Journal of Polymer Research (2019) 26:44

https://doi.org/10.1007/s10965-019-1710-z

ORIGINAL PAPER

Fabrication, characterization, and application of biocomposites

from poly(lactic acid) with renewable rice husk as reinforcement
Chin-San Wu 1 & Chi-Hui Tsou 2

Received: 9 October 2018 / Accepted: 14 January 2019

# The Polymer Society, Taipei 2019

Abstract
Filaments for three-dimensional printing were fabricated from composites based from biodegradable Poly(lactic Acid) (PLA) and
renewable rice husk (RH). Acrylic acid (AA)-grafted PLA (PLA-g-AA) and coupling agent-treated rice husk (TRH) were
incorporated to improve the properties of PLA/RH biocomposites. The biocomposite morphology, tensile properties, water
absorption, and biodegradability were investigated. PLA-g-AA/TRH demonstrated superior tensile properties than PLA/RH
because of the improved compatibility between the polymer and the TRH. TRH was evenly dispersed in the PLA-g-AA, brought
about by ester reaction; consequently, branched and three-dimensional networks structures were generated. These PLA-g-AA/
TRH biocomposites can be used as biodegradable materials or filaments for 3D printing applications because of their low cost
and excellent properties.

Keywords Poly(lactic acid) (PLA) . Rice husk (RH) . Surface treatment . Coupling agent-treated . Three-dimensional networks
structures . 3D printing application

Introduction residue. Therefore, biodegradable [8] or renewable [9] poly-

Plastics are used in a wide array of products, and their biode-
gradability is a crucial factor in sustainable global develop-
ment [1–3]. They are derived typically from petrochemical
materials because of their extensive availability and low price.
Petrochemical-based plastic products typically do not de-
grade, even after years of storage in landfill, and the cost of
recycling is high. Oil-based plastic products are solid, durable,
and convenient. Plastic waste has become a major environ-
mental pollutant on account of the marked increase in produc-
tion and use of plastic products [4–7]. Biodegradable plastics
have great potential for addressing problems of environmental
pollution, and CO2 emissions arising from the incineration of
plastics can be reduced. When biodegradable plastic waste is
buried in soil, it decomposes with little or no pollution or
* Chi-Hui Tsou
mayko0301@hotmail.com
1
Department of Applied Cosmetology, Kao Yuan University,
Kaohsiung County, Taiwan 82101, Republic of China
2
Material Corrosion and Protection Key Laboratory of Sichuan
Province, College of Materials Science and Engineering, Sichuan
University of Science and Engineering, Zigong 643000, China
mers represent a new generation of environmentally sustain-
able materials [10, 11]. Biodegradable plastics, particularly
those based on Poly(lactic Acid) (PLA), have been developed
extensively. Polycaprolactone (PCL) is one of the biodegrad-
able plastics, as the PCL has excellent biodegradability, but
low melting point and thermostability [12, 13]. Poly(lactic
Acid) (PLA) is polymerized from lactide, and is characterized
by low toxicity, high strength, and outstanding formability; it
is nonirritating and has excellent biocompatibility, which
means that products may biodegrade completely after usage
[14]. The mechanical properties of PLA are similar to those of
polypropylene. These two materials have similar transparency
and processing properties [9, 15]; however, the high cost of
PLA has limited its commercial applications.
Currently, biodegradable plastics are much more expensive
than petrochemical-based plastics. Because of their high price,
biodegradable plastics are commonly mixed with agricultural
waste products that include wheat straw, sugarcane bagasse,
rice husks (RHs), and peanut shells [15–17]. In the present
study, RH was added to a biodegradable plastic to form a com-
posite material. As RH is abundant and hard, it is suitable for
use as polymer reinforcement. Waste RH is typically buried in
soil, and when decomposed, it provides effective fertilization
for plant growth because of the high S and K content [18, 19].
 44 Page 2 of 9 J Polym Res (2019) 26:44

A fused deposition modeling method for three-dimensional used as is. AA and benzoyl peroxide (BPO) were purchased
(3D) printing is presently the most popular type of 3D printing from Sigma-Aldrich Corp. (Milwaukee, WI). BPO was used
for commercial or personal use [20]. In this connection, there as polymerization initiator, purified through dissolution in
is a growing request for filament materials for 3D printing, para-xylene and reprecipitation from methanol. RH was ob-
which has become quite popular [21]. PLA/RH composites tained from a farm in Kaohsiung, Taiwan (R.O.C.).
are excellent products for 3D printing because they are
environment-friendly wood-imitating materials. However,
PLA-g-AA copolymer
the binding force between agricultural waste reinforcements
and biodegradable plastics is weak. Yussuf et al. indicated that
The grafting reaction of AA onto PLA was carried out in a
the flexural strength of PLA decreased from 110 to 85 MPa
round-bottom flask. In a preliminary test using xylene as a
when its RH content was 20% [22]. Tsou et al. [23] reported
solvent, a mixture of AA and BPO was added in four equal
that MDI as a compatibilizer could improve the interfacial
portions to molten PLA at 2-min intervals to allow grafting to
adhesion between PLA and RH; the tensile strength of PLA/
take place. The reactions were performed in a nitrogen (N2)
RH composites (20% RH content) improved from 32.5 to
atmosphere at 60 ± 2 °C. Preliminary experiments showed that
50.6 MPa after the addition of MDI. However, PLA/RH/
equilibrium was attained in less than 12 h. Thus, reactions
MDI composites still had lower tensile strength than neat
were allowed to progress for 12 h with stirring at 60 rpm.
PLA. Therefore, the surface of agricultural waste should be
Samples of 4 g of the product were dissolved in 200 mL of
modified to increase the compatibility between the polymer
refluxing p-xylene at 60 ± 2 °C, and the solution was filtered
and the reinforcement. The modification can be done using an
through several layers of cheesecloth. The xylene-insoluble
acrylic acid (AA) coupling agent that is grafted onto a biode-
product remaining on the cheesecloth was washed with ace-
gradable plastic (PLA-g-AA) to form a compatible interfacial
tone to remove the unreacted AA, and was then dried in a
layer. In the present study, modified agricultural waste effec-
vacuum oven at 80 °C for 24 h. The AA loading of the p-
tively adhered onto the holes of long polymer chains, increas-
xylene-soluble polymer was determined by titration, and
ing the tensile strength of the composite material [24, 25]. This
expressed as the grafting percentage, which was determined
favorable condition enhanced the interfacial adhesion and ten-
using a titration method [26]; the grafting percentage was
sile properties of PLA/RH composites that were converted
approximately 6.26 wt%. The loading of BPO was maintained
into filaments for 3D printing applications.
at 0.3 wt%, and that of and AA was maintained at 10 wt%.

Experimental Processing of treated rice husk

Materials Scheme 1 illustrates the treatment of RH and the preparation of

PLA-g-AA, RH was ground and sorted through 300- and 400-
PLA (95% L-lactide and 5% meso-lactide; molecular weight, mesh sieves; the fine brown powder was then vacuum-dried at
Mw = 9.73 × 104; NatureWorks Corp., Minnetonka, NE) was 85–90 °C until the moisture content was 5 ± 2% (for 12 h).

Grafting

Scheme 1 Reaction scheme detailing processing of treated rice husk (TRH) and grafted polylactic acid (PLA-g-AA), producing filaments for 3D
printing applications
J Polym Res (2019) 26:44
The treated rice husk (TRH) was dissolved in a mixture of
cross-linking agents; the mass ratio of the TRH to cross-
linking agents was 1:8. Then, the mixture was stirred at a rotor
speed of 50 rpm at room temperature for 1 h and allowed to
stand for 2 d. The cross-linking agents were a stoichiometric
solution of tetraethyl orthosilicate or TEOS, water, and lactic
acid catalyst in tetrahydrofuran. The molar ratios were as fol-
lows: lactic acid/TEOS = 0.01; H2O/TEOS = 2.2. Finally, the
cross-linked TRH was dried under vacuum at 108–115 °C for
1 d.
Preparation of composites
First, RH and TRH samples were washed with acetone and
dried in an oven at 105 °C for 24 h. Then, composites were
prepared using an extruder at 185–195 °C. The RH or TRH
content in the hybrid (i.e., PLA/RH or PLA-g-AA/TRH) was
0, 10, 20, 30, and 40 wt%.
Fabrication of filaments for 3D printing
An extruder (Model TUSe194T, Atlas Electric Devices
Company, Chicago, IL, USA) was used to make filaments at
a temperature of 185–195 °C. A specimen (PLA or PLA-g-
AA/20wt%TRH) was loaded into the extruder and heated un-
til molten. The filament diameter was controlled at 1.75 ±
0.04 mm. Scheme 1 depicts the fabrication of filaments for
3D printing applications and provides examples of products
from a composite of PLA-g-AA/20wt%TRH [26, 27].
Characterization and data analysis
Carbon-13 nuclear magnetic resonance (13C NMR) spectra
(Bruker AMX-400 NMR spectrometer, Madison, WI) were ob-
tained at 100 MHz. Power decoupling conditions were set with
90 pulse and at a cycle time of 4 s. Infrared spectra were obtain-
ed using an FTS-7PC Fourier transform infrared (FTIR) spec-
trophotometer (Bio-Rad, Hercules, CA). Transmission spectra
were measured at 2 cm−1 resolution between 400 and 4000 cm−1
with collection time of 1 min. X-ray diffraction (XRD) intensity
(Rigaku D/max) was recorded with a Cu target and Kα (λ =
1.5418 Ǻ) at a rate of 2°/min, an accelerating voltage of 40 kV,
and an applied current ranging from 10 to 50 mA. Melting
curves were recorded over a temperature range of 0–210 °C at
a heating rate of 10 °C min−1 in an N2 atmosphere. Two parallel
specimens were measured in two heating cycles.
Evaluation of mechanical properties
A tester for mechanical properties (Model LR5K; Lloyd
Instruments, Bognor Regis, UK) was used to determine the
tensile strength according to ASTM Standard D638. Test
specimens were prepared in a press at 180 °C and conditioned
Page 3 of 9 44
at a relative humidity of 50 ± 5% for 24 h. Measurements were
made at a crosshead speed of 10 mm min−1. Five specimens
were tested, and mean values were calculated.
Determination of composite morphology
A specimen (150 × 150 × 1 mm3) was prepared using a hy-
draulic press and treated with hot water at 60 °C for 24 h. The
specimen was cut according to ASTM Standard D638. A thin
section of the fractured plane was removed and the remaining
part was coated with gold. The surface morphology was ob-
served through scanning electron microscopy (SEM, model S-
1400; Hitachi, Tokyo, Japan).
Measurement of water absorption
All biocomposites were prepared for the measurement of wa-
ter absorption according to ASTM Standard D570. They were
dried in a vacuum oven at 80 ± 2 °C for 10 h, cooled in a
desiccator, and weighed (W0). Thereafter, they were immersed
in water and kept at 25 ± 2 °C for 20–120 d. Then, the excess
water on the surface of each biocomposite was removed using
a tissue paper, and it was immediately weighed. The weight
average measured for a period of 0–120 d was calculated; this
average weight was designated as W1. The water absorption
(WA) was calculated from the following Eq. (1):
W 1− W 0
WAð%Þ ¼  100 ð1Þ
W0
Assessment of biodegradation
The biodegradability of PLA/RH and PLA-g-AA/TRH com-
posites in soil was evaluated by measuring the weight loss
over time. Composites with a dimension of 50 × 25 ×
0.5 mm3 were weighed before they were buried in alluvial-
type soil obtained from farmland topsoil. The method was
described by Nourbakhsh et al. [28]. Biocomposites were re-
trieved at 20-d intervals, washed in distilled water, dried in a
vacuum oven at 50 ± 2 °C for 2 d, equilibrated in a desiccator
for at least 1 d, and then weighed.
Results and discussion
The following research problems were investigated: (1) vari-
ation in heat of fusion (Tm, and Tg) in the case of AA-grafted
PLA in place of pure PLA in TRH-containing composites, (2)
grafting of AA, and (3) variation of the RH or TRH content.
 44 Page 4 of 9 J Polym Res (2019) 26:44

Spectral data

A strong and broad infrared absorption peak in the RH spec-

trum was found at 3342 cm−1 (Fig. 1a). This peak for TRH
shifted to 3375 cm−1 (Fig. 1b), which is indicative of the
presence of –OH groups in RH and hydrogen bonding in –
OH groups. The degree of hydrogen bonding was weak, be-
cause the absorption peak shifted to a position corresponding
to free –OH groups [29]. Moreover, characteristic absorption
peaks of network bonding for the cross-linking agent were
found at 800–850 cm −1 [30]. A weak peak at 1000–
1150 cm−1 was found for all TRH samples because of the
presence of the asymmetric stretching of Si–O–Si and/or Si–
O–C bonds [31]. The case for Si–O–Si is indicative of the
presence of cross-linking agents (silica) deposited on RH,
whereas that for Si–O–C indicates the occurrence of a con-
densation reaction between cross-linking agents and RH.
Figure 2 represents the FTIR spectra of unmodified and
modified PLA. Characteristic transitions of PLA at 3300–
3680, and 1710–1765 cm−1 appeared in the spectra of PLA
[(a) in Fig. 2] and PLA-g-AA [(b) in Fig. 2]. Two additional
peaks appeared in the spectrum of PLA-g-AA: one at
1711 cm−1, which was assigned to –C=O and the free acid,
and the other in the range of 3200–3680 cm−1, corresponding Fig. 2 FTIR spectra of (a) PLA, (b) PLA-g-AA, (c) PLA/20wt%RH and
to a broad O–H stretching mode. These peaks indicate the (d) PLA-g-AA/20wt%TRH
successful grafting of AA onto PLA [32].
The peak at 3300–3700 cm −1, assigned to the O–H
stretching mode, in the spectrum of composite PLA/ formed through a covalent reaction between the carboxyl
20wt%RH filaments intensified [(c) in Fig. 2], which is attrib- groups from PLA-g-AA and the hydroxyl groups in TRH.
uted to contributions from the O–H group of RH. The FTIR This supposition was validated from the comparison be-
spectrum of composite PLA-g-AA/20wt%TRH filaments [(d) tween the 13C NMR spectra of PLA and PLA-g-AA (Fig. 3a
in Fig. 2] exhibited a peak at 1737 cm−1, which is not present and b). Three peaks, corresponding to C atoms in the unmod-
in composite PLA/20wt%RH filaments. This peak was ified PLA (1: δ = 16.9 ppm; 2: δ = 68.8 ppm; 3: δ =
assigned to the ester group stretching vibration of the copoly- 169.2 ppm). [34]. The 13C NMR spectrum of PLA-g-AA
mer [33]. The composite PLA-g-AA/TRH filaments were showed additional peaks (4: δ = 42.5 ppm; 5: δ = 36.1 ppm;
6: -C=O δ = 175.1 ppm), an evidence that the AA monomer
was covalently bonded onto the PLA molecular chain.
The solid-state 13C NMR spectra of composite PLA/
20wt%RH filaments (Fig. 3c), composite PLA-g-AA/
20wt%TRH filaments (Fig. 3d), and RH (Fig. 3e) were ana-
lyzed. In reference to unmodified composite PLA/RH fila-
ments, extra peaks at δ = 36.1 ppm (4) and δ = 42.5 ppm (5)
were detected in the spectra of composite PLA-g-AA/TRH
filaments. Similar results were observed previously [35], indi-
cating that AA was grafted onto PLA. However, a peak at δ =
175.1 ppm (C=O; 6; Fig. 3b) was absent in composite PLA-g-
AA/20wt%TRH filaments; typically, AA is grafted onto the
PLA molecular chain.
The 13C solid-state and 29Si solid-state NMR spectra of
composite PLA/20wt%RH filaments (Fig. 3c) also exhibited
peaks not observed in neat PLA; these peaks correspond to the
cross-linking agent in TRH (i.e., Q2 δ = −91 to −93 ppm; Q3
Fig. 1 FTIR spectra of (a) rice husk and (b) treated rice husk δ = −97 to −101 ppm, and Q4 δ = −110 to −112 ppm) [36].
J Polym Res (2019) 26:44
Fig. 3 Solid-state 13C NMR spectra of (a) PLA, (b) PLA-g-AA, (c) PLA/
20wt%RH, (d) PLA-g-AA/20wt%TRH, and (e) RH
The 13C solid-state NMR peak 7 (Fig. 3d), found at δ =
176.9 ppm, was attributed to the reaction between AA in
PLA-g-AA and –OH in TRH. These results, together with
the presence of FTIR peaks at 1000–1150 cm −1 and
1737 cm−1, provide further evidence of the reaction of Si–
O–Si and/or Si–O–C, as well as ester groups, through a con-
densation reaction between PLA-g-AA and TRH. The reac-
tion of Si–O–Si/or Si–O–C and ester groups considerably af-
fected the tensile and biodegradation properties of composite
PLA-g-AA/TRH filaments.
X-ray diffraction patterns
Figure 4 represents the XRD patterns of neat PLA, composite
filaments of PLA/20wt%RH and PLA-g-AA/20wt%TRH,
and RH. Neat PLA (Fig. 4a) displayed two peaks at 16.9°
and 19.5° (designated as peaks a and b, respectively), consis-
tent with the earlier study by Aliotta [37]. Three additional
peaks were observed at 15.9°, 22.1°, and 35.2° (designated
as peaks 3, 4, and 5, respectively) for the composite PLA/RH
filaments [38]. The XRD patterns of neat RH also revealed
Page 5 of 9 44
Fig. 4 X-ray diffraction patterns of (a) PLA, (b) PLA/20wt%RH, (c)
PLA-g-AA/20wt%TRH, and (d) RH
peaks at 15.9°, 22.1°, and 35.2° (Fig. 4d). On the basis of the
comparison between the spectra of PLA/RH and RH, peaks c,
d, and e were attributed to the physical dispersion of RH
throughout the PLA matrix. An additional peak was exhibited
at 18.2° (designated as peak f) in the diffraction pattern of
composite PLA-g-AA/TRH filaments (Fig. 4c). This peak,
also identified by Danyadi et al. [39], may be attributed to
the reaction of ester groups.
Morphology and mechanical properties
RH or TRH may be considered a dispersed phase within a
PLA or PLA-g-AA matrix. SEM was used to examine the
surface morphology of composite filaments of PLA/
20wt%RH and PLA-g-AA/20wt%TRH. The SEM image of
PLA/20wt%RH illustrates that RH was unevenly distributed
in the matrix. The poor adhesion is due to the large differences
in the surface energies of the PLA matrix and the RH filler
[40]. Figure 5b reveals a more homogeneous structure of
PLA-g-AA/20wt%TRH, demonstrating a better compatibility
between PLA and TRH (as reinforcement). This improvement
in the interfacial adhesion is attributed to the higher hydrophi-
licity of PLA-g-AA and TRH than PLA and RH, which en-
abled the development of functional groups for the branched
chain of AA from PLA and three-dimensional networks struc-
tures of TRH.
 44 Page 6 of 9 J Polym Res (2019) 26:44

increased slowly as a function of TRH and leveled off at

TRH content >20 wt%. This behavior was attributed to im-
proved dispersion of TRH in the PLA-g-AA matrix, resulting
in the reaction of branch chain of AA from PLA and three-
dimensional networks structures of TRH. The tensile strength
of PLA-g-AA/TRH composites was approximately 12–
33 MPa, which is better than that of PLA/RH composites

Thermal properties

Table 1 summarizes data from DSC heating thermograms on

the heat of fusion (ΔHf) and melting temperature (Tm) of
PLA/RH and PLA-g-AA/TRH composites containing varying
RH or TRH content. Tm decreased with increasing RH or TRH
content for both composites, probably because of the expan-
sion of PLA or PLA-g-AA caused by RH or TRH, which led
to a loose polymer structure. Composite PLA/RH had a higher
Tm than composite PLA-g-AA/TRH. Tg increased with the
RH or TRH content for both composites [41]. This trend
was most likely a result of the reduced space available for
molecular motion [42]. Tg was higher for the PLA-g-AA com-
posite by 4–7 °C, suggesting that the grafting of AA onto PLA
further restricted the molecular motion.
The latent heat of fusion of neat PLA was ΔHf = 36.6 J g−1,
whereas ΔHf = 35.3 J g−1 for PLA-g-AA. PLA-g-AA had
lower ΔHf because of its graft that disturbed the chain struc-
tures of PLA. These results are similar to those previously
reported for composites of polymers and natural fibers [43].

Water absorption [44]

PLA-g-AA/TRH composites had a greater resistance to water

Fig. 5 SEM images of (a) PLA/20wt%RH and (b) PLA-g-AA/
20wt%TRH composites. c Effect of fiber content on tensile strength of
PLA/RH and PLA-g-AA/TRH composites
absorption than PLA/RH composites (Fig. 6). The water re-
sistance of PLA-g-AA/TRH composites was slow; the hydro-
phobicity of TRH was likely enhanced because of its interac-
tion with PLA-g-AA. The percent mass gain for PLA/RH and
PLA-g-AA/TRH over a 120-d test period increased with the
RH or TRH content. As the structure of polymer chains in
these systems was expected to be random, the aforementioned
results were likely due to the decreased chain movement

Table 1 Effect of RH or TRH content on thermal properties of PLA/RH

Figure 5c plots the tensile strength of PLA/RH and PLA-g- and PLA-g-AA/TRH composites
AA/TRH composites as a function of the RH or TRH content.
The tensile strength of neat PLA was 44.8 MPa, which de- RH or TRH (wt%) PLA/RH PLA-g-AA/TRH
creased to 42.2 MPa when it was grafted with AA. The tensile
Tg Tm ΔHf Tg Tm ΔHf
strength of PLA/RH composites markedly decreased with in-
creasing RH content. This decrease was attributed to the lowly 0 57.6 161.5 36.6 57.2 161.0 35.3
dispersion of RH in the PLA matrix. Consequently, such in- 10 58.9 159.1 28.9 63.3 156.5 33.1
compatibility adversely affected the composite tensile 20 60.3 158.0 25.8 66.1 153.1 32.2
strength. However, PLA-g-AA/TRH composites exhibited 30 61.0 157.4 23.9 67.3 152.6 31.6
an increase in tensile strength as a function of the TRH con- 40 61.8 156.9 21.8 68.1 152.2 31.0
tent. The tensile strength of PLA-g-AA/TRH composites
J Polym Res (2019) 26:44
Fig. 6 Percent mass gain resulting from water absorption for PLA, PLA-
g-AA, PLA/RH, and PLA-g-AA/TRH composites
caused by the greater RH content, as well as its hydrophilicity;
hence, adhesion to the hydrophobic PLA was weak. High
water absorption rates enhance biodegradation, which is ben-
eficial for 3D printing applications.
Biodegradation [45] for 3D printing filaments
Variations in morphology as a function of soil burial
period were evaluated for PLA/RH and PLA-g-AA/
TRH 3D printing filaments. Figure 7 shows SEM im-
ages that illustrate the extent of morpholocial changes
of samples obtained after 60 and 120 d of being buried
Fig. 7 SEM morphological
images of (a–c) PLA, (d–f) PLA-
g-AA/20wt%TRH, and (g–i)
PLA/20wt%RH filaments for 3D
printing as function of incubation
period in soil
Page 7 of 9 44
in soil. Composite PLA/20wt%RH 3D printing filaments
(Fig. 7h and i) exhibited randomly distributed pits,
which were larger and deeper than those of composite
PLA-g-AA/20wt%TRH 3D printing filaments (Fig. 7e
and f). These observations indicated that the biodegra-
dation of RH in PLA/20wt%RH 3D printing filaments
increased with time. The disruption of the PLA matrix
became more distinct after 60 d (Fig. 7b). This degra-
dation was consistent with the change in mass of the
PLA matrix as a function of incubation period (Fig. 8),
which reached 12% after only 120 d. The most likely
cause of this weight loss is biodegradation. The SEM
images shown in Fig. 7 indicate that composite PLA-g-AA/
20wt%TRH filaments were more readily degraded than neat
PLA. Moreover, larger pores were apparent in PLA-g-AA/
TRH 3D printing filaments than in PLA/RH 3D printing fila-
ments after 60 and 120 d (Fig. 8e and f), which was indicative
of greater biodegradation. The rate of weight loss of PLA-g-
AA/TRH 3D printing filaments was faster than that of PLA,
exceeding 35% after 120 d (Fig. 8). These results show that
adding TRH to PLA-g-AA improved the biocomposite
biodegradability.
Figure 8 appears the changes in percent mass as a function
of incubation period for PLA/RH and PLA-g-AA/TRH com-
posites buried in soil compost. The weight loss increased with
the RH or TRH content for both composites. Composites with
40 wt% RH or TRH degraded rapidly over the first 60 d,
losing mass equivalent to the RH or TRH content, and showed
a more gradual decrease in mass over the following 60 d.
PLA/RH exhibited a weight loss approximately 6–9 wt%
greater than that for the PLA-g-AA/TRH composite.
 44 Page 8 of 9
Fig. 8 Weight loss of PLA, PLA-g-AA, PLA/RH, and PLA-g-AA/TRH
as function of soil incubation period
Conclusions
We have described the fabrication of composites containing
AA-modified PLA and cross-linked RH. Solid-state 13C
NMR and 29Si NMR analyses provided evidence of conden-
sation reaction in the composites, involving the reaction be-
tween the hydroxyl groups of TRH and the carboxyl groups of
PLA-g-AA. The morphology of PLA-g-AA/TRH composites
illustrated good adhesion between the TRH phase and the
PLA-g-AA matrix. The results of tensile tests indicate better
adhesion between TRH and PLA-g-AA than between RH and
PLA; as such, the tensile properties of the composite mate-
rials, especially the tensile strength, were enhanced. Tg for
PLA-g-AA/TRH was higher than that for PLA/RH, indicating
greater inhibition of molecular motion. The water resistance of
PLA-g-AA/TRH was greater than that of PLA/RH. The de-
gree of biodegradation increased with the RH and TRH con-
tent. When the materials were incubated in soil, the biodegra-
dation rate of PLA-g-AA/TRH was slower than that of PLA/
RH, but higher than that of pure PLA. In conclusion, PLA-g-
AA/TRH composites can be used as biodegradable filaments
for 3D printing because of theirt low cost and great properties.
Acknowledgements The authors would like to thank the National
Science Council (Taipei City, Taiwan, R.O.C.) for the financial support
(MOST 103-2622-E-244 -001 -CC3) and Wuliangye Group Co. Ltd. The
authors also express their appreciation to the National Natural Science
Foundation of China, Apex Nanotek Co. Ltd., the Ratchadapisek
Sompote Fund for Postoctoral Fellowship (Chulalongkon University),
the Sichuan Province Science and Technology Support Program
(19CXRC0081), the Zigong City Science and Technology office
(2017XC16).
Publisher’s Note Springer Nature remains neutral with regard to jurisdictional
claims in published maps and institutional affiliations.
J Polym Res (2019) 26:44
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