European Polymer Journal 114 (2019) 476–484

Contents lists available at ScienceDirect

European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Bio-based polyesters based on 2,5-furandicarboxylic acid as 3D-printing T

materials: Design, preparation and performances
Yiting Genga,b,1, Zhao Wanga,b,1, Xiaoran Hud, , Yan Lia,b, Qinan Zhanga,b, Yujie Lia,b,
⁎

Runguo Wanga,b, Liqun Zhanga,c,

⁎

a
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, PR China
b
Key Laboratory of Beijing City for Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, PR China
c
Beijing Laboratory of Biomedical Materials, Beijing University of Chemical Technology, Beijing 100029, PR China
d
University of Electronic Science and Technology, Chengdu, Sichuan 611731, PR China

A RT ICLE INFO ABSTRACT

Keywords: The 3D-printing technology allows to manufacture polymers into desired shape. This work presents novel bio-
3D-printing based copolyesters (PHPF) prepared by the polycondensation of 2,5-furandicarboxylic acid, 1,6-hexanediol and
Bio-based 1,2-propanediol as 3D-printed materials. These PHPF exhibit superior thermal stability. By tailoring the contents
Toughness of 1,2-PDO, the PHPF exhibit optimum mechanical properties with tensile strength of 42.7 Mpa, elongation at
2,5-Furandicarboxylic acid
break of 515% and impact strength of 35.62 KJ/m2, respectively. The 3D-printed PHPF shows a satisfactory
mechanical properties obtained from tensile test and reliable microstructure observed by SEM. Both the thermal
stability and mechanical properties of PHPF were far beyond polylactide, a present most used bio-based 3D-
printed polymer, which revealed PHPF deserve to be promising 3D-printing materials.

1. Introduction
Three-dimensional (3D) -printing technology, as the core tech-
nology of the third industrial revolution, has developed rapidly since
1980s [1]. Nowadays, it is widely involved in custom labware [1],
medicine [2–4], construction [5], food [6,7], electronic components
[8–10], daily supplies [11], and many other fields. The principle of 3D-
printing technology is additive manufacturing, it allows to choose the
appropriate materials and fabricate the final products according to the
three-dimensional models from a computer-aided design (CAD) [12].
Several printing processes are developed to fabricate polymers [13–15],
such as fused deposition modeling (FDM), stereolithography (SLA), and
selective laser sintering (SLS). Among them, FDM 3D-printing tech-
nology is most extensively used for its low-cost, simple process and
convenient preparation in producing thermoplastic materials. The
process of FDM, is to fabricate a 3D model by extruding thermoplastic
materials and depositing the materials above their softening point onto
a stage layer by layer. Such process is popularly applied to desktop
printers whose products primarily cover toys and daily necessities.
Nowadays, the best printable polymers available for FDM, also the
most commonly used, are polylactic acid (PLA) [12,16] and acryloni-
trile butadiene styrene (ABS). Since we are facing the serious petroleum
crisis [17,18], ABS as well as other petroleum based materials with
good strength and toughness encounters a tough challenge. By contrast,
bio-based PLA is a preeminent candidate for FDM due to its renewable
origins, nontoxicity, biocompatibility and good processability [19–23],
and having attracted increasingly attention. Giordano and coworkers
[24] prepared test bars by 3D-printing of low and high molecular PLA.
The printed bars performed qualified tensile strength, ranging from
16.0 to 17.4 MPa, but the elongation at break, which is 2–6%, thermal
stability are barely satisfying, which needs to be modified to meet the
3D-printing requirements of materials. FDM 3D-printing of modified
PLA materials has also been reported. Serra et al. [25] employed PEG/
PLA to fabricate 3D-printed scaffolds. Kulinski and Piorkowska [26]
found that the incorporation of PEG into PLA facilitated scaffolds pro-
cessing, but still had difficulties in raising the elongation at break over
20%. Senatov et al. [27] obtained porous scaffolds by 3D-printing HA/
PLA blends, which displayed tensile strength and elongation at break
with the value of 14.5 MPa and 15%, separately. Fustier et al. [28]
found that PEG/PLA copolymer began its degradation at an approx-
imate temperature of 200 °C. In short, the toughness and the thermal
stability of current PLA-based products are not perfectly satisfying the
requirement for 3D-printed materials. Thus, the goal of preparing 3D-
printing polymers with bio-based monomers is to combine the

⁎
Corresponding authors at: State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, PR China.
E-mail address: zhanglq@mail.buct.edu.cn (L. Zhang).
1
Yiting Geng and Zhao Wang contribute equally to this paper.

https://doi.org/10.1016/j.eurpolymj.2018.10.041
Received 29 July 2018; Received in revised form 26 October 2018; Accepted 27 October 2018
Available online 29 October 2018
0014-3057/ © 2018 Published by Elsevier Ltd.
Y. Geng et al. European Polymer Journal 114 (2019) 476–484

Table 1
Mechanical properties of furan-aromatic polyesters.
Polyesters Tensile strength/ Elongation at break/ Tensile modulus/
(MPa) (%) MPa

PEF 66.7 4.2 2070

PTF 68.2 46 1550
PBF 19.8 2.8 1110
PHF 35.5 210 493
POF 20.3 15 340

Table 2
Thermal properties of furan-aromatic polyesters.
Samples DSC TGA

Tg/(°C) Tm/(°C) Td,5%/(°C) Td,max/(°C)

PEF 89.9 210.4 389.3 407.4

PET 79.0 246.0 407.3 440.0
PTF 57.9 no 375.3 396.4 Fig. 2. 1H NMR spectra of PHPF.
PTT 45 229.0 382.2 399.3
PBF 30.5 172.2 373.1 392.2
PBT 48.5 227.1 384.0 407.0 (POF). Mechanical data demonstrated the incorporation of FDCA im-
PHF 28.1 148.2 374.8 389.0 prove tensile strength, tensile modulus, and elongation at break, from
PHT 36.1 150.7 386.1 400.0
19.8 to 68.2 MPa, from 340 to 2070 MPa, and from 4.2 to 210%, re-
POF 21.8 148.6 375.1 390.7
POT 17.4 132.8 385.5 403.6 spectively, as shown in Table 1. The researchers also found the thermal
properties of FDCA-based copolyesters were similar to corresponding
PTA-based copolyesters, as shown in Table 2,. Ma et al. [40] synthe-
advantages of both PLA and ABS so that the materials could manifest sized 2,5-furandicarboxylic acid (FDCA) with ethylene glycol (EG) and
renewable source, advantageous toughness and thermal stability. 1,4-butylene glycol (BG) via polytransesterification, and found that the
Employing bio-based monomers with a cyclic structure could be an thermal properties of the final copolyesters could be adjusted by
effective idea to improve mechanical performances and thermal stabi- changing EG/BG molar ratios in the copolyesters. The renewable ori-
lity of polymers. For instance, 2,5-furandicarboxylic acid (FDCA), a bio- gins, excellent mechanical strength, and thermal stability of FDCA-
based cyclic monomer with similar structure to p-phthalic acid(PTA) based copolyesters will endow them to be a viable alternative to con-
[29], is identified as one of the “Top 12” potential building-block ventional ABS or PLA-based 3D-printing materials. However, to date,
chemicals from biomass by the US Department of Energy [30]. To date, there is still no report on the application of FDCA-based copolyesters in
numerous interests have been cast on developing FDCA [31–34], and its 3D-printing materials.
copolymers using other aliphatic or aromatic monomers [35–37]. Inspired by the previous study, in this article, we prepared a series
Moore and Kelly et al. [38] focused on the synthesis of poly(hexylene of novel bio-based copolyesters based on 2,5-furandicarboxylic acid,
2,5-furandicarboxylate) by both melt polytransesterification and solu- 1,6-hexanediol and 1,2-propanediol by melting polycondensation. The
tion polycondensation. Jiang et al. [39] studied a selection of copo- composition and structure, thermal and crystalline properties, me-
lyesters based on FDCA, viz. poly(1,2-ethylene 2,5-furandicarboxylate) chanical properties, contact angles, and 3D-printing tests were char-
(PEF), poly(1,3-propylene 2,5-furandicarboxylate) (PPF), poly(1,4-bu- acterized and investigated in detail.
tylene 2,5-furandicarboxylate) (PBF), poly(1,6-hexylene 2,5-fur-
andicarboxylate) (PHF) and poly(1,8-octylene 2,5-furandicarboxylate)

OH
HOOC o COOH
OH HO
+ HO +

2,5-FDCA 1,6-HDO 1,2-PDO

ºC ºC ºC
TBT Catalyst
ºC

O * O
O O
O C o O C o
C O C O
O O
m n

Fig. 1. Polymerization reactions of PHPF.

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Y. Geng et al. European Polymer Journal 114 (2019) 476–484

Table 3
Compositions and molecular weights of PHPF.
Sample Molar compositions FDCA/1,6-HDO/1,2-PDO Molecular weights ρ/(g·cm−3)

Feeda Copolyesterb Mn × 10−4/(g/mol)c PDIc

PHF 1.00/1.00/0.00 1.00/1.00/0.00 2.98 2.81 1.26

PHPF-10 1.00/0.90/0.10 1.00/0.80/0.20 3.17 2.57 1.23
PHPF-20 1.00/0.80/0.20 1.00/0.76/0.24 2.71 2.37 1.23
PHPF-30 1.00/0.70/0.30 1.00/0.68/0.32 2.57 2.38 1.18
PHPF-40 1.00/0.60/0.40 1.00/0.58/0.42 2.47 2.35 1.21
PHPF-50 1.00/0.50/0.50 1.00/0.51/0.49 1.73 2.03 1.32
PPF 1.00/0.00/1.00 1.00/0.00/1.00 1.27 1.92 1.31

a
Molar ratio in the initial feed.
b
Molar ratio in the copolyester, determined by 1H NMR.
c
Number-average molecular weights (Mn) and polydispersity index (PDI) determined by GPC in CH3Cl3 against PS standards.

was denoted as PHPF-X, the copolyester only containing FDCA and 1,2-
PDO was called PPF, the copolyester only containing FDCA and 1,6-
HDO was called PHF.

2.3. 3D-printing of PHPF

The PHPF were changed into filaments with a diameter of 1.75 mm,
and then they were printed using a FDM 3D printer.

2.4. Characterization and measurements

Fig. 3. FTIR spectra of PHPF.
2. Experimental section
2.1. Reagents and materials
2,5-furandicarboxylic acid (FDCA) (purity 99%) was supplied by
Innochem, 1,6-hexanediol (HDO) (purity 97%) was supplied by
JKchemical, 1,2-propanediol (PDO) (purity > 99.0%) was supplied by
TCI, tetrabutyltitanate (TBT) were supplied by Aladdin. Chloroform and
methanol were purchased from Beijing Chemical Works.
2.2. Preparation of PHPF
The PHPF with different molar ratio of 1,2-propanediol were ob-
tained via direct esterification and polycondensation method under
solvent-free condition with TBT as catalyst, as depicted in Fig. 1. The
molar ratios 2,5-furandicarboxylic acid/1,6-hexanediol varied from
1:1.2 to 1:0.5 and 1,2-propanediol/1,6-hexanediol was fixed at 2:1.
Typically, calculated PHPF-10, 2,5-FDCA (28.89 g, 0.185 mol), 1,6-
HDO (19.69 g, 0.167 mol), 1,2-PDO (25.41 g, 0.334 mol) were heated at
170 °C for 3 h, 190 °C for 2 h and 200 °C for 1 h with TBT (0.1 wt%
relative to all chemicals) as the catalyst in a 100-ml three-neck flask
equipped with a mechanical stirrer and under a dry nitrogen atmo-
sphere. Then the polymerization was performed at 235 °C for 3 to 5 h
under reduced pressure (< 300 Pa) with TBT (0.1 wt% relative to all
chemicals) as the catalyst until the Weisenberg effect was observed. The
obtained copolyester was dissolved in chloroform and precipitated in
excess methanol to remove any unreacted monomers and remaining
oligomers. Finally, the copolyester was collected by filtration, ex-
tensively washed with methanol, and dried in vacuum at 60 °C. The
copolyester containing X mol% of 1,2-propanediol relative to all diols
1
H NMR measurements of the copolyesters were collected on a
Bruker AV600 spectrometer. TFA was used as the solvent for the
measurements. The FTIR spectra of the copolyesters were recorded on a
BrukerTensor 27 spectrometer. The spectra were obtained in the wa-
venumber ranging from 4000 to 500 cm−1 at a resolution of 4 cm−1.
The average molecular weight was determined by gel permeation
chromatographic (GPC) on a Waters Breeze2 instrument equipped with
three columns (PLgel MIX-D and PLgel MIX-C) using trichloromethane
as the solvent and a Waters 2414 refractive index detector. A poly-
styrene standard was used for calibration. The densities of copolyesters
were calculated by Eq. (1):
= m /(V1 V2) (1)
where ρ is the density (kg/m3), m is the quality of the sample (kg), V1 is
the volume of water in cylinder (m3), and V2 is the volume of water in
cylinder in which solid sample immerged (m3).
The thermal stability was determined by thermogravimetric ana-
lysis (TGA) on a STARe system TGA/DSC1 apparatus (Mettler-Toledo
International Inc., Switzerland). A sample of 10 mg was heated from 25
to 800 °C at a heating rate of 10 °C/min under a nitrogen flow of 50 ml/
min. Differential scanning calorimetry (DSC) measurements were ob-
tained with a Mettler-Toledo DSC instrument under nitrogen. A sample
was heated to 200 °C at 10 °C/min and kept isothermal for 5 min to
remove any previous thermal history. Then it was cooled to −50 °C at
10 °C/min and reheated up to 200 °C at 10 °C/min. X-ray diffraction
(XRD) measurements were carried out on a D/Max2500 VB2t/PC X-ray
diffractometer (Rigaku, Japa) with a Cu target radiation in a 2θ range
from 5° to 90° at an angular resolution of 0.5°.Tensile tests were carried
out on a CMT 4104 Electrical Tensile Instrument (Shenzhen SANS Test
Machine Co., Ltd., China) equipped with a 10kN load cell. The samples
for tensile test were obtained by being pressed under 10 MPa at 170 °C
for 10 min and then 10 MPa at 25 °C for 5 min, finally cut into
Dumbbell-shaped samples. The Dumbbell-shaped samples (1 mm thick
and 4 mm wide) were measured at 25 °C and a crosshead speed of
5 mm/min. For each measurement, five samples were tested and the
average was selected. Impact tests were conducted on a XJJD pendulum
impact testing machine (Chengde Jinjian Testing Instrument Co., Ltd.,
China). The samples for impact test were obtained by being pressed
under 10 MPa at 170 °C for 10 min and then 10 MPa at 25 °C for 5 min

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Y. Geng et al.
Fig. 4. (a) TGA traces of PHPF under inert atmosphere; (b) derivative curves of PHPF.
in a mould (4 mm thick, 10 mm wide and 80 mm length), finally breach
a 2 mm notch using a JJNAM-11 Milling Notch Testing Machine
(Chengde Jinjian Testing Instrument Co., Ltd., China).
Morphology was observed by a scanning electron microscope (SEM)
(S4800, Hitachi Co., Japan) at 5 kV. Tensile-fractured surfaces of the
copolyesters were coated with a thin layer of gold before being ob-
served under the microscope. Contact angle were measured with an
OCA 15EC contact angle goniometer (Dataphysics Instruments GmbH,
Germany) at room temperature and the results reported were the mean
values of three replicates.
The 3D-printed samples were fabricated by a BFB 3000 3D-printer
(3D system, USA) at 220 °C. Stress-strain curves were obtained using a
CMT 4104 Electrical Tensile Instrument (Shenzhen SANS Test Machine
Co., Ltd., China). Morphology was investigated by a scanning electron
microscope (SEM) (S4800, Hitachi Co., Japan) at 5 kV.
3. Results and discussions
3.1. Molecular weights and structure characterization of PHPF
The number-average molecular weights of the copolyesters range
from 1.27 × 104 to 3.17 × 104 g/mol and polydispersities (PDI) range
from 1.92 to 2.81 shown in Table 1.
The compositions of the PHPF are confirmed by 1H NMR and FTIR. A
representative 1H NMR spectrum of PHPF-50 is shown in Fig. 2. In Fig. 2,
all proton signals from the repeating units of the copolyesters are found
at the expected chemical shift values with matching multiplicities. The
singlet at 7.44 ppm confirms the presence of 2,5-furandicarboxylic acid.
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European Polymer Journal 114 (2019) 476–484
The signals of protons belonging to the methylene groups in 1,6-hex-
anediol eOeCH2eCH2eCH2eCH2eCH2eCH2eOe are found at 4.58,
1.97, and 1.65 ppm, respectively. The chemical shifts at 4.80 ppm,
4.69 ppm, 5.77 ppm and 1.62 ppm are attributed to eOeCH(H)eCH
(CH3)eOe belonging to the methine group, methylene group, and me-
thyl group provided by 1,2-propanediol. The molar ratios of each
monomer (FDCA/HDO/PDO) in PHPF are calculated by integrating of
the peak area in the 1H NMR spectrum, and the results are shown in
Table 3. The molar ratios of each monomers in PHPF are similar to their
feed ratios.
In Fig. 3, all the FTIR spectra exhibit similar absorptions. The ab-
sorptions at 2962 cm−1 and 2858 cm−1 are assigned to the symmetric
and the asymmetric stretching vibration of methylene (eCH2), respec-
tively. The stretching vibration absorption at 3115 cm−1 and
1042 cm−1 belonging to the ]CH groups and furan ring characteristic
peak in 2,5-FDCA, respectively. The intense absorption at 1727 cm−1 is
associated with the stretching vibration of the carbonyl group (C]O),
an indication of the formation of ester bonds. The absorption at
1277 cm−1 confirms the presence of the CeOeC]O groups of ester
bonds. These results prove we succeed in introducing three monomers
into the macromolecular chains of PHPF.
3.2. Thermal and crystalline properties of PHPF
Thermogravimetric analysis (TGA) measurements are conducted to
evaluate the thermal stability of the PHPF. In Fig. 4, a one-step de-
gradation occurred in all samples. The temperature at 5% weight loss
(Td, 5%) of PHPF are above 350 °C, and the temperature at the
Y. Geng et al. European Polymer Journal 114 (2019) 476–484

Fig. 6. WAXD patterns of PHPF.

deteriorate the mobility and flexibility of the molecular chains [41].

The crystallization behaviour of PHPF is corroborated by wide-angle
X-ray diffraction (WAXD), and the diffraction patterns are shown in
Fig. 6. Diffractogram of PHF displayed three sharp signals at
2θ = 13.82°, 17.4°, 24.54°, respectively. Whereas, the sharp diffraction
peaks tend to decrease in height with an increasing content of 1,2-
propanediol, indicating a decrease in crystallinity. The decreased
crystallinity is due to a diminished chain mobility and or difficulty in
chain packing, which also confirms that 1,2-propanediol has the ability
to restrict the crystallization of copolyesters, in accordance with the
DSC results.
Fig. 5. DSC curves of PHPF: (a) cooling; (b) second heating.

Table 4 3.3. Mechanical properties of PHPF

The results of DSC and TGA of PHPF.
Samples DSC TGA The mechanical properties of copolyesters are tested by tensile and
impact measurements. Thereinto, PHPF-50 and PPF are too brittle to
Tg/(°C) Tm/(°C) Td,5%/(°C) Td,max/(°C) cut into unbroken Dumbbell-shaped samples. In Fig. 7 and Table 3,
PHPF exhibit desirable results in terms of toughness and elongation at
PHF 10.0 144.5 358.7 389.3
PHPF-10 17.5 – 358.0 385.7 break, which ranges from 216 to 515%, far exceeding that of PLA
PHPF-20 22.3 – 356.0 385.0 ranging from 2 to 6% [24]. The increasing amount of 1,2-propanediol
PHPF-30 29.1 – 354.7 382.7 could decrease not only the tensile strength but also the elongation at
PHPF-40 35.6 – 351.3 381.0
break of PHPF by lowering the molecular weights. The morphology of
PHPF-50 41.1 – 348.7 378.3
PPF 92.2 – 340.0 365.7 tensile fracture surface of PHPF-10 and PHPF-40 is investigated by
SEM. Obviously, PHPF-10 presents a ductile fracture surface with fibrils
Tg, the glass-transition temperature. while PHPF-40 shows a mirror-like smooth brittle fracture surface,
Tm, melting point. which confirms the better toughness of PHPF-10.
Td,5%, the temperature at 5% weight loss. Impact strength of PHPF with different 1,2-propanediol content is
Td,max, the temperature at the maximum rate of their degradation. depicted in Fig. 8 and Table 5. The impact strength of PHPF was firstly
increased with increasing content of 1,2-PDO due to the promoting
maximum rate of their degradation (Td, max) are above 380 °C, as mobility of macromolecular chains and then decreased because of the
presented in Table 2. Moreover, both the Td,5% and Td,max of these co- decreased molecular weights. According to previous literature [42],
polyesters decreasing slightly with increasing content of 1,2-propane- The impact strength of PHPF-10 was about 13.2 times over that of PLA
diol in the copolyesters which is attribute to the decreasing molecular (2.7 KJ/m2) indicating the outstanding toughness of PHPF-10. The SEM
weight of PHPF. Obviously, the Td,5% and Td,max of the PHPF are higher micrographs are presented in Fig. 8. The impact fracture surface of
than those of PLA, which indicates that PHPF possesses a better thermal PHPH-10 presented a deformed matrix with new surface and wrinkles
stability than PLA due to the introduction of FDCA with a rigid cyclic and fibrils on it, indicating a ductile fracture when subjected stress.
structure. However, the impact fracture surface of PHPH-40 shows a brittle
Differential scanning calorimetry (DSC) measurements are con- fracture evidenced by the mirror-like smooth surface. According to the
ducted to evaluate the thermal properties of the PHPF. The cooling and tensile and impact measurements, PHPF-10 seems to have the optimum
second heating DSC traces of the PHPF are depicted in Fig. 5, and the mechanical properties.
thermal data from TGA and DSC are compared in Table 4. The crys- Fig. 9 shows that the contact angles of PHPF are about 83.8–108.1°,
tallization of PHPF gradually decreased with increasing content of 1,2- which indicates that they are transforming from hydrophilic to hydro-
propanediol, as confirmed by the decreased intensity of sharp crystal- phobic with an increasing 1,2-propanediol content. The introduction of
lization peak which is because the side methyl group of 1,2-propanediol hydrophobic groups to these materials makes it possible for them to
could increase steric hindrance of the molecular chains and further block the water and to be self-cleaning.

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Y. Geng et al. European Polymer Journal 114 (2019) 476–484

Fig. 7. Stress-strain curves of PHPF with SEM micrographs of tensile surface ((a) and (b)).

Fig. 8. Impact strength of PHPF with SEM micrographs of impact fracture surface ((a) and (b)).

Table 5 3.4. 3D-printing performances of PHPF

The results of mechanical properties of PHPF.
copolyesters Tensile strength/ Elongation at break/ Impact strength/
Considering PHPF-10 and PHPF-20 behave better mechanical
(MPa) (%) (KJ/m2) properties than materials with other 1,2-propanediol ratio, we fabricate
tensile samples of PHPF-10 and PHPF-20 by FDM 3D-printing tech-
PHF 38.6 282 15.85 nology, as shown in Fig. 10. Generally, the FDM 3D printing method
PHPF-10 42.7 515 35.62
PHPF-20 40.7 424 21.41
utilize the melting state of the thermoplastic crystallized plastics. Dif-
PHPF-30 36.6 361 6.98 ferent with these material, the amorphous materials with no melting
PHPF-40 24.0 216 2.88 point could also be processed with 3D printing by utilizing their low Tg.
PLA 40 2–6 2.70 Above the Tg, the materials show a viscoelasticity property. Although
PHPF-10 has no Tm, but at the processing temperature, PHPF-10 has
very low viscosity that ensured it could be easily extruded and printed.

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Fig. 9. Contact angles of PHPF.

Fig. 10. 3D-printing tensile samples.

Fig. 12. Mechanical properties of compressive tensile sample and 3D-printing

tensile samples.

Fig. 11 shows the SEM micrographs of tensile fracture surface of the 3D-
printed samples. The presence of pores is evident and all the pores are
open and interconnected through networks of channel, the layers are
visible and are firmly interconnected.
The mechanical properties of 3D-printing samples in comparison
with conventional compressive samples are investigated by tensile test.
In Fig. 12, though the tensile strength of 3D-printing samples are lower
than that of compressive samples, but still satisfy ordinary requirements
of 3D-printing polymers. Moreover, with an increasing content of 1,2-
propanediol, the tensile strength of 3D-printing samples decrease as
well as that of compressive samples. The elongation at break of the
samples are better than that of compressive samples, indicating the
eminent toughness of materials fabricated through FDM 3D-printing
possesses. Additionally, several 3D-printed products are shown in
Fig. 13, indicating the practicability of the 3D-printing PHPF. Table 6
shows several performances of PHPF-10 in comparison with that of
PLA, PHPF-10 exhibits better thermal stability and toughness than PLA,
which means PHPF-10 deserve to be promising 3D-printing materials.
Fig. 11. SEM micrographs of fracture surface of 3D-printing samples.

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Y. Geng et al. European Polymer Journal 114 (2019) 476–484

contact angles of PHPF ranged from 83.8° to 108.1°, implied that they
were transforming from hydrophilic to hydrophobic. The tensile tests
indicated favorable mechanical properties of 3D-printing PHPF. The
SEM micrographs confirmed reliable microstructure of PHPF. The re-
newable sources, perfect toughness and qualified 3D-printing perfor-
mances enable the PHPF to be suitable candidates in 3D-printing ap-
plications.

Acknowledgements

This work was supported by the National Key Research and

Development Program of China (2017YFB0306900
(2017YFB0306904)). National Science Foundation for Young Scientists
of China (51703007), and Innovative Research Groups (51221002 and
51521062).

Data availability

The raw/processed data required to reproduce these findings cannot

be shared at this time as the data also forms part of an ongoing study.

Appendix A. Supplementary material

Supplementary data to this article can be found online at https://

doi.org/10.1016/j.eurpolymj.2018.10.041.

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