coatings

Article
Morphology, Structure, and Properties of Conductive
Polylactide Fibers Prepared Using Polyvinyl Acetate
and Multiwalled Carbon Nanotubes
Qingsheng Liu 1,2,3, *, Yuqi Zhou 1 , Ying Shen 1 , Yuhao Li 4 , Haiyang Guo 5 , Bingyao Deng 1 and
Yonggui Li 2, *
1 Key Laboratory of Eco-Textiles, Ministry of Education, Jiangnan University, Wuxi 214122, China
2 Fujian Key Laboratory of Novel Functional Textile Fibers and Materials, Minjiang University,
Fuzhou 350108, China
3 Shenghong Group Co., Ltd., Shengze 215228, China
4 China Nonwovens & Industrial Textiles Association, Beijing 100020, China
5 Jiangsu Doway New Materials Science & Technology Co. Ltd., Suqian 223800, China
* Correspondence: qsliu@jiangnan.edu.cn (Q.L.); lygwxjd@sina.com (Y.L.);
Tel.: +86-0510-8591-2007 (Q.L.); +86-0591-8376-0411 (Y.L.); Fax: +86-0510-8591-2009 (Q.L.)




Received: 26 August 2019; Accepted: 6 October 2019; Published: 9 October 2019


Abstract: Two kinds of conductive polylactide fibers—polylactide pre-oriented yarns (PLA-POY) and
PLA-drawn textured yarns (PLA-DTY) are prepared by coating method using ethyl acetate as solvent,
multiwalled carbon nanotubes (MWCNTs) as conductive filler, and polyvinyl acetate (PVAc) as
dispersing agent and coating agent. The PLA fibers are characterized by scanning electron microscope
(SEM), Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC),
resistance meter, and tensile test. The results show that PLA-POY and PLA-DTY have been coated
successfully by PVAc and MWCNTs. After PLA-POY fibers are treated by ethyl acetate, the highly
porous structures form because of swelling and the subsequent solvent-induced crystallization of
PLA-POY fibers with low crystallinity. This causes the tensile force to decrease. However, PVAc
can improve the tensile force of the treated PLA-POY fibers. For PLA-DTY fibers, the effect of ethyl
acetate on surface morphology is small. Therefore, the treated PLA-DTY fibers own higher tensile
properties than original PLA-DTY fibers due to the existence of PVAc. With the increase of PVAc and
MWCNTs, the conductive properties of the PLA fibers will increase. The electrical conductivity of
PLA-POY and PLA-DTY fibers can reach 0.53 and 0.13 µs/cm, respectively.

Keywords: polylactide fibers; conductive properties; multiwalled carbon nanotubes; polyvinyl

acetate; ethyl acetate

1. Introduction
Polylactide (PLA) is a type of biodegradable polyester with thermoplastcity, biodegradability,
and biocompatibility [1,2]. PLA has been extensively used for fiber materials due to its similarity
with polyethylene terephthalate (PET) fibers, ecofriendly nature, and ease of processing [3].
The melt-spinning method is optimal for manufacturing PLA fibers because of its thermoplastcity [3]
and a wide melt-processing window.
The effects of processing conditions on the structure and properties of melt-spun PLA fibers have
been studied widely [4–6]. Especially, Liu et al. [3] studied the effect of air drawing on structure and
properties of PLA fibers. Solarski et al. [7] introduced plasticizer and clay to PLA and manufactured
PLA fibers by melt-spinning process. The obtained PLA fibers presented an improvement in thermal
and shrinkage properties. Polylactide/poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PLA/PHBV)

Coatings 2019, 9, 651; doi:10.3390/coatings9100651 www.mdpi.com/journal/coatings

Coatings 2019, 9, 651 2 of 12

blend fibers were manufactured via the conventional two-step melting-spinning and hot-drawing
process by Li et al. [8] Compared with traditional PLA fibers, the prepared fibers showed significantly
reduced boiling water shrinkages and superior softness. Hufenus et al. [9] prepared PLA/PHBV
core–sheath bicomponent fibers. When the PLA was chosen as the raw material of sheath layers,
the fibers could be successfully spun. However, when the PHBV was used as the raw material of
sheath layers, it was difficult to produce PLA/PHBV bicomponent fibers. The tensile properties of
bicomponent fibers with a PHBV core and a PLA sheath were determined by PLA. Zhang et al. [10]
prepared high-performance PLA fibers via tailoring crystallization with the aid of an active nucleating
agent (NA). Compared with neat PLLA fibers, a prominent increase of 78% in tensile strength and a
substantial decline of 1069% in boiling water shrinkage were achieved in the obtained fibers with 0.3
wt.% NA [10].
Although melt-spun PLA fibers have been widely explored, few studies [11,12] on functional
PLA fibers have been performed. It is well known that conductive fibers are important and highly
functional, and that they can be used as flexible electronic devices including solar cells, displays,
radio identification, sensor tapes, capacitors, and batteries [13,14]. Rentenberger et al. [12] prepared
conductive PLA/poly(ε-caprolactone)/multiwalled carbon nanotubes (PLA/PCL/MWCNTs) fibers using
the double percolation method. The double percolation method can efficiently prepare conductive
fibers. Conductive fillers are added into immiscible polymer blends. The two phases in immiscible
polymer blends form a co-continuous blend morphology. Conductive fillers are selectively located in
one of the two polymer matrices, or their interface, so that the percolation threshold of conductive
fillers decreases [15]. However, the double percolation method is complicated.
Coating is thought as a simple and efficient way to manufacture conductive fibers. However, for
coating, the key difficulties include the uniform dispersity of the conductive fillers and the strong
bonding force between coating agent and fiber. Here, the two kinds of conductive polylactide fibers,
including PLA pre-oriented yarns (PLA-POY) and PLA-drawn textured yarns (PLA-DTY), were
prepared by coating method using ethyl acetate as solvent, multiwalled carbon nanotubes (MWCNTs)
as conductive filler, and polyvinyl acetate (PVAc) as dispersing agent and coating agent. PVAc can
make unmodified MWCNTs disperse uniformly in ethyl acetate. Moreover, PVAc is compatible
completely with PLA, which is a good coating agent for PLA fibers. The strong bonding force will
form between PVAc and PLA fibers. Ethyl acetate has low toxicity, and it can be used an additive in
foods and drugs to improve their flavor. In addition, the morphology, chemical structure, thermal
behavior, conductive properties, and tensile properties of the prepared conductive PLA fibers were
characterized by SEM, FTIR, differential scanning calorimetry (DSC), resistance meter, and tensile test.

2. Experimental Details

2.1. Materials
Polyvinyl acetate (PVAc) (Mη = 3.0 × 105 g/mol) was obtained from Yantai Nuoda Chemical
Co., Ltd. (Yantai, China). Multiwalled carbon nanotubes (MWCNTs) with diameter of 40–60 nm
and length of less than 2 µm were purchased from Shenzhen Nanotech Port Co., Ltd. (Shenzhen,
China). Ethyl acetate was purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China).
Polylactide pre-oriented yarns (PLA-POY) and drawn textured yarns (PLA-DTY) were manufactured
by Hengtian Changjiang Biological Materials Co., Ltd. (Changshu, China). Each PLA-POY contains 72
fibers. The diameter of each fiber in PLA-POY is ~20 µm. PLA-DTY was prepared by drawing and
twisting/untwisting simultaneously PLA-POY. The diameter of each fiber in PLA-DTY is ~14 µm.

2.2. The Preparation of Conductive PLA Fiber

First, PVAc was added to ethyl acetate and dissolved by stirred for 3 h with a magnetic stirrer to
prepare PVAc in ethyl acetate solution. Second, the required amounts of MWCNTs were added into
PVAc in ethyl acetate solution, stirred for 30 min by a magnetic stirrer, and then sonicated for 2 h to
Coatings 2019, 9, x FOR PEER REVIEW 3 of 12

First, PVAc was added to ethyl acetate and dissolved by stirred for 3 h with a magnetic stirrer to
Coatings 2019, 9, 651 3 of 12
prepare PVAc in ethyl acetate solution. Second, the required amounts of MWCNTs were added into
PVAc in ethyl acetate solution, stirred for 30 min by a magnetic stirrer, and then sonicated for 2 h to
obtain
obtain the suspension
suspension of of MWCNTs
MWCNTs and PVAc in ethyl acetate. Here, the concentration
concentration ofof MWCNTs
MWCNTs
and PVAc in ethyl acetate is 2–10 and 10–50 mg/mL, respectively. Last, conductive PLA fibers were
prepared by coating method; the coating method is shown in Figure 1. The The temperature
temperature of of the
the water
water
bath in the ultrasonic cleaner was room temperature. The take-up speed of conductive fibers was ~1 ~1
m/min. The obtained
obtainedconductive
conductivefibers
fiberswere
weredried
dried naturally
naturally in fume
in fume hood.
hood. TheThe treated
treated PLA-POY
PLA-POY and
and PLA-DTY
PLA-DTY fibers fibers are denoted
are denoted by OCxPy
by OCxPy and and TCxPy,
TCxPy, respectively.
respectively. Here,
Here, the letter
the letter “O” “O” in OCxPy
in OCxPy and
and the letter
the letter “T” in“T” in TCxPy
TCxPy stand
stand for for PLA-POY
PLA-POY and PLA-DTY,
and PLA-DTY, respectively.
respectively. C andforx MWCNTs
C and x stand stand for
MWCNTs and the concentration
and the concentration of MWCNTs,ofrespectively.
MWCNTs, respectively.
P and y standPfor and y stand
PVAc and theforconcentration
PVAc and the of
concentration
PVAc, respectively.of PVAc, respectively.

The schematic
Figure 1. The schematic of
of the
the coating
coating method.

2.3. Differential
2.3. Differential Scanning
Scanning Calorimetry
Calorimetry
The crystallization
The crystallization behaviors
behaviors andand melting
melting behaviors
behaviors of
of the
the samples
samples were
were characterized
characterized byby
differential scanning
scanning calorimetry
calorimetry that
that used
used a ®
differential a DSC
DSC Q200
Q200 (TA
(TA Instruments
Instruments®,, Inc.,
Inc., New
New Castle,
Castle, DE,
DE,
USA). Nitrogen was used at a flow rate of 50 mL/min. The instrument was calibrated with
USA). Nitrogen was used at a flow rate of 50 mL/min. The instrument was calibrated with In and Pb.In and Pb.
The weight of the samples was between 4 and 6 mg. Each sample was heated from 0 to 200 ◦ C at
The weight of the samples was between 4 and 6 mg. Each sample was heated from 0 to 200 °C at
◦ C/min.
10 °C/min.
10
2.4. Scanning Electron Microscope
2.4. Scanning Electron Microscope
Scanning electron microscopy (SEM) measurements of the longitudinal surface and cross section
Scanning electron microscopy (SEM) measurements of the longitudinal surface and cross
of fibers were carried out by a Model SU1510 scanning electron microscope (Hitachi, Tokyo, Japan).
section of fibers were carried out by a Model SU1510 scanning electron microscope (Hitachi, Tokyo,
The samples were sputtered with gold before the SEM observation. The morphologies of the cross
Japan). The samples were sputtered with gold before the SEM observation. The morphologies of the
sections of samples were observed at a working voltage of 5 kV. Here, the fiber bundles first are
cross sections of samples were observed at a working voltage of 5 kV. Here, the fiber bundles first
embedded by using collodion. Then, cross-section slices were prepared by using Y172 Hardy’s thin
are embedded by using collodion. Then, cross-section slices were prepared by using Y172 Hardy’s
cross-section device (Changzhou Depu Textile Technology Co., Ltd., Changzhou, China).
thin cross-section device (Changzhou Depu Textile Technology Co., Ltd., Changzhou, China).
2.5. Fourier Transform Infrared-Attenuated Total Reflection Spectroscopy
2.5. Fourier Transform Infrared-Attenuated Total Reflection Spectroscopy
The spectra of Fourier transform infrared-attenuated total reflection (FTIR-ATR) were recorded
on a The spectra
Nicolet FTIRofspectroscope
Fourier transform
(Nexus infrared-attenuated
670, Waltham, MA,total reflection
USA). (FTIR-ATR)
Each spectrum waswere recorded
recorded with
on a Nicolet FTIR spectroscope (Nexus −1670, Waltham, MA, USA). Each spectrum
−1 was recorded
a total of 16 scans from 4000 to 500cm ; each scan had a resolution of 4 cm at room temperature. with
aThe
total of 16were
spectra scanssubtracted
from 4000against
to 500cm −1; each scan had a resolution of 4 cm−1 at room temperature.
a background air spectrum. OMNIC Nicolet Software (version 8.1)
The
was spectra
used forwere subtracted
spectra analysis.against a background air spectrum. OMNIC Nicolet Software (version
8.1) was used for spectra analysis.
2.6. Conductive Properties
2.6. Conductive Properties
The conductive properties of the treated PLA fibers with high resistivity were tested by Keithley
65167B high resistance meter (Cleveland, OH, USA). The conductive properties of the treated PLA
fibers with low resistivity were tested using a TENMARS TM-87 digital multimeter (Taipei, Taiwan).
Coatings 2019, 9, x FOR PEER REVIEW 4 of 12

The conductive properties of the treated PLA fibers with high resistivity were tested by
Keithley 65167B high resistance meter (Cleveland, OH, USA). The conductive properties of the
Coatings PLA9, 651
treated2019, fibers with low resistivity were tested using a TENMARS TM-87 digital multimeter 4 of 12
(Taipei, Taiwan). The length of the tested fibers is 0.08m. The electrical resistivity of the untreated
PLA fibers was characterized by a YG321 fiber-specific resistance tester. Five gram samples were
The length of the tested fibers is 0.08m. The electrical resistivity of the untreated PLA fibers was
used every time. The tests were carried out at room temperature with relative humidity of 65%.
characterized by a YG321 fiber-specific resistance tester. Five gram samples were used every time.
The tests were carried out at room temperature with relative humidity of 65%.
2.7. Tensile Test
2.7. Tensile Test properties of PLA fibers were determined on an YG061-1500 yarn tensile tester
The tensile
(Laizhou Electron
The tensile Instrument
properties Co.,fibers
of PLA Ltd.,were
Laizhou, China)on
determined at an
room temperature.
YG061-1500 yarn The cross-head
tensile speed
tester (Laizhou
and gauge length were 250 mm/min and 250 mm, respectively, and the pre-tension was 5 cN.
Electron Instrument Co., Ltd., Laizhou, China) at room temperature. The cross-head speed and gauge
length were 250 mm/min and 250 mm, respectively, and the pre-tension was 5 cN.
3. Results and Discussion
3. Results and Discussion
3.1. Morphology of PLA Fibers
3.1. Morphology of PLA Fibers
Figure 2 illustrates the SEM photographs of the PLA-POY fibers treated by MWCNTs and PVAc
Figure
in ethyl 2 illustrates
acetate. The SEM thephotographs
SEM photographs of the2a,b
in Figure PLA-POY fibers
show that thetreated
surface byofMWCNTs
PLA-POY and PVAc
fibers is
in ethyl and
smooth acetate. The SEM
the cross photographs
section is round. in Figure 2a,b
However, whenshow
the that the surface
PLA-POY fibersofare
PLA-POY fibers
treated by is
ethyl
smooth
acetate, aand thenumber
large cross section
of poresisappear
round.inHowever,
the surfacewhen the PLA-POY
and cross-section of fibers
PLA-POY, are treated
which isbyshown
ethyl
acetate,
in Figure a large
2c. number of poresporous
The highly appear structure
in the surface and cross-section
formed because of ofswelling
PLA-POY,and which is shown
subsequent
in Figure 2c. The highly
solvent-induced porous structure
crystallization of PLA-POY formed because
fibers withoflow
swelling and subsequent
crystallinity solvent-induced
[11]. Figure 2d–f reveals
crystallization
that in PLA-POY of PLA-POY fibers
fibers treated by with
MWCNTslow crystallinity
and PVAc in [11]. Figure
ethyl 2d–f
acetate reveals
with that in PLA-POY
the concentration of 8
fibers
mg/mL treated
MWCNTs by MWCNTs and PVAc
and 40 mg/mL in ethyl
PVAc, the acetate with the
single fibers theconcentration of 8 mg/mL
of multifilaments adhereMWCNTs and
to each other.
40
In mg/mL
addition, PVAc, the single fibers
the MWCNTs the of on
are coated multifilaments
the surface adhere to eachfibers,
of PLA-POY other. which
In addition,
can bethe MWCNTs
observed in
are coated
Figure 2e,f.on the surface of PLA-POY fibers, which can be observed in Figure 2e,f.

Figure 2. The SEM photographs of PLA pre-oriented yarns (PLA-POY) fibers treated by multiwalled
carbon nanotubes
nanotubes(MWCNTs)
(MWCNTs) andand
PVAc in ethyl
PVAc in acetate. (a,b) Original
ethyl acetate. PLA-POYPLA-POY
(a,b) Original fibers. (c) fibers.
PLA-POY (c)
fibers
PLA-POYtreated by treated
fibers ethyl acetate for acetate
by ethyl 30 min forat room temperature.
30 min (d,e) PLA-POY
at room temperature. (d,e) fibers
PLA-POYtreated by
fibers
MWCNTs
treated byand PVAc inand
MWCNTs ethylPVAc
acetate
in with
ethylconcentration
acetate with of 8 mg/mL MWCNTs
concentration and 40MWCNTs
of 8 mg/mL mg/mL PVAc.and 40(f)
The enlargement of the part in white square frame of panel e.
mg/mL PVAc. (f) The enlargement of the part in white square frame of panel e.

Figure
Figure 33 shows
showsthetheSEMSEMphotographs
photographs of of
PLA-DTY
PLA-DTY fibers treated
fibers by MWCNTs
treated by MWCNTs and PVAc in ethyl
and PVAc in
acetate. The SEM photographs in Figure 3a,b show that the surface of PLA-DTY
ethyl acetate. The SEM photographs in Figure 3a,b show that the surface of PLA-DTY fibers is fibers is smooth
and the and
smooth crossthe
section
crossissection
flat. When
is flat.the PLA-DTY
When fibers are
the PLA-DTY treated
fibers are with
treatedethyl acetate,
with it can beitseen
ethyl acetate, can
from Figure 3c that a small quantity of longitudinal grooves exists on the surface
be seen from Figure 3c that a small quantity of longitudinal grooves exists on the surface of PLA-DTY fibers.
of
However, the change of cross section of PLA-DTY fibers is difficult to observe. The effect of ethyl acetate
on PLA-DTY fibers is small because PLA-DTY fibers own high crystallinity [11]. DTY is prepared by
drawing and twisting/untwisting simultaneously POY so that PLA-DTY fibers own high crystallinity.
 Coatings 2019, 9, x FOR PEER REVIEW 5 of 12

Coatings 2019, 9, 651 5 of 12

PLA-DTY fibers. However, the change of cross section of PLA-DTY fibers is difficult to observe. The
effect of ethyl acetate on PLA-DTY fibers is small because PLA-DTY fibers own high crystallinity
[11]. DTY is prepared by drawing and twisting/untwisting simultaneously POY so that PLA-DTY
Figure 3d–f illustrates that in PLA-DTY fibers treated by MWCNTs and PVAc in ethyl acetate with the
fibers own high crystallinity. Figure 3d–f illustrates that in PLA-DTY fibers treated by MWCNTs and
concentration of 8 mg/mL MWCNTs and 40 mg/mL PVAc, the single fiber of multifilaments adheres
PVAc in ethyl acetate with the concentration of 8 mg/mL MWCNTs and 40 mg/mL PVAc, the single
to each other.
fiber In addition,adheres
of multifilaments the MWCNTs are coated
to each other. on the
In addition, surface
the MWCNTsof PLA-DTY
are coated fibers, which of
on the surface can be
observed in Figure 3e,f.
PLA-DTY fibers, which can be observed in Figure 3e,f.

FigureFigure 3. SEM
3. The The SEM photographs
photographs of PLA-DTY
of PLA-DTY fibers
fibers treated
treated bybyMWCNTs
MWCNTsand andPVAc
PVAcininethyl
ethylacetate.
acetate. (a,b)
(a,b) Original PLA-DTY fibers. (c) PLA-DTY fibers treated by ethyl acetate for 30
Original PLA-DTY fibers. (c) PLA-DTY fibers treated by ethyl acetate for 30 min at room temperature. min at room
(d,e) PLA-DTY fibers treated with MWCNTs and PVAc in ethyl acetate with concentration of with
temperature. (d,e) PLA-DTY fibers treated with MWCNTs and PVAc in ethyl acetate 8 mg/mL
concentration of 8 mg/mL MWCNTs and 40 mg/mL PVAc. (f) The enlargement of the part in white
MWCNTs and 40 mg/mL PVAc. (f) The enlargement of the part in white square frame of panel e.
square frame of panel e.
3.2. DSC Analysis
3.2. DSC Analysis
The original PLA-POY fibers, original PLA-DTY fibers, and the PLA fibers treated by MWCNTs
The original PLA-POY fibers, original PLA-DTY fibers, and the PLA fibers treated by MWCNTs
and PVAc in ethyl acetate were analyzed by DSC. The DSC curves are shown in Figure 4. Figure 4a
and PVAc in ethyl acetate were analyzed by DSC. The DSC curves are shown in Figure 4. Figure 4a
shows that that
shows in the
in DSC curve
the DSC curveof of
PLA-POY
PLA-POYfibers,
fibers, the glasstransition
the glass transitiondistrict,
district,
coldcold crystallization
crystallization peak,peak,
and melting peak can be observed. In addition, the glass transition district and
and melting peak can be observed. In addition, the glass transition district and cold crystallizationcold crystallization
peak peak
overlap partly ininthe ◦ C. However, in the DSC curves of the PLA-POY
overlap partly therange
range of of6060toto
9090°C. However, in the DSC curves of the PLA-POY fibers
fiberstreated
treatedbybyMWCNTs
MWCNTs and and PVAc
PVAc in in ethyl
ethyl acetate,
acetate, thethe glass
glass transition
transition temperature
temperature (Tg) (Tg ) cold
and and cold
crystallization
crystallization temperature
temperature (Tcc ) (Tcc) disappear.
disappear. ThisThis illustrates
illustrates that compared
that compared withoriginal
with the the original
PLA-POY
fibers,PLA-POY fibers, the
the crystallinity of crystallinity
the PLA-POY of the PLA-POY
fibers treated fibers treated by
by MWCNTs andMWCNTs
PVAc in andethylPVAc in ethyl
acetate increases.
This is due to the ethyl acetate inducing the crystallization of PLA-POY fibers. However,fibers.
acetate increases. This is due to the ethyl acetate inducing the crystallization of PLA-POY Figure 4b
However, Figure 4b shows that compared with the original PLA-DTY fibers, an obvious change in
shows that compared with the original PLA-DTY fibers, an obvious change in DSC curves of PLA-DTY
DSC curves of PLA-DTY fibers treated by MWCNTs and PVAc in ethyl acetate cannot be observed.
fibers treated by MWCNTs and PVAc in ethyl acetate cannot be observed. This illustrates that the effect
This illustrates that the effect of ethyl acetate on the structure of PLA-DTY fibers is small because of
of ethyl
theiracetate on the structure of PLA-DTY fibers is small because of their high crystallinity.
high crystallinity.
Coatings 2019, 9, x FOR PEER REVIEW 6 of 12

Figure 4.Figure 4. Differential

Differential scanning scanning calorimetry
calorimetry (DSC) curves
(DSC) curves of PLA-POY
of PLA-POY (a) and(a) and PLA-DTY
PLA-DTY (b) fibers
(b) fibers treated
treatedand
by MWCNTs by PVAc
MWCNTs andacetate
in ethyl PVAc in ethyl
with acetate MWCNTs
8 mg/mL with 8 mg/mL MWCNTsPVAc
and different and concentration.
different PVAc
concentration.

3.3. FTIR-ATR Analysis

The FTIR-ATR spectra of PLA-POY fibers treated by MWCNTs and PVAc in ethyl acetate with
concentration of 8 mg/mL MWCNTs, original PLA-POY fibers, and PVAc are illustrated in Figure 5.
In Figure 5, for PVAc, the peak at 1729 cm−1 corresponds to the amorphous C=O stretching. The
Coatings 2019, 9, 651 6 of 12

3.3. FTIR-ATR Analysis

The FTIR-ATR spectra of PLA-POY fibers treated by MWCNTs and PVAc in ethyl acetate
with concentration of 8 mg/mL MWCNTs, original PLA-POY fibers, and PVAc are illustrated in
Figure 5. In Figure 5, for PVAc, the peak at 1729 cm−1 corresponds to the amorphous C=O stretching.
The vibration bands at 2970 cm−1 are ascribed to CH3 asymmetric stretching. The band at 2926 cm−1
corresponds to CH2 asymmetric stretching. The bands at 1433 and 1370 cm−1 correspond to asymmetic
and symmetric bending vibrations of CH3 , respectively. The peaks at 1225 and 1118 cm−1 are attributed
to C–O–C asymmetric and symmetric vibrations, respectively. The peak at 946 cm−1 is assigned to CH
bending vibration [15]. For PLA, the peak at 1749 cm−1 corresponds to C=O stretching. The bands at
2995 and 2945 cm−1 are attributed to CH3 asymmetric and symmetric vibrating, respectively. The bands
at 2881 cm−1 correspond to CH vibrating. The peaks at 1452 and 1382 cm−1 are assigned to CH3
asymmetric deformation and CH3 symmetric deformation, respectively. The peaks at 1359 or 1363 cm−1
are ascribed to CH deformation and crystalline CH3 symmetric deformation. The peaks at 1181, 1128,
1083, and 1043 cm−1 correspond to C–O–C stretching, CH3 rocking, C–O–C stretching, and C–CH3
stretching, respectively [16]. Figure 5b shows that when the concentration of PVAc is 20 mg/mL,
the FTIR-ATR spectra of the treated PLA-POY fibers are similar to those of the original PLA-POY fibers.
However, when the concentration of PVAc is 40 mg/mL, the FTIR-ATR spectra of the treated PLA-POY
fibers are similar to that of original PVAc. In addition, when the concentration of PVAc is 20 mg/mL,
the C=O stretching band occurs at 1743 cm−1 , which is located at the middle district between the C=O
stretching band of PLA and that of PVAc. Generally, FTIR-ATR is used to characterize the chemical
structure of the surface of materials. This revealed that PLA-POY fibers are partly coated by PVAc
or the PVAc layer on the surface of PLA-POY fibers is very thin. However, when the concentration
of PVAc is 40 mg/mL, the C=O stretching band occurred at 1729 cm−1 , which is identical to the
wavenumber of C=O in PVAc. This shows that the PLA-POY fibers have been coated completely
by PVAc. The FTIR-ATR spectra of PLA-DTY fibers treated by MWCNTs and PVAc in ethyl acetate
with the concentration of 8 mg/mL MWCNTs, original PLA-DTY, and PVAc are illustrated in Figure 6;
similar results
Coatings are
2019, 9, found.
x FOR PEER REVIEW 7 of 12

Figure
Figure 5. FTIR-ATR
5. FTIR-ATR spectra
spectra of PLA-POY
of PLA-POY fibersfibers treated
treated by MWCNTs
by MWCNTs and PVAcandinPVAc in ethylwith
ethyl acetate
theacetate
concentration
with the of concentration
8 mg/mL MWCNTs and different
of 8 mg/mL MWCNTsPVAcand
concentration: (a) 4000–500
different PVAc cm−1 and
concentration: (a) (b)
1800–800 cm−1
4000–500 cm. −1 and (b) 1800–800 cm−1.

Figure 6. ATR-FTIR spectra of PLA-DTY fibers treated by MWCNTs and PVAc in ethyl
 Figure 5. FTIR-ATR spectra of PLA-POY fibers treated by MWCNTs and PVAc in ethyl
acetate
Coatings 2019, with the concentration of 8 mg/mL MWCNTs and different PVAc concentration: (a)
9, 651 7 of 12
4000–500 cm−1 and (b) 1800–800 cm−1.

Figure
Figure 6. ATR-FTIR
6. ATR-FTIR spectra
spectra of PLA-DTY
of PLA-DTY fibers by
fibers treated treated by MWCNTs
MWCNTs and PVAcand PVAc
in ethyl in ethyl
acetate solution
with the concentration of 8 mg/mL MWCNTs and different PVAc concentration: (a) 4000–500 −1
cmPVAcand (b)
acetate solution with the concentration of 8 mg/mL MWCNTs and different
1800–800 cm−1 . (a) 4000–500 cm−1 and (b) 1800–800 cm−1.
concentration:

3.4.3.4.
Conductive
Conductive Properties
Properties
TheTheconductive
conductive properties
properties of PLA-POY
of PLA-POY and andPLA-DTY
PLA-DTY fibers treated
fibers byby
treated MWCNTs
MWCNTs and andPVAc
PVAcin in
ethyl acetate have been characterized by a Keithley 65167B high-resistance
ethyl acetate have been characterized by a Keithley 65167B high-resistance meter, TENMARS TM-87 meter, TENMARS TM-87
digital
digitalmultimeter,
multimeter, andandYG321YG321 fiber-specific
fiber-specificresistance
resistance tester. TheThe
tester. results of electrical
results conductivity
of electrical conductivity
areare
listed in Tables 1 and 2. It can be seen that the electrical conductivity of
listed in Tables 1 and 2. It can be seen that the electrical conductivity of the treated PLA the treated PLA fibers is is
fibers
much higher than that of the untreated PLA fibers. The values of electrical
much higher than that of the untreated PLA fibers. The values of electrical conductivity of PLA conductivity of PLA fibers
show thatshow
fibers with the
thatincrease
with the of the concentration
increase of the of MWCNTs orofPVAc,
concentration the electrical
MWCNTs or PVAc,conductivity of
the electrical
PLA-DTY and PLA-POY fibers increases. However, when the concentration
conductivity of PLA-DTY and PLA-POY fibers increases. However, when the concentration of of MWCNTs is 2 mg/mL,
with the increase
MWCNTs is 2ofmg/mL,
the concentration of PVAcof
with the increase from
the 10 to 20 mg/mL,ofthe
concentration electrical
PVAc from conductivity
10 to 20 mg/mL, of thethe
treated PLA-POY and PLA-DTY fibers increased significantly from 1.2 × 10 −3 to 1.43 × 10−2 µs/cm, 0.7
electrical conductivity of the treated PLA-POY and PLA-DTY fibers increased significantly from 1.2
× 10 −3 to 8.3 × 10−3 µs/cm, respectively, whereas with the increase in concentration of PVAc from 20 to
× 10−3 to 1.43 × 10−2 μs/cm, 0.7 × 10−3 to 8.3 × 10−3 μs/cm, respectively, whereas with the increase in
50 concentration
mg/mL, those of of the
PVAc PLA-POY
from 20and to PLA-DTY
50 mg/mL,fibersthosebarely
of thechange
PLA-POYfrom and × 10−2 to 1.47
1.43 PLA-DTY × 10
fibers
−2
barely
and from −3
8.3 × 1.43
10 ×to108.9 × 1.47 −3
10 ×µs/cm, respectively.
µs/cm
change −2 to 10−2 μs/cm and 8.3 ×When 10−3 tothe
8.9concentration
× 10−3 μs/cm, of MWCNTs is
respectively. morethe
When
than 2 mg/mL, the effect of PVAc on with electrical conductivity of the treated
concentration of MWCNTs is more than 2 mg/mL, the effect of PVAc on with electrical conductivity PLA-POY and PLA-DTY
fibers
of theis obvious. However,
treated PLA-POY and when the concentration
PLA-DTY of PVAc
fibers is obvious. reacheswhen
However, 40 mg/mL, with the further
the concentration of PVAc
increase
reaches 40 mg/mL, with the further increase of the concentration of PVAc, the changePLA-POY
of the concentration of PVAc, the change of electrical conductivity of the treated of electrical
andconductivity
PLA-DTY fibers of theistreated
small. PLA-POY and PLA-DTY fibers is small.
When
Table the
1. The concentration
electrical of of
conductivity PVAc is 10fibers
PLA-POY mg/mL,
treatedwith the increase
by MWCNTs and PVAcof the concentration
in ethyl acetate of
MWCNTs from 2
(unit: 10−3 µs/cm). to 4 mg/mL, the electrical conductivity of the treated PLA-POY and PLA-DTY
fibers increases significantly from 1.2 × 10−3 to 5.3 × 10−3 μs/cm and 0.7 × 10−3 to 2.7 × 10−3 μs/cm,
Sampleswhereas,
respectively; Electrical
with theConductivity Samples of MWCNTs
increase of the concentration Electrical
from 4Conductivity
to 10 mg/mL, those
of thePLA-POY
PLA-POY and PLA-DTY 10 −5
9.5 ×fibers increase inapparently
OC6P30from 5.3 × 10 to 7.7 22.7
−3 × 10−3 μs/cm, and 2.7
OC2P10 1.2 OC6P40 181.8
OC2P20 14.3 OC6P50 204.1
OC2P30 14.1 OC8P10 6.8
OC2P40 14.3 OC8P20 14.1
OC2P50 14.7 OC8P30 245.2
OC4P10 5.3 OC8P40 409.6
OC4P20 13.7 OC8P50 371.4
OC4P30 15.6 OC10P10 7.7
OC4P40 21.7 OC10P20 14.1
OC4P50 37.0 OC10P30 129.1
OC6P10 15.4 OC10P40 270.3
OC6P20 17.2 OC10P50 526.3
Coatings 2019, 9, 651 8 of 12

Table 2. The electrical conductivity of PLA-DTY fibers treated by MWCNTs and PVAc in ethyl acetate
(unit: 10−3 µs/cm).

Samples Electrical Conductivity Samples Electrical Conductivity

PLA-DTY 1.1 × 10−4 TC6P30 14.0
TC2P10 0.7 TC6P40 60.5
TC2P20 8.3 TC6P50 106.6
TC2P30 8.8 TC8P10 4.0
TC2P40 8.9 TC8P20 9.0
TC2P50 8.9 TC8P30 76.8
TC4P10 2.7 TC8P40 103.7
TC4P20 8.5 TC8P50 127.0
TC4P30 9.4 TC10P10 4.8
TC4P40 39.2 TC10P20 9.0
TC4P50 73.9 TC10P30 69.2
TC6P10 3.6 TC10P40 118.0
TC6P20 9.7 TC10P50 130.8

When the concentration of PVAc is 10 mg/mL, with the increase of the concentration of MWCNTs
from 2 to 4 mg/mL, the electrical conductivity of the treated PLA-POY and PLA-DTY fibers increases
significantly from 1.2 × 10−3 to 5.3 × 10−3 µs/cm and 0.7 × 10−3 to 2.7 × 10−3 µs/cm, respectively;
whereas, with the increase of the concentration of MWCNTs from 4 to 10 mg/mL, those of the PLA-POY
and PLA-DTY fibers increase inapparently from 5.3 × 10−3 to 7.7 × 10−3 µs/cm, and 2.7 × 10−3 to 4.8
× 10−3 µs/cm, respectively. When the concentration of PVAc is 20 mg/mL, with the increase of the
concentration of MWCNTs from 2 to 10 mg/mL, the electrical conductivity of the treated PLA-POY and
PLA-DTY fibers almost does not change. However, when the concentration of MWCNTs is more than
30 mg/mL, the effect of MWCNTs on the electrical conductivity of the treated PLA-POY and PLA-DTY
fibers is significant. However, when the concentration of MWCNTs is more than 8 mg/mL, with the
further increase of the concentration of MWCNTs, the change of electrical conductivity of the treated
PLA-POY and PLA-DTY fibers is not obvious.
Here, MWCNTs are used as the conductive additives. Therefore, with the increase in the
concentration of MWCNTs, the conductive network can easily form so that the conductive properties
increase. PVAc is used as a dispersing agent to make the MWCNTs disperse uniformly in ethyl
acetate. Therefore, with the increase of PVAc, MWCNTs can be efficiently used by dispersing MWCNTs
uniformly in ethyl acetate so that the conductive properties increase. When the concentration of
MWCNTs is low (2 mg/mL), the PVAc concentration of 10 mg/mL is enough large to make MWCNTs
disperse uniformly in ethyl acetate, so that further increasing the concentration of PVAc cannot improve
the conductivity of the PLA fibers. In addition, when the concentration of PVAc is low (less than
20 mg/mL), it is difficult to make a large number of MWCNTs uniformly in ethyl acetate. Therefore,
MWCNTs cannot be used efficiently, thus further increasing the concentration is meaningless.

3.5. Tensile Properties

Figure 7 illustrates the curves of load-strain relationship of PLA-POY fibers treated by MWCNTs
and PVAc in ethyl acetate. The values of tensile force (F), elongation at break (ε), and work of rupture
(W) are listed in Table 3. As can be seen in Figure 7, the original PLA-POY fibers and treated PLA-POY
fibers present a typical tough fracture. It can be seen from Figure 7 and Table 3 that the tensile force of
the treated PLA-POY fibers is much higher than that of the original PLA-POY fibers. The reason is as
follows; the PLA-POY fibers have relatively low crystallinity when the PLA-POY fibers are treated
by MWCNTs and PVAc in ethyl acetate. The ethyl acetate first will make amorphous district of the
PLA-POY fibers swell. Then, when the PLA-POY fibers are taken out from the solution, ethyl acetate
will evaporate to induce crystallization of PLA-POY fibers to form a highly porous structure, which
makes the tensile force decrease obviously.
 the tensile force of the treated PLA-POY fibers is much higher than that of the original PLA-POY
fibers. The reason is as follows; the PLA-POY fibers have relatively low crystallinity when the
PLA-POY fibers are treated by MWCNTs and PVAc in ethyl acetate. The ethyl acetate first will
make amorphous district of the PLA-POY fibers swell. Then, when the PLA-POY fibers are taken out
from2019,
Coatings the solution,
9, 651 ethyl acetate will evaporate to induce crystallization of PLA-POY fibers to9form
of 12 a
highly porous structure, which makes the tensile force decrease obviously.

Figure Tensile
7. 7.
Figure properties
Tensile ofofPLA-POY
properties PLA-POYfibers
fiberstreated
treatedby
byMWCNTs
MWCNTsand
andPVAc
PVAcininethyl
ethylacetate:
acetate: (a)
30 (a)
mg/mL PVAc PVAc
30 mg/mL and (b) 8 mg/mL
and MWCNTs.
(b) 8 mg/mL MWCNTs.

Table 3. Tensile properties of PLA-POY fibers treated by MWCNTs and PVAc in ethyl acetate.
Table 3. Tensile properties of PLA-POY fibers treated by MWCNTs and PVAc in ethyl acetate.
Samples Tensile Force (cN) Elongation at Break (%) Work of Rupture (J)
Samples Tensile Force (cN) Elongation at Break (%) Work of Rupture (J)
PLA-POY
PLA-POY 9 ±9
566 ±566 ± 1± 1
46 46 0.40 ± 0.02
0.40 ± 0.02
OC2P30 304 ± 60 67 ± 14 0.4 ± 0.1
OC2P30 304 ± 60 67 ± 14 0.4 ± 0.1
OC4P30 286 ± 13 73 ± 6 0.36 ± 0.04
OC4P30
OC6P30 286 ± 13
251 ± 67 73 ± 6
61 ± 16 0.36 ± 0.04
0.3 ± 0.1
OC6P30
OC8P30 251 ± 67
288 ± 32 61 ± 16
49 ± 3 0.3 ± 0.1
0.25 ± 0.03
OC10P30
OC8P30 288 ± 32
318 ± 20 49 ± 3
95 ± 9 0.25 ± 0.03
0.51 ± 0.05
OC8P10
OC10P30 20 ± 10
318 ±211 ±±
9541 9 22 0.2 ± 0.1
0.51 ± 0.05
OC8P20 320 ± 53 53 ± 12 0.29 ± 0.08
OC8P10 211 ± 10 41 ± 22 0.2 ± 0.1
OC8P40 347 ± 35 81 ± 12 0.45 ± 0.09
OC8P20
OC8P50 320 ±401
53 ± 54 ± 12
53 87 ± 14 0.29
0.6 ± 0.08
± 0.1
OC8P40 347 ± 35 81 ± 12 0.45 ± 0.09
OC8P50 401 ± 54 87 ± 14 0.6 ± 0.1
Figure 7a and Table 3 illustrate that when the concentration of PVAc is 30 mg/mL, the effect
of MWCNTs concentration on tensile properties of PLA-POY fibers is small. However, Figure 7b
Figure 7a and Table 3 illustrate that when the concentration of PVAc is 30 mg/mL, the effect of
and Table 3 show that when the concentration of MWCNTs is 8 mg/mL, with the increase of PVAc
MWCNTs concentration on tensile properties of PLA-POY fibers is small. However, Figure 7b and
concentration from 10 to 50 mg/mL, the tensile force, strain, and work of rupture of the PLA-POY fibers
Table 3 show that when the concentration of MWCNTs is 8 mg/mL, with the increase of PVAc
increase from 211 to 401 cN, 41% to 87%, and 0.2 to 0.6 J, respectively. The reason is as follows; PVAc
concentration from 10 to 50 mg/mL, the tensile force, strain, and work of rupture of the PLA-POY
and PLA are compatible completely when the PLA-POY fibers are treated by MWCNTs and PVAc in
fibers increase from 211 to 401 cN, 41% to 87%, and 0.2 to 0.6 J, respectively. The reason is as follows;
ethyl acetate. The PVAc will coat the PLA-POY fibers and fill the pores to improve the tensile property
PVAc and PLA are compatible completely when the PLA-POY fibers are treated by MWCNTs and
of PLA-POY.
PVAc in ethyl acetate. The PVAc will coat the PLA-POY fibers and fill the pores to improve the
In addition, the curve of the PLA-POY fibers treated by MWCNTs and PVAc in ethyl acetate
tensile property of PLA-POY.
with 8 mg/mL MWCNTs and 10 mg/mL (OC8P10) is different from those of the PLA-POY fibers
In addition, the curve of the PLA-POY fibers treated by MWCNTs and PVAc in ethyl acetate
treated by MWCNTs and PVAc in ethyl acetate with more than 20 mg/mL. The latter owns an obvious
with 8 mg/mL MWCNTs and 10 mg/mL (OC8P10) is different from those of the PLA-POY fibers
stress-hardening district, whereas the stress-hardening district cannot be observed in the former,
treated by MWCNTs and PVAc in ethyl acetate with more than 20 mg/mL. The latter owns an
because the content of PVAc in the former is low. This further shows that the PVAc and PLA fibers
obvious stress-hardening district, whereas the stress-hardening district cannot be observed in the
have good adhesive force. PVAc can improve the tensile properties of highly porous PLA-POY fibers.
Figure 8 illustrates the curves of load–strain relationship of PLA-DTY fibers treated by MWCNTs
and PVAc in ethyl acetate. The values of tensile force (F), elongation at break (ε), and work of rupture
(W) are listed in Table 4. Figure 8 shows that the curve of original PLA-DTY fibers has a similar shape to
those of the treated PLA-DTY fibers; they present a typical tough fracture. It can be seen from Figure 8
and Table 4 that the tensile force of the treated PLA-DTY fibers is larger than that of original PLA-DTY
fiber. The reason is as follows; the effect of ethyl acetate on PLA-DTY is small, and the PVAc on the
surface of PLA-DTY fiber can improve the mechanical properties. However, Figure 8b shows that with
the increase of PVAc, the tensile properties of the treated PLA-DTY fibers almost do not change.
 has a similar shape to those of the treated PLA-DTY fibers; they present a typical tough fracture. It
can be seen from Figure 8 and Table 4 that the tensile force of the treated PLA-DTY fibers is larger
than that of original PLA-DTY fiber. The reason is as follows; the effect of ethyl acetate on PLA-DTY
is small, and the PVAc on the surface of PLA-DTY fiber can improve the mechanical properties.
However, Figure 8b shows that with the increase of PVAc, the tensile properties of the treated
Coatings 2019, 9, 651 10 of 12
PLA-DTY fibers almost do not change.

Figure 8. Tensile
Figure properties
8. Tensile of of
properties PLA-DTY fibers
PLA-DTY treated
fibers byby
treated MWCNTs and
MWCNTs PVAc
and inin
PVAc ethyl acetate:
ethyl acetate:(a)
30 mg/mL PVAc and
(a) 30 mg/mL (b)and
PVAc 8 mg/mL MWCNTs.
(b) 8 mg/mL MWCNTs.

Table 4. Tensile properties of PLA-DTY fibers treated by MWCNTs and PVAc in ethyl acetate.

Table 4. Tensile properties

Samples of PLA-DTY
Tensile Force (cN) fibers treated at
Elongation byBreak
MWCNTs
(%) and Work
PVAcof
inRupture
ethyl acetate.
(J)
PLA-DTY
Samples 85.0 ±(cN)
Tensile Force 0.8 Elongation12.6 ± 0.4 (%)
at Break 0.022of± Rupture
Work 0.001 (J)
TC2P30 111 ± 6 19 ± 3 0.041 ± 0.009
PLA-DTY 85.0 ± 0.8 12.6 ± 0.4 0.022 ± 0.001
TC4P30 107 ± 4 19 ± 2 0.041 ± 0.006
TC2P30
TC6P30 111 ± 6
103 ± 2 19 ± 3
19 ± 1 0.041 ± 0.009
0.037 ± 0.002
TC4P30
TC8P30 107 ±96 4±5 19 ±162 ± 3 0.041
0.030 ± 0.006
± 0.006
TC6P30
TC10P30 103 ±98 2±6 19 ±161 ± 2 0.037
0.031 ± 0.002
± 0.005
TC8P10
TC8P30 96 ± 94
5 ±4 16 ±133 ± 2 0.024
0.030 ± 0.006
± 0.005
TC8P20 95 ± 7 15 ± 3 0.027 ± 0.007
TC10P30 98 ± 6 16 ± 2 0.031 ± 0.005
TC8P40 86 ± 4 10 ± 2 0.018 ± 0.004
TC8P10
TC8P50 94 ± 4
95 ± 4 13 ± 2
14 ± 2 0.024
0.026 ± 0.005
± 0.005
TC8P20 95 ± 7 15 ± 3 0.027 ± 0.007
TC8P40 86 ± 4 10 ± 2 0.018 ± 0.004
It can be seen from Table 3 that for PLA-POY, the tensile properties of the treated PLA fibers are
TC8P50 95 ± 4 14 ± 2 0.026 ± 0.005
much smaller than those of the untreated PLA fibers. However, it is exciting that OC8P40 and OC8P50,
both with highbeelectrical
It can seen from conductivity,
Table 3 thatown high tensilethe
for PLA-POY, properties (Tables 1 of
tensile properties andthe3).treated
For PLA-DTY,
PLA fibers
although the tensile properties of the treated PLA fibers are much larger
are much smaller than those of the untreated PLA fibers. However, it is exciting that than those of the OC8P40
untreatedand
PLA fibers (Table
OC8P50, 4), the
both with TC8P50
high withconductivity,
electrical the highest electrical
own high conductivity does not
tensile properties have the
(Tables highest
1 and 3). For
strength
PLA-DTY,(Tables 2 and 4).
although theHowever, the difference
tensile properties of thebetween
treated PLAthe tensile
fibers strength
are muchoflarger
TC8P50 and
than the of
those
highest strength is small. Therefore, it can be concluded that PLA-POY and PLA-DTY,
the untreated PLA fibers (Table 4), the TC8P50 with the highest electrical conductivity does not both with high
electrical
have the conductivity, own satisfactory
highest strength (Tables 2 and tensile properties.the difference between the tensile strength of
4). However,
TC8P50 and the highest strength is small. Therefore, it can be concluded that PLA-POY and
4. Conclusions
PLA-DTY, both with high electrical conductivity, own satisfactory tensile properties.
The conductive PLA-POY and PLA-DTY fibers are produced successfully by coating method using
ethyl acetate as solvent, MWCNTs as conductive filler, and PVAc as dispersing agent and coating agent.
4. Conclusions
The PLA fibers are characterized by SEM, FTIR, DSC, resistance meter, and tensile test. The larger the
PVAc concentration is, the more uniformly the MWCNTs disperse in ethyl acetate. MWCNTs have
successfully coated the surface of PLA-POY and PLA-DTY fibers. The highly porous structures form
when PLA-POY fibers are treated by ethyl acetate, decreasing the tensile forces. The tensile force of
original PLA-POY fibers is 566 cN, whereas that of the treated PLA-POY fibers ranges from 211 to
401 cN. However, the PVAc can improve the tensile force of the treated PLA-POY fibers. When the
concentration of MWCNTs is 8 mg/mL, coupled with the increase of PVAc concentration from 10 to
50 mg/mL, the tensile force of the PLA-POY fibers increases from 211 to 401 cN. For PLA-DTY fibers,
the effect of ethyl acetate on surface morphology is small. Therefore, the treated PLA-DTY fibers own
higher tensile properties. With the increase of PVAc and MWCNTs, the conductive properties of the
PLA fibers increase. The electrical conductivity of PLA-POY and PLA-DTY fibers can reach 0.53 and
0.13 µs/cm, respectively.
Coatings 2019, 9, 651 11 of 12

Author Contributions: Formal Analysis, Q.L. and Y.Z.; Investigation, Q.L., Y.Z. and Y.S.; Data Curation, Y.Z.;
Writing—Original Draft Preparation, Q.L.; Writing—Review and Editing, Q.L. and B.D.; Supervision, Q.L., Y.L.
(Yuhao Li), H.G. and Y.L. (Yonggui Li); Funding Acquisition, H.G. and Y.L. (Yonggui Li).
Funding: This research was supported by the Equipment Pre-Research Fund (61409220412); the Chinese
Postdoctoral Science Foundation (2019M651699); the National Defense Cultivation Project of Fundamental
Research Funds for the Central Universities (JUSRP41904); the Key Research and Development Program (Industry
Forward and Common Key Technology) of Suqian City (H201708); the Open Project Program of Fujian Key
Laboratory of Novel Functional Textile Fibers and Materials, Minjiang University, China (FKLTFM1714); the Jiangsu
Overseas Research Training Program for University Prominent Young and Middle-Aged Teachers and Presidents;
the Foundation of Key Laboratory of Pulp and Paper Science and Technology of Ministry of Education/Shandong
Province of China (KF201714); the 111 Project (B17021); the Priority Academic Program Development of Jiangsu
Higher Education Institutions; and the Top-Notch Academic Programs Project of Jiangsu Higher Education
Institutions (PPZY2015B147).
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Liu, Q.S.; Zhao, M.M.; Zhou, Y.Q.; Yang, Q.B.; Shen, Y.; Gong, R.H.; Zhou, F.L.; Deng, B.Y. Polylactide single-polymer
composites with a wide melt-processing window based on core-sheath PLA fibers. Mater. Des. 2018, 139, 36–44.
[CrossRef]
2. Liu, Q.S.; Wu, C.; Zhang, H.X.; Deng, B.Y. Blends of polylactide and
poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with low content of hydroxyvalerate unit: Morphology,
structure, and property. J. Appl. Polym. Sci. 2015, 132, 42689. [CrossRef]
3. Liu, Q.S.; Sun, Y.Y.; Xia, S.N.; Zhang, H.X.; Tao, X.L.; Liu, Y.Y.; Deng, B.Y. Structure and mechanical property
of polylactide fibers manufactured by air drawing. Text. Res. J. 2016, 86, 948–959. [CrossRef]
4. Schmack, G.; Tändler, B.; Optiz, G.; Vogel, R.; Komber, H.; Häuβler, L.; Voigt, D.; Weinmann, S.; Heinemann, M.;
Fritz, H.-G. High-speed melt spinning of various grades of polylactides. J. Appl. Polym. Sci. 2004, 91, 800–806.
[CrossRef]
5. Takasaki, M.; Ito, H.; Kikutani, T. Development of stereocomplex crystal of polylactide in high-speed melt
spinning and subsequent drawing and annealing process. J. Macromol. Sci. Part B Phys. 2003, B42, 403–420.
[CrossRef]
6. Furuhashi, Y.; Kimura, Y.; Yamane, H. Higher order structural analysis of stereocomplex-type poly(lactic
acid) melt-spun fibers. J. Polym. Sci. Part B Polym. Phys. 2007, 45, 218–228. [CrossRef]
7. Solarski, S.; Mahjoubi, F.; Ferreira, M.; Devaux, E.; Bachelet, P.; Bourbigot, S.; Delobel, R.; Coszach, P.;
Murariu, M.; Ferreira, A.D.S.; et al. (Plasticized) Polylactide/clay nanocomposite textile: Thermal mechanical,
shrinkage and fire properties. J. Mater. Sci. 2007, 42, 5105–5117. [CrossRef]
8. Li, L.Z.; Huang, W.; Wang, B.J.; Wei, W.F.; Gu, Q. Properties and structure of polylactide/poly
(3-hydroxybutyrate-co-3-hydroxyvalerate) (PLA/PHBV) blend fibers. Polymer 2015, 68, 183–194. [CrossRef]
9. Hufenus, R.; Reifler, F.A.; Maniura-Weber, K.; Spierings, A.; Zinn, M. Biodegradable bicomponent fibers from
renewable sources: Melt-spinning of poly(lactic acid) and poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)].
Macromol. Mater. Eng. 2012, 297, 75–84. [CrossRef]
10. Zhang, H.X.; Bai, H.W.; Liu, Z.W.; Zhang, Q.; Fu, Q. Toward high-performance poly(L-lactide) fibers via
tailoring crystallization with the aid of fibrillar nucleating agent. ACS Sustain. Chem. Eng. 2016, 4, 3939–3947.
[CrossRef]
11. Liu, Q.S.; Yang, Q.B.; Zhou, Y.Q.; Zhao, M.M.; Shen, Y.; Zhou, F.L.; Gong, R.H.; Deng, B.Y. A facile method of
preparing highly porous polylactide microfibers. J. Appl. Polym. Sci. 2018, 135, 45860. [CrossRef]
12. Rentenberger, R.; Cayla, A.; Villmow, T.; Jehnichen, D.; Campagne, C.; Rochery, M.; Devaux, E.; Pötschke, P.
Multifilament fibres of poly(ε-caprolactone)/poly(lactic acid) blends with multiwalled carbon nanotubes as
sensor materials for ethyl acetate and acetone. Sens. Actuat. B Chem. 2011, 160, 22–31. [CrossRef]
13. Zhang, X.H.; Lu, W.B.; Zhou, G.H.; Li, Q.W. Understanding the Mechanical and Conductive Properties of
Carbon Nanotube Fibers for Smart Electronics. Adv. Mater. 2019, 1902028. [CrossRef] [PubMed]
14. Zhao, Y.T.; Sun, X.T.; Zhao, H.T.; Tian, M.W.; Zhang, X.S.; Zhu, S.F. A simple and scalable production of
conductive fibers with excellent washing resistance. Mater. Lett. 2019, 239, 9–12. [CrossRef]
Coatings 2019, 9, 651 12 of 12

15. Liu, Q.S.; Jiang, J.Z.; Zhang, H.X.; Wang, J.C.; Li, X.M.; Li, Y.H.; Deng, B.Y. Miscibility and phase morphology
of polylactide/poly(vinyl acetate-co-vinyl alcohol) blends obtained by melt mixing. Polym.-Plast. Technol.
2014, 53, 1590–1597. [CrossRef]
16. Liu, Q.S.; Zhang, H.X.; Zhu, M.F.; Dong, Z.; Wu, C.; Jiang, J.Z.; Li, X.R.; Luo, F.; Gao, Y.X.; Deng, B.Y.; et al.
Blends of polylactide/thermoplactic elastomer: Miscibility, physical aging and crystallization behaviors.
Fibers Polym. 2013, 14, 1688–1698. [CrossRef]

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).