Journal of Polymer Research (2019) 26:227

https://doi.org/10.1007/s10965-019-1882-6

ORIGINAL PAPER

Preparation and characterization of renewable composites

from Polylactide and Rice husk for 3D printing applications
Chi-Hui Tsou 1,2 & Wei-Hua Yao 3 & Chin-San Wu 4 & Chih-Yuan Tsou 1 & Wei-Song Hung 5,6 & Jui-Chin Chen 3 & Jipeng Guo 1 &
Shuai Yuan 1 & Ehua Wen 1 & Ruo-Yao Wang 5 & Maw-Cheng Sunn 7 & Shi-Chih Liu 7 & Manuel Reyes De Guzman 1

Received: 25 March 2019 / Accepted: 9 August 2019

# The Polymer Society, Taipei 2019

Abstract
Blends of polylactide (PLA) and rice husk (RH) were prepared using a twin-screw extruder and characterized for mechanical
properties, and microstructure. Scanning electron micrographs illustrated the occurrence of phase separation in PLA/RH blends,
leading to poor tensile properties. To strengthen the blend mechanical properties, methylene diphenyl diisocyanate (MDI) was
added as an interfacial compatibilizer, which would improve the tensile strength and notched Izod impact of the composites
containing RH (20–50 wt%). A porous morphology showing several connected voids was observed on the surface of all PLA/RH
and PLA/RH/MDI composites buried in soil for specific periods of time. The size of the voids considerably increased with the
RH content. RH would be an excellent filler, compatibilized with MDI, to enhance the biodegradation and mechanical properties
of the resultant environment-friendly composites for 3D printing applications.

Keywords Polylactide . Rice husk . 3D printing . Mechanical properties . Biodegradation

Introduction nanoplatelet (GNP) and graphene oxide (GO) have been used
as additives in PLA. They cause PLA to deliver higher per-
Polylactide (PLA) is a biodegradable polymer produced from formance in biomedical applications (e.g., tissue engineering
corn starch. PLA exhibits promising properties, but its high and drug transport) [24]. A study on the surface properties of
cost, poor tearing strength, and low toughness restrict its ap- PLA/GO and PLA/GNP films [25] reported that GO and
plications [1]. Using fillers is a good way to decrease the cost graphene could be safely incorporated into PLA to improve
of PLA. Popular fillers are organic or inorganic materials [2], its mechanical properties for biomedical engineering. GNP
talc [3], paper pulp [4], sisal [5], carbon blacks [6], banana with a thickness of 2 nm and a length of 1–2 μm was used
fiber [7], starch [8], jute [9], oyster shell [10], flax [11–13], as reinforcement filler in PLA. The incorporation of GNP
kenaf [9], bamboo [14], ammonium salt [15], corn starch [16], improved the thermostability and tensile strength. Even small
tapioca [17], wood flour [18], carbon nanotubes [19], some amounts of GNP (≤ 0.25 wt%) exhibited excellent biocompat-
polymers [20, 21], and plasticizers [17, 22, 23]. Graphene ibility [26]. GNP was blended with PLA, and the blend

* Chi-Hui Tsou 4
Department of Applied Cosmetology, Kao Yuan University,
[email protected] Kaohsiung 82101, Taiwan, Republic of China
* Manuel Reyes De Guzman 5
Department of Materials Science and Engineering, National Taiwan
[email protected] University of Science and Technology, Taipei 10607, Taiwan,
Republic of China
1
Material Corrosion and Protection Key Laboratory of Sichuan
6
Province, College of Materials Science and Engineering, Sichuan R&D Center for Membrane Technology, Department of Chemical
University of Science and Engineering, Zigong 643000, China Engineering, Chung Yuan University, Chung-Li 32023, Taiwan,
2
Department of Materials Science, Chulalongkorn University, Republic of China
Bangkok 10330, Thailand 7
Department of Fashion Business Administration, Lee-Ming Institute
3
Department of Materials and Textiles, Oriental Institute of of Technology, Taishan, New Taipei City 24305, Taiwan, Republic of
Technology, Pan-Chiao 22064, Taiwan, Republic of China China
 227 Page 2 of 10 J Polym Res (2019) 26:227

hydrolytic degradation after 6 months was determined. improving PLA/RH composites were investigated: (1)
Compared with neat PLA, PLA/GNP composites demonstrat- grafting with MAH to hydrophilize PLA; (2) using a methy-
ed firmer adhesion to human skin fibroblasts. They did not lene diphenyl diisocyanate (MDI) additive to enhance the
release toxins after the hydrolytic degradation [27]. Marconi compatibility between the polymer and the filler; (3) combin-
[28] blended GNP with PLA to produce a material for 3D ing methods (1) and (2) to enhance the bonding between PLA
printing; the addition of GNP did not improve both the stress and RH by first grafting PLA with MAH to prepare PLA-g-
and the strain, but enhanced the stiffness. However, both GO MAH, then using MDI to compatibilize PLA-g-MAH and RH
and GNP are extremely expensive and nonbiodegradable. composites. The second method (using an MDI additive) was
Hence, sustainable and renewable fillers for PLA should be demonstrated to be the most effective; however, the degrad-
explored. Rice husk (RH) is ideal not only because it is avail- ability was not reported. Our present study obtained remark-
able free-of-charge but also because it is nonabrasive, renew- able results from the biodegradation and biological activity of
able, biodegradable, and low in density. It has potential as a PLA/RH/MDI composites. This favorable condition en-
low-cost feedstock for fuel ethanol production through dilute hanced the interfacial compatibility between the components
acid pretreatment [20, 29]. Some studies on polymers and RH and the mechanical properties of renewable PLA/RH/MDI
composites have been reported [30–35]. Zhao et al. [30] re- composites that were processed into filaments for 3D printing
ported that RH was blended with polycaprolactone to prepare applications. Finally, PLA and PLA/RH/MDI filaments with
biodegradable composites; the biodegradation increased with varying RH content were evaluated by submitting them to 3D
the RH content. Wang et al. [31] demonstrated that RH rein- printing technology.
forced high-density polyethylene (HDPE) that was thermo-
treated, and the results indicated that the mechanical proper-
ties were substantially improved. However, HDPE was non-
Experimental
biodegradable. Arayapranee [34] investigated RH ash as filler
for natural rubber; the results revealed that the filler improved
Materials and preparation of composites
hardness but decreased tensile strength and tear strength. Jamil
[35] blended RH with natural rubber and HDPE, and showed
The PLA resin used in this study, with a trade name of
that the tensile and impact properties of HDPE/natural rubber
Biopolymer 4032D (Mw = 9.73 × 104) was obtained from
decreased with the RH content, but the hardness increased.
Natural Works. RH was produced by a husking machine that
Other reports [36–38] have discussed RH as filler in PLA.
separated the husk from Penglai rice, which was obtained
Hua et al. [36] modified maleic anhydride (MAH) with RH,
from Lu-Chu in Taiwan. Scheme 1 illustrates the preparation
and then blended it with PLA; the mechanical properties of the
of RH. PLA and RH were dried in a vacuum oven at 80 °C for
composite improved and the water absorbability decreased.
10 h. Varying weight ratios of dried PLA and RH were melt-
Battegazzore et al. [35] extracted silica powder from RH and
blended using a twin-screw extruder (SHJ-20 twin-screw ex-
used various amounts of the powder as filler in PLA; adding
truder, Nanjing Jiant, ZENIX, Taiwan) at a temperature of
the silica improved the storage modulus and reduced the ox-
190 °C; the screw speed was maintained at 180 rpm. Process
ygen permeability of PLA; however, the tensile strength was
conditions were chosen on the basis of the melting tempera-
weakened [37]. Tran et al. [36] treated RH with two kinds of
ture of polymer, which approached 170 °C; the manufacturing
organosilanes―γ-aminopropyltriethoxysilane and γ-
temperature was 15–20 °C higher than the polymer melting
glycidoxypropyltrimethoxysilane―to reduce the moisture
point. Two composites were produced: PLA x RH y and
sensitivity and increase the surface energy of RH; the results
PLAxRHyMDI, where x = wt% of PLA and y = wt% of RH.
showed that both silane treatments enhanced the interfacial
These two compounds (with and without MDI) were then hot-
adhesion between PLA and RH [38]. A hydrophilic RH had
pressed at 190 °C and 8 MPa for 3 min. Table 1 summarizes
a poor dispersion in PLA, which was a hydrophobic thermo-
the compositions of the prepared specimens.
plastic; in other words, PLA was incompatible with RH.
Ineffective adhesion between the filler and the polymer result-
ed in PLA/RH blends with weak tensile strength. Modifying Mechanical properties
the filler and the matrix can increase the interfacial compati-
bility between the filler and PLA. Wu et al. [39] fabricated 3D The tensile properties of PLA, PLAxRHy, and PLAxRHyMDI
printing filaments from biodegradable PLA and RH; acrylic specimens at 25 °C were determined using a tensile testing
acid-grafted PLA was incorporated with RH that was treated machine (model AG-10KNA, Shimadzu). All specimens were
with a synthesized coupling agent to enhance the properties of prepared according to ASTM D638 (Type 4). A 35-mm dog-
the PLA/RH composites. The results showed excellent tensile bone-shaped gauge was used for tensile tests. The tensile
properties, but the process was complicated and unsuitable for strength and elongation at break were based on the average
industrialization. In our recent work [40], three methods of tensile results of five specimens.
J Polym Res (2019) 26:227 Page 3 of 10 227

Crushed sieve
analysis

Water
Rice Husk

Pulverizer Rice Husk Powder Washing Drying

Chaff
Brown Rice
Rice Paddy
Rice huller

Rice Cooked Rice

PLAxRHy Poly (lactic) acid

Biodegradation
Brabender Methylenediphenyl
PLAxRHy MDI diisocyanate
Rice Husk

Renewable-Based
Composites Melt blending

Scheme 1 Preparation of biodegradable composites from rice husk.

Notched Izod impact tests were conducted using DG-1B dimension of 110 × 13 × 0.2 mm3. Soil was placed in a plastic
(Toyo Seiki) according to ASTM 256; the specimen dimen- box with a dimension of 20 × 14 × 8 cm3, wherein the soil was
sions were 64 mm × 12.7 mm (length × width); sharp notches kept moistened with deionized water (30%) at 21–25 °C (ambi-
of 2.5-mm depth were made using a cutter. For each compos- ent temperature) [16, 17]. After every 30 days during the soil test,
ite, five replicated specimens were considered to represent an a specimen of buried PLA, PLAxRHy, and PLAxRHyMDI was
average value. taken and washed with water and then dried in an oven at 35 °C.
The weight loss percentage was based on the average result of at
Fourier transform infrared spectroscopy least five measurements.

FTIR measurements were conducted using a PerkinElmer

spectrometer (model Spectrum One). The spectra of speci- Morphology
mens were obtained by averaging 20 scans with a resolution
of 2 cm−1 and a wave number range of 4000 to 1350 cm−1. The morphology of specimens before and after degradation
was observed using a scanning electron microscope (SEM,
Hitachi, model SU1510). Specimens with an area of 2 ×
Biodegradation
2 cm2 were fixed on a holder with the help of adhesives, and
were then coated with a thin layer of gold (15 keV for 15 s) to
The biodegradability of PLA, PLAxRHy, and PLAxRHyMDI
improve the image resolution. SEM examinations were con-
composites buried in soil was evaluated in terms of the percent-
ducted at 1.00 K magnification and a low voltage (2.1 kV).
age weight loss, as suggested by Yeh [41]. Hot-pressed speci-
mens were sectioned to form rectangular composites with a

Table 1 Compositions Water absorption

of PLA, PLAxRHy, and Specimen PLA RH MDI
PLAxRHyMDI (%) (%) (phr) Five specimens (5 × 5 × 1 mm3) were used for water absorp-
specimens
tion measurement. All specimens were weighed, immersed in
PLA 100 – –
distilled water at 24 °C for 1 day, and then dried by lightly
PLA80RH20 80 20 –
pressing a tissue on the specimen surface. Water absorption
PLA70RH30 70 30 –
(WA) was calculated using the following equation:
PLA60RH40 60 40 –
PLA50RH50 50 50 –
W 1− W 0
PLA80RH20MDI 80 20 1 WAð%Þ ¼  100% ð1Þ
W0
PLA70RH30MDI 70 30 1
PLA60RH40MDI 60 40 1
PLA50RH50MDI 50 50 1
where W0 was the original weight of the dry specimen and W1
was the weight of the wet specimen.
 227 Page 4 of 10 J Polym Res (2019) 26:227

Fig. 1 Tensile strength (○,●) and

elongation at break (□,■) as
function of rice husk content of
following specimens: (○,□)
PLAxRHy; (●,■) PLAxRHyMDI

In vitro cytotoxicity test formazan solutions was measured at 570 nm on an enzyme-

linked immunosorbent assay microplate reader. Proliferation
All composites were sterilized using an alcohol blast burner. at 72 h was calculated as follows:
The standard used for the in vitro cytotoxicity test [19] was
Proliferation% ¼ Ac=Ao ð2Þ
ISO 10993-5. Cell culture media and L929 fibroblasts were
purchased from the Food Industrial Research and where Ac was the specimen absorbance and Ao was the con-
Development Institute in Hsinchu, Taiwan. Processes for sam- trol absorbance on day 0.
ple extraction consisted of culturing the cells in a 5% CO2 Cell viability was quantitatively determined using an MTT
incubator at 37 °C for 24 h. Subsequently, the culture medium assay [19, 38, 39]. For each composite, three replicated spec-
was removed and replaced with sample extracts and negative imens were considered to represent an average value. The
and positive control solutions. Thereafter, the cells were again relative growth rate (RGR) of a cell culture was calculated
cultured for 24 h, and analyzed using methyl tetrazolium as follows:
(MTT; Sigma, Saint Louis, Missouri, USA) assay after 72 h
of incubation; the fluid was recovered and analyzed without OD of sample
RGR ¼  100% ð3Þ
buffering, diluting, or filtering. The optical density (OD) of the OD of blank

Fig. 2 Notched Izod impact of

following specimens: (◆) PLA;
(○) PLAxRHy; (□) PLAxRHyMDI
J Polym Res (2019) 26:227 Page 5 of 10 227

Fig. 3 FTIR spectra of following

specimens: (a) PLAxRHy; (b)
PLAxRHyMDI

between MDI and RH, because the isocyanate acted as binder

[43].
Figure 2 compares the notched Izod impact of PLA,
Results and discussion PLAxRHy, and PLAxRHyMDI specimens, and indicates that
the notched Izod impact of PLA was only 20.6 J/m. Increasing
Tensile and notched Izod impact properties the RH content of the composite led to a substantial reduction
in the toughness and impact energy of PLAxRHy. However,
Figure 1 provides data on tensile strength and elongation at break when MDI was added as a coupling agent, PLA50RH50MDI
of PLAxRHy and PLAxRHyMDI specimens. The tensile strength was more than three times tougher than PLA50RH50. This
and elongation at break of neat PLA were 48.7 MPa and 3.6%, fairly strong mechanical property was due to the compatibility
respectively. When PLA was blended with RH, PLAxRHy spec- between PLA and RH. MDI was an excellent cross-linking
imens exhibited decreases in tensile strength and elongation at agent in PLAxRHy composites; therefore, the Izod impact
break. When the RH content increased from 0 to 50 wt%, the with MDI was higher than that for pure PLA.
tensile strength and elongation at break of PLAxRHy specimens
decreased from 48.7 to 19.3 MPa and from 3.6 to 1.7%, respec- Fourier transform infrared spectroscopy
tively. It is due to the incompatibility between PLA and RH. The
poor adhesion to each other caused defective bonding between Figure 3 represents the FTIR spectra of PLAxRHy, and
them. However, when MDI was added, the tensile strength of PLA x RH y MDI specimens. PLA blended with RH,
PLAxRHyMDI specimens improved relative to PLAxRHy spec- PLAxRHy [(a) in Fig. 3], exhibited peaks in the spectra at
imens. For instance, the tensile strength of PLA50RH50MDI absorption bands of 1750, 2823, and 2922 cm−1 and a broad
specimen was 42.6 MPa; whereas that of PLA50RH50 specimen peak at 3660–2990 cm−1, corresponding to the –OH stretching
was 19.3 MPa. This improvement in tensile strength was due to vibration of RH. The FTIR spectra of PLAxRHy did not differ
the increase in interfacial compatibility between PLA and RH much from the spectra of PLAxRHyMDI [(b) in Fig. 3].
and the isocyanate linkage between PLA and MDI, as well as However, absorption bands at 2990–3660 cm−1, originally
shown in the FTIR spectra of PLAxRHy, were replaced by a
(a) (b) new absorption band at 3316 cm−1 that corresponded to –NH
groups. The smaller peak depicted by bending absorption
bands at 3660–2990 cm−1 and the appearance of –NH groups
at 3316 cm−1 might be attributed to the interaction between
the–OH groups of RH and the isocyanate (N=C=O) groups of
MDI or to the interaction between the –COOH groups of PLA
and the isocyanate groups of MDI throughout the
(c) (d)
compounding process. Figure 3 also proposes a probable
mechanism for the formation of PLAxRHyMDI.

Morphology

Figure 4 illustrates the surface morphology of cryofractured

neat PLA, neat RH, PLA70RH30, and PLA70RH30MDI. The
surface of fractured PLA [Fig. (4a)] was brittle and smooth.
Fig. 4 SEM images of following specimens: (a) PLA; (b) RH; (c) PLA70 RH particles [Fig. (4b)] had different shapes and an average
RH30; (d) PLA70RH30MDI particle size of 5–30 μm. RH dispersed and blended well in
 227 Page 6 of 10 J Polym Res (2019) 26:227

(a) (b) (c) (d) (e)

(f) (g) (h) (i)

Fig. 5 Surface SEM micrographs of following specimens buried in soil for 90 days: (a) PLA; (b) PLA80RH20; (c) PLA70RH30MDI; (d) PLA60RH40; (e)
PLA50RH50; (f) PLA80RH20 MDI; (g) PLA70RH30 MDI; (h) PLA60RH40 MDI; (i) PLA50RH50MDI

the PLA matrix [Fig. 4(c)]. Numerous cavities were formed surfaces with several cracks after burying them in soil for
because of the incompatibility between PLA and RH, several days; the size of the cracks considerably increased
resulting in a weak mechanical property, which is consistent with the burial time. Similarly, at the same burial time, the size
with the results in Figs. 2 and 3. The compatibility of compo- of the voids on the surface of PLAxRHyMDI specimens sub-
nents in PLA70RH30 specimen was improved when MDI was stantially increased as the RH content increased. However,
added [Fig. 4(d)]; the morphology showed compatibility (i.e., fungi-decomposed PLAxRHyMDI specimens had fewer voids
without the formation of voids) because of the enhanced in- than PLAxRHy specimens. This result might be attributed to
terfacial adhesion between PLA and RH. The compatibility in the increased packing density and reduced hydrophilic char-
PLA70RH30MDI specimen was due to the interaction between acteristics of PLA. As evidenced by the FTIR analysis, the
the –OH groups of RH and the isocyanate groups of MDI and reaction of the carboxylic acid groups of PLA molecules and
between the carboxylic acid groups of PLA and the isocyanate the hydroxyl groups of RH with the isocyanate groups of MDI
groups of MDI. Therefore, the two phases had strong affinity molecules occurred during the melt-blending processes in-
with each other, which would lead to favorable mechanical volving PLAxRHyMDI specimens.
properties.
Figure 5 compares and contrasts the surface SEM micro- Biodegradation
graphs of PLAxRHy and PLAxRHyMDI specimens buried in
soil for 30 and 90 days. As expected, PLA x RH y and Figure 6 gives the percentage of weight loss of PLA,
PLAxRHyMDI specimens were observed to have porous PLA x RHy, PLA xRH yMDI specimens buried in soil for

Fig. 6 Percentage of weight loss

of following specimens: (◆) PLA;
(−□-) PLA80RH20; (−△−)
PLA70RH30MDI; (−○-)
PLA60RH40; (−◇-) PLA50RH50;
(−-□–) PLA80RH20MDI;
(−-△ − -) PLA70RH30 MDI;
(−-○–) PLA60RH40MDI; (−-◇–)
PLA50RH50MDI
J Polym Res (2019) 26:227 Page 7 of 10 227

Fig. 7 Water absorption of

following specimens: (◆) PLA;
(○) PLAxRHy; (□) PLAxRHyMDI

varying amounts of time. The weight loss of PLAxRHy and Water absorption
PLAxRHyMDI specimens increased with the RH content.
PLAxRHyMDI specimens exhibited lower weight loss than Figure 7 plots water absorption data for PLA, PLAxRHy, and
either PLA or PLAxRHy specimens at the same burial time. PLAxRHyMDI specimens, and indicates a trend of increasing
The SEM micrographs in Fig. 5 indicated that PLAxRHy spec- water absorption (0.58%–18.57%) with the RH content (0%–
imens were more readily degraded than PLAxRHyMDI spec- 50%). Increasing the RH content enhanced the water absorp-
imens. Figures 5 and 6 show that the degradations and weight tion because of the hydrophilic property of RH. At the same
losses of PLAxRHy and PLAxRHyMDI specimens consider- RH content, PLAxRHyMDI specimens exhibited higher resis-
ably increased with the amount of RH. Therefore, adding RH tance against water absorption than PLAxRHy specimens. The
can enhance the biodegradability of PLA, and adding MDI to improved water resistance of PLAxRHyMDI is attributed to
PLAxRHy composites decreased the biodegradation because the dense packing because of the cross-linking in the compos-
of the cross-linking between PLA and RH; thus, the surface of ites. According to the FTIR analysis, several hydrophilic OH
PLAxRHy was difficult to degrade. groups from RH reacted with the NCO groups of MDI.

Fig. 8 MTT assay results from 3-

day culture for positive control,
negative control, PLA, PLAxRHy,
and PLAxRHyMDI composites
 227 Page 8 of 10 J Polym Res (2019) 26:227

Fig. 9 L929 fibroblasts cultured for 3 days with following specimens: (1) original control; (2) positive control; (3) negative control; (a) PLA;
(b)PLA80RH20; (c) PLA70RH30; (d) PLA60RH40; (e) PLA50RH50; (f) PLA80RH20MDI; (g) PLA70RH30 MDI; (h) PLA60RH40MDI; (i) PLA50RH50MDI

Cytotoxicity test [42] Evaluation of filament performance during 3D

printing operations
Figures 8 reports the results of MTT assay for PLA,
PLAxRHy, and PLAxRHyMDI specimens. The RGR of An extruder (Model TUSe194T, Atlas Electric Devices
PLAxRHy increased with the RH content, on account of Company, Chicago, IL, USA) was used to make filaments.
the biotic nature of RH, which was derived from crops. PLA and all composites were loaded into the extruder at a tem-
However, PLAxRHyMDI specimens showed slightly low- perature of 185–195 °C. The filament diameter was controlled at
er RGR than PLAxRHy specimens at the same RH con- 1.75 ± 0.04 mm. Scheme 1 diagrams the fabrication of renewable
tent, because the MDI coupling agent was a mild cyto- composites (PLAxRHy and PLAxRHyMDI), which were made
toxic additive. Specifically, the RGRs of PLA50RH50 and into filaments for 3D printing purposes. Table 2 provides an
PLA50RH50MDI specimens were nearly the same, sug- evaluation of specimens as to their performance for 3D printing.
gesting that the biotic RH partially absorbed the cytotox- The results in Table 2 indicated that neat PLA and
icity of MDI. Figure 9 delineates images of L929 fibro- PLA80RH20MDI filaments performed well. PLAxRHyMDI fila-
blasts incubated for 3 days with extracts of PLA, ments with 30%–40% RH content did not perform well, as the
P L A x R H y, a n d P L A x R H y M D I s p e c i m e n s . B o t h RH fibers blocked the 3D printer. The 3D printer could not
PLAxRHy and PLAxRHyMDI specimens exhibited more operate when the RH content was 50% because of excessive
proliferation than the neat PLA. Overall, Figs. 8 and 9 RH fibers, causing the PLAxRHyMDI filaments to melt at a very
establish that the renewable composites were low rate. Moreover, RH fibers were carbonized when they
noncytotoxic. blocked the 3D printer during operation.

Table 2 Performance of PLA and

PLAxRHyMDI specimens during Specimen Performance
3D printing operations
PLA Good (3D printer ran smoothly for more than 72 h)
PLA80RH20MDI Good (3D printer ran smoothly for more than 72 h)
PLA70RH30MDI Mediocre (3D printer ran for few hours, but got blocked easily)
PLA60RH40MDI Poor (3D printer ran with difficulty; got blocked often)
PLA50RH50MDI Very poor (3D printer was inoperable)
J Polym Res (2019) 26:227 Page 9 of 10 227

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Technology (2017XC16; 2019CXRC01), the Opening Project of 18. Tsou CY, Wu CL (2015) Tsou CH et al. Polym Sci Ser B 57(5):
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Process Equipment and Control, Sichuan University of Science and icity of a poly(lactic acid)/Nanosilver-doped multiwall carbon
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