a vacuum oven at 60°C for 24 h to obtain samples
with dimensions of 150 × 150 × 1  mm3. Specimens were cut
according to ASTM D638 specifications. Following failure, a
thin section of the fracture plane was removed, coated with
gold and imaged using scanning electron microscopy (SEM;
Model S-1400; Hitachi, Tokyo, Japan) to observe the fracture
surface morphology.
2.7 Water absorption
Samples were prepared for water absorption measurements
by cutting the composites into 45 × 25 mm2 strips (150 ± 5 μm
in thickness) in accordance with ASTM Standard D570. The
samples were dried in a vacuum oven at 50 ± 2°C for 12 h,
cooled in a desiccator, and then immediately weighed to
the nearest 0.001 g. This mass was designated mc. Thereaf-
ter, the samples were immersed in distilled water and main-
tained at 30 ± 2°C for a 120-day period, during which they
were removed from the water at 20-day intervals, gently
blotted with tissue paper to remove excess water from the
surfaces, immediately weighed to the nearest 0.001 g three
times, and then returned to the water. The average of the
mass measured at the 20-day intervals was calculated;
these average masses were designated mw. The percentage
mass increase because of water absorption, mf, which was
calculated to the nearest 0.01% as follows:
mw − mc
%m f = × 100%
mc (1)
Brought to you by | Iowa State University
Authenticated
Download Date | 1/14/17 9:41 AM
4      C.-S. Wu and H.-T. Liao: Polyester/wood flour composites

2.8 Antibacterial assay

Escherichia coli (BCRC10239) was obtained from the Biore-
source Collection and Research Center, Hsinchu, Taiwan.
E. coli was maintained in nutrient broth medium (3 g of
beef extract and 5 g of peptone in 1 l of distilled water, pH
7.0). The samples were incubated at 37 ± 1°C at a relative
humidity of ca. 90%.
The Japanese Industrial Standard JIS Z 2801:2000, a
method typically used to estimate the antibacterial activ-
ity, was used to determine the antibacterial activity of
membranes of PHA or PHA-g-AA and its WF composites
[22]. This method determines the antibacterial index (ABI)
and kill-bacterial index (KBI) according to the following:
ABI = log B − log C (2)

KBI = log A − log C (3) Figure 1: FT-IR spectra of (A) PHA, (B) PHA-g-MA, (C) PHA/WF
(20 wt%), (D) PHA-g-MA/WF (20 wt%), and (E) WF.
where A is the number of bacteria recovered from the
inoculated unfilled WF sample (native PHA or PHA-g-MA)
shoulders observed at 1785 and 1851 cm − 1 for PHA-g-MA.
immediately following inoculation, B is the number of
These features are characteristic of MA groups; similar
bacteria remaining in the inoculated unfilled WF sample
results have been reported previously [23]. The shoulders
after 18 h, and C is the number of bacteria remaining in the
in the spectra represent the anhydride carboxyl groups in
inoculated filled WF sample after 18 h.
the modified polymer, signifying grafting of MA onto PHA.
Changes in the peaks at 2800–3000 cm −1 in Figure 1A–D
were attributed to changes in alkane C-H bonds caused by
2.9 Bacteria inhibition
grafting of MA onto PHA and/or composite formation of
WF with PHA.
Escherichia coli cells were activated in the liquid medium
Peaks at 3200–3700  cm − 1 correspond to the O-H
and then transferred to fresh medium for 18 h of cultiva-
stretching mode of the -OH group of WF; these were more
tion. The samples (100 μl) were then dropped into the
intense in the PHA/WF (20  wt%) composite (Figure 1C)
culture dish. Next, a sterilized triangular glass rod was
and appeared with an extra shoulder at 3286 cm − 1. Further
used to spread the bacteria in the dish. Additionally, the
comparison of the spectra of the PHA/WF (20  wt%) and
specimen (ca. 1.30 cm in diameter and 0.05 cm thick) was
PHA-g-MA/WF (20 wt%) hybrids (Figure 1C and D) revealed
wiped with 75% alcohol for sterilization and placed into
that the vibrational band of the -OH group in WF shifted
a culture dish with clippers. The culture dish edges were
from 3286 to 3221  cm − 1. The above observations demon-
sealed using sealing membrane and placed in an incuba-
strated the existence of strong hetero-associated hydrogen
tor at 37 ± 1°C for 1 day of cultivation to evaluate the bacte-
bonds between carboxylic groups of the PHA-g-MA matrix
rial inhibitory effects.
and saccharide hydroxyl groups of the WF. Notably, the
FT-IR spectrum of the PHA-g-MA/WF (20  wt%) compos-
ite (Figure 1D) exhibited a peak at 1736 cm − 1 that was not

3 Results and discussion
3.1 C
 haracterization of PHA and its
composites
Figure 1A and B shows the FT-IR spectra of unmodified
PHA and PHA-g-MA, respectively. The characteristic transi-
tions of PHA at 3300–3700, 1700–1760, and 500–1500 cm − 1
appeared in the spectra of both polymers, with two extra
present in the FT-IR spectrum of the PHA/WF (20  wt%)
composite. This peak was assigned to the ester carbonyl
stretching vibration of the PHA-g-MA/WF (20 wt%) com-
posite [24]. These data suggest the formation of branched
and cross-linked macromolecules in the PHA-g-MA/WF
composite via covalent bonding of the anhydride car-
boxyl groups in PHA-g-MA with the saccharide hydroxyl
groups of WF. Hence, an interfacial interaction was clearly
evident in PHA-g-MA/WF. The WF spectrum in Figure 1E is
similar to that reported by Zhang et al. [25].

Brought to you by | Iowa State University

Authenticated
Download Date | 1/14/17 9:41 AM
 C.-S. Wu and H.-T. Liao: Polyester/wood flour composites      5

The solid-state 13C NMR spectra of PHA and PHA-g-

MA are shown in Figure 2A and B, respectively. Three
peaks were observed, corresponding to carbon atoms in
the unmodified PHA (1, 6: δ = 169.3; 2: δ = 38.5; 3: δ = 72.0;
4: δ = 26.9; 5: δ = 9.2; 7: δ = 40.9; 8: δ = 67.7; 9: δ = 19.6 ppm)
[26]. The 13C NMR spectrum of PHA-g-MA exhibited addi-
tional peaks (10: δ = 36.1; 11: δ = 42.3; 12: δ = 171.9  ppm).
These peaks confirmed the grafting of MA onto PHA [27].
The 13C NMR spectra of PHA/WF (20  wt%), PHA-g-
MA/WF (20 wt%), and WF are shown in Figure 2C–E. The
spectra of the WF composites are similar to those reported
by Delmotte et  al. [28]. Relative to the unmodified poly-
ester, additional peaks (peaks 10–12, Figure 2B) were
observed in the spectra of composites containing PHA-g-
MA. However, the peak at δ = 171.9 ppm (C=O) (peak 12 of
Figure 2B), which is also typical for MA grafted onto PHA,
was absent in the solid-state spectrum of PHA-g-MA/WF
(20  wt%). This absence is probably because of an addi-
tional condensation reaction between the anhydride car-
boxyl group of MA and the OH group of WF, which caused
the peak at δ = 171.9 ppm to split into two bands (at δ = 175.9
and 178.7  ppm). This additional reaction converted the
-OH groups in the original WF to esters (represented by
peaks 13 and 14 in Figure 2D) and did not occur between
PHA and WF, as indicated by the absence of correspond-
ing peaks in the FT-IR spectrum of PHA/WF (20 wt%) in
Figure 1D. The formation of ester groups significantly
affected the mechanical properties of PHA-g-MA/WF, and
this is discussed in greater detail in the following sections. Figure 2: Solid-state 13C NMR spectra of (A) PHA, (B) PHA-g-MA, (C)
The crystallization properties of neat PHA, PHA/WF PHA/WF (20 wt%), (D) PHA-g-MA/WF (20 wt%), and (E) WF.
(20  wt%), PHA-g-MA/WF (20  wt%), and WF were also
examined by XRD (Figure 3). Similar to the result proposed
by Ribeiro et al. [29], neat PHA (Figure 3A) exhibited seven
peaks at ca. 13.1°, 16.8°, 19.8°, 21.5°, 22.5°, 25.5° and 27.2°.
Comparison of the XRD patterns of neat PHA and the PHA/
WF composite (Figure 3A and B, respectively) indicated
that there was only one extra peak, at about 15.3°, in the
spectrum of the latter, which derived from the structure of
WF [30]. This result revealed that the WF was physically
dispersed in the PHA matrix. Compared with Figure 3B, a
new peak appeared at 18.1° in the XRD pattern of the PHA-
g-MA/WF composite (Figure 3C) [31].

3.2 T
 hermal properties of PHA, PHA-g-MA Figure 3: XRD patterns for (A) PHA, (B) PHA/WF, (C) PHA-g-MA/WF
and its composites and (D) WF.

Figure 4 shows the effects of WF content and mixing time the melt. Therefore, the resulting polymer composite con-
on the melt torque of the PHA/WF and PHA-g-MA/WF tained powdered filler. The torque decreased with increas-
composites. When preparing the PHA/WF or PHA-g-MA/ ing WF content and mixing time and leveled off after 8 min
WF, the polymer was first melted and WF was added to of mixing. The final torque decreased with increasing WF

Brought to you by | Iowa State University

Authenticated
Download Date | 1/14/17 9:41 AM
6      C.-S. Wu and H.-T. Liao: Polyester/wood flour composites

A 1010

E′ (Pa)
WF wt%
109
40
20
20
0
PHA-g-MA/WF 0
PHA/WF
108
– 60 – 40 – 20 0 20 40 60

B
108

E′′ (Pa)
WF wt%
40
Figure 4: Torque values as a function of mixing time for the PHA/WF 20
20
and PHA-g-MA/WF composites for various WF contents. 0
107 0

– 40 – 20 0 20 40 60
content because the melt torque of WF was lower than
that of PHA or PHA-g-MA. Additionally, because of the soft C 2.0
WF wt%
PHA-g-MA/WF
ester groups formed by reaction of PHA-g-MA and WF, the 0
1.5 0 PHA/WF
melt torque of the PHA-g-MA/WF was significantly lower 20
Tan(δ)

than that of the PHA/WF for a given WF content. 1.0

The dynamic mechanical properties of the PHA/WF
and PHA-g-MA/WF composites were measured and used to
evaluate the compatibility of hybrids. Figure 5A–C shows
the variation of the storage modulus (E′), the loss tensile
modulus (E″), and the loss tangent (tan δ) as a function
of temperature for the neat PHA/WF and PHA-g-MA/WF
composites. Regardless of the WF content, E′ (Figure 5A)
decreased whilst E″ (Figure 5B) increased with increasing
temperature, and there existed a transition at ca. – 5 to 3°C
for E″. These phenomena may be related to the Tg of the
PHA, which occurs at this temperature. At the Tg, the heat of
deformation and molecular motions lead to energy dissipa-
tion. Note that the temperature dependences of E′ and E″ for
the PHA-g-MA/WF composites were lower than those for the
PHA/WF composites; i.e. E′ and E″ of the PHA-g-MA blends
remained relatively high over a wide temperature range.
This was attributed to the formation of ester bonds.
Figure 5C shows that tan δ increased sharply at a
particular temperature, which corresponded to the onset
of segmental motion. The temperature of maximum
damping shifted to higher values with increasing WF
content because of the underlying influence of the Tg
of the amorphous phase in the semicrystalline PHA-g-
MA. In the presence of 20 wt% of WF, the peak damping
temperature had shifted by ca. 9.0°C. The shift resulted
from enhanced restriction of the motion of the amor-
phous phase, suggesting increased adhesion between the
polymer and WF in these composites. In the case of the
PHA/WF composites, the tan δ curve generally broadened
20
40
0.5
0.0
– 40 – 20 0 20 40 60
Figure 5: Dynamic viscoelastic behavior of (A) storage modulus (E′),
(B) the loss tensile modulus (E″), and (C) the loss tangent (tan δ) of
PHA/WF and PHA-g-MA/WF composites containing various amounts
of WF.
and decreased in intensity with increasing WF content.
It is clear that the damping temperature of the PHA/WF
composites only slightly increased (by ca. 5.0°C) as the WF
content increased from 0 to 20 wt%, suggesting a smaller
enhancement in the restricted motion of the amorphous
phase of the PHA/WF composites; this related to the poor
compatibility between the WF and PHA phases. Further-
more, these results indicated only a small enhancement
in the restricted motion of the amorphous phase and a
decrease in the chain mobility of the PHA-g-MA/WF com-
posites because of the poor compatibility between the
PHA and WF. The ΔHf, Tm, and Tg of the PHA/WF and PHA-
g-MA/WF composites with different WF contents were
determined using DSC. The results are shown in Figure 6
and Table 1. For both composites, the Tm decreased with
increasing WF content, reflected by the aforementioned
decreasing molecular weight [32]. For the same WF
content, the PHA/WF composite had a higher Tm than did
the PHA-g-MA/WF composite. This trend was consistent

Brought to you by | Iowa State University

Authenticated
Download Date | 1/14/17 9:41 AM
 C.-S. Wu and H.-T. Liao: Polyester/wood flour composites      7

PHA-g-MA/WF were ca. 4–10 J g − 1 higher than those of

PHA/WF, probably because of condensation reactions,
as discussed above. The ΔHf may be used as an indicator
of blend crystallinity. Although the ΔHf of both the PHA/
WF and PHA-g-MA/WF blends decreased with increasing
WF content (Table 1), the extent of the decrease was sig-
nificantly greater in PHA/WF, indicating a lower degree of
crystallinity. These results are similar to those obtained else-
where with composites of polymers and natural fibers [34].

3.3 M
 orphology and mechanical properties
of PHA, PHA-g-MA and their composites

For most composites, effective wetting and uniform dis-

persion of all components in a given matrix, as well as
strong interfacial adhesion between phases, is required
for satisfactory mechanical properties. Here, WF may be
considered as a dispersed phase within the PHA or PHA-
Figure 6: DSC heating thermograms of PHA-g-MA and its blends g-MA matrix. SEM images were acquired to evaluate the
with different contents of WF (A (0 wt%), B (10 wt%), C (20 wt%), morphology of the composite and to examine the tensile
D (30 wt%), and E (40 wt%)). fracture surfaces of PHA/WF (20  wt%) and PHA-g-MA/
WF (20  wt%). The micrographs of PHA/WF (20  wt%)
Table 1: Effect of WF content on the thermal properties of PHA/WF (Figure  6A) revealed that the WF in this composite was
and PHA-g-MA/WF composites.
evenly dispersed throughout the matrix. However, poor
adhesion between the WF and the PHA matrix occurred
WF (wt%) PHA/WF PHA-g-MA/WF
because of the formation of hydrogen bonds within WF
Tg Tm ∆Hf Tg Tm ∆Hf and the difference between the hydrophilicities of PHA
0 − 9.8 136.0 41.3 − 10.0 135.6 40.2 and WF. Poor wetting in these composites was also noted
10 − 7.0 135.1 35.0 − 3.3 134.2 38.9 (Figure 7A), which was attributed to the large difference
20 − 4.9 134.0 29.8 − 0.1 132.9 37.1 in surface energies between the PHA and WF matrix [35].
30 − 4.0 133.1 26.9 0.9 131.6 35.1
The SEM micrograph of PHA-g-MA/WF (20  wt%) shown
40 − 3.1 132.3 23.9 1.6 131.3 33.9
in Figure 7B revealed more uniform adhesion and better
wetting of WF in the PHA-g-MA matrix, as indicated by
with the corresponding torque measurements shown in the complete coverage of PHA-g-MA on the WF and the
Figure 4. The lower melt torque indicated that PHA-g-MA/ removal of both materials when WF was pulled from the
WF was more processable than PHA/WF. On the other bulk. The improved interfacial adhesion was attributed
hand, the Tg increased with increasing WF content for to similar hydrophilicities of PHA-g-MA and WF, which
both PHA/WF and PHA-g-MA/WF. This increase is prob- allowed the formation of bonds between them.
ably a result of the reduced space available for molecular Figure 7C shows the tensile strength at failure as a
motion with increasing WF content in the composites [33]. function of the WF content in the PHA/WF and PHA-g-MA/
The Tg values were higher for the PHA-g-MA composites by WF composites. The tensile strength at failure of neat PHA
approximately 6.5–12.5°C. As comparison with the values was 16.3 MPa and decreased to 15.8 MPa following grafting
examined by the DMA test (Figure 5), it can be seen that with MA. For the PHA/WF composites, the tensile strength
the DMA examinations gave slightly high Tg values due to at failure markedly decreased with increasing WF content
larger and thicker samples. and was attributed to poor dispersion of WF in the PHA
The ΔHf of pure PHA and PHA-g-MA were 41.3 and matrix. The effect of this incompatibility on the mechani-
40.2 J g − 1, respectively. The lower ΔHf of PHA-g-MA is likely cal properties of the composites was substantial. The PHA-
to be because of grafted branches that disrupted the reg- g-MA/WF composites, however, exhibited an increase in
ularity of the chain structures in PHA and increased the tensile strength at failure with increasing WF content,
spacing between polymer chains. The values of ΔHf for reaching saturation at WF > 20  wt%. This behavior was

Brought to you by | Iowa State University

Authenticated
Download Date | 1/14/17 9:41 AM
8      C.-S. Wu and H.-T. Liao: Polyester/wood flour composites
Figure 7: SEM images showing the distribution and wetting of WF
in (A) PHA/WF (20 wt%) and (B) PHA-g-MA/WF (20 wt%) composites.
(C) Effect of WF content on the tensile strength at failure for PHA/WF
and PHA-g-MA/WF composites.
attributed to improved dispersion of WF in the PHA-g-MA
matrix, resulting from the formation of branched or cross-
linked macromolecules. The tensile strength of the PHA-g-
MA/WF composites was ca. 6–18 MPa greater than that of
the PHA/WF composites.
3.4 W
 ater absorption of PHA, PHA-g-MA, and
their composites
At a given fiber content, the PHA-g-MA/WF composites
had greater resistance to water absorption than did the
PHA/WF composites (Figure 8). The water resistance of
Figure 8: Percent mass gain from the absorption of water for PHA,
PHA-g-MA, PHA/WF, and PHA-g-MA/WF composites.
the PHA-g-MA/WF composites was moderate, and it is
probable that the hydrophobicity of WF was enhanced
by interactions with PHA-g-MA. For both PHA/WF and
PHA-g-MA/WF, the percent mass gain over the 120-day
test period increased with increasing WF content. As the
arrangement of the polymer chains in these systems was
expected to be random, the above results were probably
due to decreased chain mobility at high WF contents and
the hydrophilicity of WF, which adhered weakly to the
more hydrophobic PHA matrix.
3.5 A
 ntibacterial activity of PHA, PHA-g-MA,
and its composites
Figure 9 illustrates the antibacterial properties of PHA,
PHA-g-MA, and their composites. Figure 9A shows that the
composites displayed antibacterial zones; pure PHA-g-MA
did not possess antibacterial properties. However, some
micro-antibacterial zones were found with the PHA-g-MA/
WF membrane specimens having 20 wt% WF content. The
antibacterial zone became more apparent with increasing
WF content because of easier detection.
Antibacterial activity was evaluated using clinically
infectious E. coli. Figure 9B shows that when in contact
with PHA or PHA-g-MA, the E. coli cell count increased
with time from 1.36 × 106 to 2.36 × 108 CFU ml − 1 and from
1.36 × 106 to 1.30 × 108 CFU ml − 1, respectively, after incu-
bation at 37°C for 24 h. Conversely, under the same con-
ditions, the bacterial cell count rapidly decreased to
nearly zero when in contact with PHA/WF or PHA-g-MA/
WF membranes containing more than 20  wt% WF. At
20  wt% WF, the onset of E. coli reduction was observed
at 3  h, which was significantly shorter than the ca. 6  h
Brought to you by | Iowa State University
Authenticated
Download Date | 1/14/17 9:41 AM
 C.-S. Wu and H.-T. Liao: Polyester/wood flour composites      9

A corresponding samples of PHA/WF. This antibacterial

effect behavior was enhanced in PLA-g-MA/WF because
the PHA-g-MA is stabilized in a fixed orientation by WF
resulting in bacteria death due to increasing effective con-
centration of WF to bacteria or contacting time elongation.

4 Conclusions
The fabrication, structure, antibacterial activity, and
mechanical and thermal properties of 3D printing strips
made of PHA/WF and PHA-g-MA/WF composites were
PHA
PHA-g-MA investigated. FT-IR, 13C-NMR, and XRD analyses revealed
that condensation reactions occurred between WF
PHA/WF (10 wt%)
PHA-g-MA/WF (10 wt%)
B PHA/WF (20 wt%)
PHA-g-MA/WF (20 wt%) and anhydride carboxylic groups in PHA-g-MA, which
1010 PHA/WF (20 wt%)
resulted in significantly different structures in the two
PHA-g-MA/WF (20 wt%)
Concentration of E. coli (CFU)

109
108 materials. The morphology of the various PHA-g-MA/WF
107 composites was consistent, with good adhesion between
106 the WF phase and the PHA-g-MA matrix. Mechanical
105 tests showed that improved adhesion between WF and
104
PHA-g-MA enhanced the mechanical properties of the
103
102 composite, especially the tensile strength. Although
101 DSC tests revealed that the melting temperatures of both
100 PHA/WF and PHA-g-MA/WF decreased with increasing
0 3 6 9 12 15 18
Exposure time (h) WF content, the PHA-g-MA/WF composites were more
processable because of their lower melting tempera-
Figure 9: Exposure time course of the (A) inhibition zones and (B)
tures. The glass transition temperature of PHA-g-MA/WF
growth of E. coli cells during exposure to PHA or PHA-g-MA and its
composite surfaces.
was higher than that of PHA/WF, indicating more hin-
dered molecular motion. The water resistance of PHA-g-
MA/WF was greater than that of PHA/WF. Antibacterial
onset time observed for the 20 wt% WF composites. This activity was enhanced with the addition of 20  wt% WF
effect is probably because of a difference in WF surface to PHA-g-MA or PHA, resulting in ABI and KBI values of
densities. As noted in Table 2, according to the guidelines more than 8.00 and 6.00, respectively. The antibacte-
set forth by JIS L 1902:1998 and the JAFET, PHA/WF and rial properties of PHA-g-MA/WF were superior to those
PHA-g-MA/WF suppressed the growth of E. coli. Further- of PHA/WF. Thus, the current study demonstrated an
more, all of the samples containing PHA-g-MA/WF exhib- enhancement in the compatibility between PHA and WF,
ited a higher degree of bacterial suppression than did the which resulted in improved antibacterial properties.

Table 2: Effect of WF content on the antibacterial properties of PHA/WF and PHA-g-MA/WF composites.

  PHA/WF   PHA-g-MA/WF
   
10 wt%   20 wt%   40 wt% 10 wt%   20 wt%   40 wt%

A   1.36 × 106   1.36 × 106   1.36 × 106   1.36 × 106   1.36 × 106   1.36 × 106

B   2.36 × 108   2.36 × 108   2.36 × 108   1.30 × 108   1.30 × 108   1.30 × 108
C   4.91 × 103   0   0   2.31 × 103   0   0
ABI   4.68   > 8.37   > 8.37   4.75   > 8.11   > 8.11
KBI   2.44   > 6.13   > 6.13   2.77   > 6.13   > 6.13

A, number of bacteria recovered from the inoculated unfilled WF sample (native PHA or PHA-g-MA) immediately following inoculation;
B, number of bacteria remaining in the inoculated unfilled WF sample after 18 h; C, number of bacteria remaining in the inoculated filled WF
sample after 18 h.

Brought to you by | Iowa State University

Authenticated
Download Date | 1/14/17 9:41 AM
10      C.-S. Wu and H.-T. Liao: Polyester/wood flour composites
Acknowledgments: The authors thank the Ministry of
Science and Technology (Taipei City, Taiwan, R.O.C.) for
financial support (MOST 104-2221-E-244-011-).
References
[1] Stansbury JW, Idacavage MJ. Dent. Mater. 2016, 32, 54–64.
[2] Rayna T, Striukova L. Technol. Forecasting Social Change. 2016,
102, 214–224.
[3] Berman B. Bus. Horiz. 2015, 55, 155–162.
[4] Postiglione G, Natale G, Griffini G, Levi M, Turri S. Composites
Part A 2015, 76, 110–114.
[5] Casavola C, Cazzato A, Moramarco V, Pappalettere C. Mater.
Des. 2016, 90, 453–458.
[6] Ning F, Cong W, Qiu J, Wei J, Wang S. Composites Part B 2015,
80, 369–378.
[7] Nuñez PJ, Rivas A, García-Plaza E, Beamud E, Sanz-Lobera A.
Procedia Eng. 2015, 132, 856–863.
[8] McCullough EJ, Yadavalli VK. J. Mater. Process. Technol. 2013,
213, 947–954.
[9] Terzopoulou ZN, Papageorgiou GZ, Papadopoulou E,
­Athanassiadou E, Alexopoulou E, Bikiaris DN. Ind. Crop Prod.
2015, 68, 60–79.
[10] Bikiaris DN. Polym. Degrad. Stab. 2013, 98, 1908–1928.
[11] Commereuc S, Askanian H, Verney V, Celli A, Marchese P, Berti
C. Polym. Degrad. Stab. 2013, 98, 1321–1328.
[12] Kumar M, Gupta A, Thakur IS. Bioresour. Technol. 2016, 213,
249–256.
[13] Modjinou T, Lemechko P, Babinot J, Versace DL, Langlois V,
Renard E. Eur. Polym. J. 2015, 68, 471–479.
[14] Laycock B, Halley P, Pratt S, Werker A, Lan P. Prog. Polym. Sci.
2013, 38, 536–583.
[15] Imberger KT, Chiu CY. Soil Biol. Biochem. 2002, 34, 711–720.
[16] Pavela R. Ind. Crop Prod. 2015, 76, 174–187.
[17] Hsieh YH, Kuo PM, Chien SC, Shyur LF, Wang SY. Phytomedicine
2007, 14, 675–680.
[18] Obayashi J, Okochi T. Dendrochronologia 2013, 31, 52–57.
[19] Chen Z, Lei Q, He RL, Zhang ZF, Chowdhury AJK. Saudi J. Biol.
Sci. 2016, 23, 142–147.
[20] Wu CS. Polym. Degrad. Stab. 2009, 94, 1076–1084.
[21] Wu CS. Mater. Sci. Eng. C 2015, 48, 310–319.
[22] Wu CS. Mater. Sci. Eng. C 2016, 69, 27–36.
[23] Ma P, Cai X, Lou X, Dong W, Chen M, Lemstra PJ. Polym. Degrad.
Stabil. 2014, 100, 93–100.
[24] Vaidya AA, Gaugler M, Smith DA. Carbohydr. Polym. 2016, 136,
1238–1250.
[25] Zhang K, Zong L, Tan Y, Ji Q, Yun W, Shi R, Xia Y. Carbohydr.
Polym. 2016, 136, 121–127.
[26] Phukon P, Radhapyari K, Konwar BK, Khan R. Mater. Sci. Eng. C
2014, 37, 314–320.
[27] Schoukens G, Martins J, Samyn P. Polymer 2013, 54,
349–362.
[28] Delmotte L, Ganne-Chedeville C, Leban JM, Pizzi A, Pichelin F.
Polym. Degrad. Stab. 2008, 93, 406–412.
[29] Ribeiro PLL, da Silva ACMS, Filho JAM, Druzian JI. Ind. Crop
Prod. 2015, 69. 212–223.
[30] Liu R, Peng Y, Cao J, Chen Y. Compos. Sci. Technol. 2014, 103,
1–7.
[31] Yang Y, Tang Z, Xiong Z, Zhu J. Int. J. Biol. Macromol. 2015, 77,
273–279.
[32] Tnasea EE, Popa ME, Râpa M, Popa O. Agric. Agric. Sci. Proce-
dia 2015, 6, 608–616.
[33] Majhi SK, Nayak SK, Mohanty S, Unnikrishnan L. Int. J. Plast.
Technol. 2010, 14, S57–S75.
[34] Wu CS, Liao HT. Polym. Bull. 2013, 70, 3443–3462.
[35] Abdullah NM, Ahmad I. Fibers Polym. 2013, 14, 584–590.
Brought to you by | Iowa State University
Authenticated
Download Date | 1/14/17 9:41 AM