polymers

Article
Effect of Thermal Processing and Heat Treatment
Condition on 3D Printing PPS Properties
Peng Geng, Ji Zhao, Wenzheng Wu *, Yulei Wang, Bofan Wang, Shuobang Wang and Guiwei Li
School of Mechanical and Aerospace Engineering, Jilin University, Changchun 130025, Jilin, China;
gengpeng15@mails.jlu.edu.cn (P.G.); jzhao@jlu.edu.cn (J.Z.); yulei15@mails.jlu.edu.cn (Y.W.);
wangbf1415@mails.jlu.edu.cn (B.W.); wangsb1416@mails.jlu.edu.cn (S.W.); ligw15@mails.jlu.edu.cn (G.L.)
* Correspondence: wuwz@jlu.edu.cn; Tel.: +86-138-948-14109




Received: 13 July 2018; Accepted: 30 July 2018; Published: 6 August 2018


Abstract: Polyphenylene sulfide (PPS) is a high-performance semi-crystalline thermoplastic polymer

that is widely used in the automotive, electronics, and aerospace industries, as well as other fields.
However, PPS introduces several challenges in fused deposition modeling owing to its inherent
properties of crystallization and thermal crosslinking. The present study demonstrates the effects
of the thermal processing and heat treatment conditions on the accuracy and mechanical properties
of PPS samples three-dimensionally printed through fused deposition modeling. By measuring the
degree of crystallinity and thermal crosslinking of three-dimensionally printed PPS samples, we found
that the thermal history affects the three-dimensionally printed PPS properties. Results show that the
accuracy of three-dimensionally printed PPS samples can be improved by means of air-forced cooling
in fused deposition modeling. The balance between mechanical strength and ductility was regulated
by altering the heat treatment conditions. This approach is applicable to eliminating the warpage of
semi-crystalline polymer in three-dimensional printing (not only for PPS) and provides a method of
improving the mechanical properties of three-dimensionally printed PPS samples.

Keywords: 3D printing; additive manufacturing; polyphenylene sulfide; thermal processing condition;

heat treatment condition

1. Introduction
Polyphenylene sulfide (PPS) is a semi-crystalline thermoplastic material having an asymmetrical
rigid backbone chain comprising para-substituted phenylene rings and sulfur atoms. It is a polymer
material having good dimensional stability, high-temperature stability, chemical resistance, and flame
retardance, and it is easily processed. It also possesses the characteristics of aging resistance, radiation
resistance, and nontoxicity [1–5]. PPS can be used in the electronics, automotive, and aerospace
fields owing to its superior properties. The process of heating of PPS as a typical semi-crosslinking
polymer obviously affects the final mechanical properties owing to the crystalline and cross-linking
properties being dependent on the heat treatment history, ambient temperature, and other ambient
conditions [6,7]. Park et al. [8] analyzed the solid-phase crosslinking process of PPS resin in the
temperature range of 200–250 ◦ C. Their results show that a higher oxygen concentration and ambient
temperature increase the crosslinking rate and crosslinking degree of PPS.
Three-dimensional (3D) printing technology manufactures parts layer by layer from bottom to
top [9]. 3D printing technology has surpassed traditional manufacturing methods in many respects:
it provides more design freedom, is capable of quickly forming complex structural parts, and has the
advantages of low manufacturing costs, a short development cycle, and high production efficiency [10].
Fused filament fabrication (FFF) is the most widely used technology in 3D printing. An object
is deposited on a build platform by melting and extruding the polymer filament following the

Polymers 2018, 10, 875; doi:10.3390/polym10080875 www.mdpi.com/journal/polymers

Polymers 2018, 10, 875 2 of 12

deposition trajectory, and 3D parts are ultimately built through accumulation layer by layer [11].
The materials commonly used with this technology are acrylonitrile butadiene styrene, polylactic acid,
polycaprolactone and polycarbonate [12–16]. Most studies on 3D printing with PPS have focused on
the exploration of printable parameters of PPS and its composites and the effect of printing parameters
on warpage. Kishore et al. [17] formed high-performance semi-crystalline thermoplastic PPS and
polyether ketone ketone and analyzed the rheological properties and thermal properties of these
materials. On this basis, the parameters important to printability were determined. Fitzharris et al. [18]
analyzed warpage due to residual stresses during the cooling of PPS and PP for different printing
speeds through finite element analysis. DeNardo et al. [19] developed a CAMRI system for printing
high-performance PPS with 50 wt. % carbon fibers. The system replaced the traditional molten extrusion
system with a single screw extrusion system.
Complex thermal conditions affect the degree of crystallinity and the degree of crosslinking
of the extruded material in the melting and deposition processes of a typical heat crosslinking
semi-crystalline PPS. Controlling the thermal properties of the material in the forming process is
important to improving the forming quality and accuracy of fused deposition modeling samples.
Yang et al. [20] analyzed the effects of the ambient temperature and heat treatment conditions on
the tensile properties of 3D-printed poly(ether ether ketone) (PEEK) samples. By controlling the
thermal condition, PEEK samples with different elongations at break and tensile strengths were
built. Wang et al. [21] analyzed the effects of the build platform temperature and layer thickness
on the impact properties of 3D-printed polylactic acid samples. Their results showed that when the
thickness of the layer was 0.2 mm and the substrate temperature was 160 ◦ C, the 3D-printed samples
had greater impact strength than injection molding samples. This greater impact strength is mainly
due to the smaller cell sizes and lower molecular degradation compared with the injection sample.
Kishore et al. [22] improved the surface temperature of the printing layer before the FFF process
by means of infrared heating in a large-area 3D printing system to improve adhesion between the
acrylonitrile butadiene styrene materials. The above studies reveal that the thermal condition in the
process of FFF affects the mechanical properties of 3D-printed samples.
The present study therefore focuses on the thermal history of 3D-printed PPS samples and
analyzes the effects of the thermal processing conditions and heat treatment condition on the
mechanical properties (i.e., tensile strength, fracture resistance and impact strength) of the 3D-printed
PPS samples. The degree of crystallinity, oxidation crosslinking and temperature distribution in the
printing process under different thermal conditions were measured to reveal the relationships between
the thermal history and the microstructure and mechanical properties of 3D-printed PPS samples.
The mechanical properties of 3D-printed PPS samples can be controlled by adjusting the thermal
treatment conditions.

2. Materials and Methods

2.1. Materials
Crosslinking PPS resin pellets (A900) were obtained from Toray Industries Co., Ltd. (Tokyo, Japan).
The PPS filament with a diameter of 1.75 mm was extruded by a twin-screw extruder (sjzs-10z, Ruiming
Experimental Instrument Co., Ltd., Wuhan, China). The temperatures of the three heating zones were
270, 289 and 280 ◦ C. Before extrusion, PPS pellets were dried at 120 ◦ C for 12 h to remove moisture.

2.2. Experimental Procedure

A self-made PPS 3D printing system was adopted to print PPS samples. The 3D printing of PPS
under an air-forced cooling condition and natural cooling condition was realized with a fan installed
on the extrusion head. Figure 1 presents a schematic diagram of the PPS 3D printing and experimental
equipment, while Table 1 gives the PPS 3D printing parameters. The temperature distribution of
the upper/lower surface during printing was measured separately using an infrared thermograph
Polymers 2018, 10, 875 3 of 12

Polymers 2018, 10, x FOR PEER REVIEW 3 of 13

(A310, FLIR System Inc, Boston, MA, USA). The lower surface temperature distribution was observed
throughFLIR
germanium
System Inc,infrared
Boston,optical windows,
MA, USA). which
The lower weretemperature
surface installed on the build was
distribution platform of the 3D
observed
through germanium infrared optical windows, ◦
which were installed on the build
printer. All measurements were performed at 27 C air temperature and a relative humidity of 60%. platform of the 3D
printer.between
The distance All measurements
the camerawerelens
performed
and theat 27 °C air temperature
sample’s surface wasand aabout
relative humidity
0.55 m. The of 60%.
emissivity
The distance between the camera lens and the sample’s surface was about 0.55 m. The emissivity
coefficient of the 3D-printed samples was set at 0.91. The 3D-printed PPS models printing on the x–y
coefficient of the 3D-printed samples was set at 0.91. The 3D-printed PPS models printing on the x–y
plane with a with
plane layera thickness of 0.3
layer thickness mm
of 0.3 mm(z-direction)
(z-direction) for mechanical
for mechanical performance
performance testing
testing are shown
are shown in in
Figure 2.
Figure 2.
Polymers 2018, 10, x FOR PEER REVIEW 3 of 13

FLIR System Inc, Boston, MA, USA). The lower surface temperature distribution was observed
through germanium infrared optical windows, which were installed on the build platform of the 3D
printer. All measurements were performed at 27 °C air temperature and a relative humidity of 60%.
The distance between the camera lens and the sample’s surface was about 0.55 m. The emissivity
coefficient of the 3D-printed samples was set at 0.91. The 3D-printed PPS models printing on the x–y
plane with a layer thickness of 0.3 mm (z-direction) for mechanical performance testing are shown in
Figure 2.

Figure 1. PPS 3D printing: (a) Schematic diagram of PPS 3D printing; (b) image of the extrusion head.
Figure 1. PPS 3D printing: (a) Schematic diagram of PPS 3D printing; (b) image of the extrusion head.
Table 1. Printing parameters of 3D-printed PPS.
Table 1. Printing parameters of 3D-printed PPS.
Parameter Value
Nozzle diameter 0.4 mm
Parameter
Nozzle temperature 285 °CValue
Figure 1. PPS 3D printing: (a) SchematicPrinting
diagramspeed
of PPS1 3D printing; (b) image of the extrusion head.
680 mm/min
Nozzle diameter 0.4 mm
Layer thickness 0.3 mm ◦
Nozzle temperature
Table 1. Printing parameters of 3D-printed 285 C
Number of contours
1 1 PPS.
PrintingInfillspeed 680 mm/min
pattern Rectilinear
LayerParameter
thickness Value
0.3 mm
NozzleRaster angle 0.4 mm45°/−45°
diameter
Number ofRaster width 285 °C 0.4 mm 1
contours
Nozzle temperature
Infill pattern
Printing speed gap
Raster 1 680 mm/min Rectilinear
0 mm
Raster
Layer anglemultiplier0.3 mm 0.9
thickness
Extrusion 45◦ /−45◦
Number width
Raster of contours 1 0.4 mm
Outline overlap 0.06 mm
Infill pattern Rectilinear
Raster
1 The first-layer printing speed
Raster
gap was reduced
angle by 50%0tomm
45°/−45° improve bed adhesion.
Extrusion
Raster multiplier
width 0.4 mm 0.9
Outline overlap
Raster gap 0 mm 0.06 mm
1 Extrusion multiplier 0.9
The first-layer printing speed
Outline was reduced
overlap by 50% to improve bed adhesion.
0.06 mm
1 The first-layer printing speed was reduced by 50% to improve bed adhesion.

Figure 2. Dimensions for the 3D-printed PPS samples: (a) Tensile sample geometry; (b) Izod notched
notched impact sample geometry; (c) compact tensile sample geometry.
Figure 2. Dimensions for the 3D-printed PPS samples: (a) Tensile sample geometry; (b) Izod notched
Dimensions
Figure 2.notched for the
impact sample 3D-printed
geometry; PPS
(c) compact samples:
tensile (a) Tensile sample geometry; (b) Izod notched
sample geometry.
notched impact sample geometry; (c) compact tensile sample geometry.

To analyze the effects of heat treatment conditions on the properties of 3D-printed PPS samples,
samples printed under the air-forced cooling condition were heated in air from room temperature
 Polymers 2018, 10, x FOR PEER REVIEW 4 of 13
Polymers 2018, 10, 875 4 of 12
To analyze the effects of heat treatment conditions on the properties of 3D-printed PPS samples,
samples printed under the air-forced cooling condition were heated in air from room temperature to
to different heat treatment
different temperatures
heat treatment overa period
temperatures over a period of min.
of 100 100 The
min. The
heat heat treatment
treatment conditions
conditions of 3D- of
3D-printed PPS PPS
printed samples
samplesunder
underair-forced cooling
air-forced cooling conditions
conditions are shown
are shown in Figurein3.Figure 3.

FigureFigure 3. Heat
3. Heat treatment
treatment conditions of
conditions of3D-printed
3D-printedPPSPPS
samples.
samples.

2.3. Testing of Mechanical Properties

2.3. Testing of Mechanical Properties
Tensile tests, impact tests and Mode-I fracture tests were carried out according to ISO 527, ISO
Tensile
180tests,
and ISOimpact tests and Mode-I
13586 respectively. fractureoftests
The dimensions were were
test models carried out according
adjusted to ensure thetouniformity
ISO 527, ISO 180
of thickness
and ISO 13586 of each layer
respectively. after
The slicing the 3Dof
dimensions model
test compared
models were with the standardto
adjusted model.
ensureTensile
theand uniformity
fracture tests were carried out on an electronic universal testing machine (UTM5000, Shenzhen SUNS
of thickness of each layer after slicing the 3D model compared with the standard model. Tensile and
Technology Stock Co. Ltd., Shenzhen, China). The loading rate in the tensile test was 1 mm/min,
fracture tests
whilewere carried
that in out test
the fracture on was
an electronic
10 mm/min.universal testing
An Izod notched machine
impact test was(UTM5000,
carried out onShenzhen
a Ceast SUNS
Technology Stock Co. Ltd., Shenzhen, China). The loading rate in
pendulum impact tester (JJ-20, Changchun Intelligent Instrument and Equipment Co., Ltd., the tensile test was 1 mm/min,
Changchun, China) with a pendulum energy of 5.5 J. Each
while that in the fracture test was 10 mm/min. An Izod notched impact test was carried value of a mechanical property is the out on
average value of five samples under different thermal conditions.
a Ceast pendulum impact tester (JJ-20, Changchun Intelligent Instrument and Equipment Co., Ltd.,To improve the measurement
accuracy of the dimensions of 3D-printed samples, a noncontact 3D scanner (EaScan-T, Hangzhou
Changchun, China) with a pendulum energy of 5.5 J. Each value of a mechanical property is the
Shining 3D Tech Co., Ltd., Hangzhou, China) was employed to scan the 3D-printed samples and
average value
obtain of
the five
pointsamples
cloud dataunder different
of the printed thermal
sample. conditions.
In Mode-I To toimprove
fracture tests, ensure that the
themeasurement
crack
accuracy extended
of the dimensions of 3D-printed
along the pre-notch samples,
in the loading process a andnoncontact 3D scanner
reduce the residual stresses(EaScan-T, Hangzhou
at the crack tip,
a natural crack having a depth of 2 mm, as recommended in the test standard,
Shining 3D Tech Co., Ltd., Hangzhou, China) was employed to scan the 3D-printed samples and obtain was created during
the printing process by adjusting the print layer thickness at the front end of the notch (from 0.3 to
the point cloud data of the printed sample. In Mode-I fracture tests, to ensure that the crack extended
0.2 mm). In the experiment, the curve of the force (P) versus displacement (δ) was recorded, and Pmax
along the and
pre-notch
PQ were in the loading
obtained according process andsecant
to the 5% reducelinethe residual
criterion of thestresses at the crack
force–displacement tip, a natural
relation.
crack having a depth
The critical of 2intensity
stress mm, asfactorrecommended in the
KIC was calculated as test standard, was created during the printing
process by adjusting the print layer thickness 𝐾 = 𝑃 ⁄𝐵𝑊
at the ⁄ front end of the notch (from 0.3 to 0.2 mm).
𝑓 𝑥 , 𝑥 = 𝑎⁄𝑊 (1)
In the
experiment, the curve of the force (P) versus displacement (δ) was recorded, and Pmax and PQ were
obtained according
where 0.2 < xto< the
0.8, a5% secant
is the crackline criterion
length, W is theof the force–displacement
samples width, and relation. The critical stress
intensity factor KIC was calculated as
2 + 𝑥 0.886 + 4.64𝑥 13.32𝑥 + 14.72𝑥 5.6𝑥
𝑓 𝑥 = (2)
KQ = PQ /BW 1/21 f (𝑥x ), x = a/W
 
(1)

where 0.22.4.
< xDifferential
< 0.8, a isScanning Calorimetry Analysis
the crack length, W is the samples width, and
A thermal analysis differential scanning calorimeter (Q2000, TA Instruments, New Castle, DE,
13.32x2 +PPS 3 −under
5.6x4different thermal


USA) was used to determine(2 +the
x )thermal
0.886 response
+ 4.64x of−3D-printed samples
14.72x
x ) = were heated from room temperature
conditions. Allf (samples 3 to 350 °C under a nitrogen atmosphere (2)
(1 − x ) 2 3–5 mg samples were cut from the inside
at a rate of 10 °C/min. To ensure the accuracy of crystallinity,

2.4. Differential Scanning Calorimetry Analysis

A thermal analysis differential scanning calorimeter (Q2000, TA Instruments, New Castle, DE,
USA) was used to determine the thermal response of 3D-printed PPS samples under different thermal
conditions. All samples were heated from room temperature to 350 ◦ C under a nitrogen atmosphere at
a rate of 10 ◦ C/min. To ensure the accuracy of crystallinity, 3–5 mg samples were cut from the inside
of the fracture tensile samples. The degree of crystallinity (Xc ) under different thermal conditions was
calculated as
Xc = [(∆Hm + ∆Hc )/∆Hθ ] × 100% (3)
of the fracture tensile samples. The degree of crystallinity (Xc) under different thermal conditions was
calculated as
𝑋 = ∆𝐻 + ∆𝐻 ⁄∆𝐻 × 100% (3)
Polymers 10, c875
2018,ΔH
where 5 of 12
and ΔHm are respectively the enthalpies of recrystallization and melting. The melting
enthalpy of 100% crystalline PPS (ΔHθ) is 77.5 J/g [23].
where ∆Hc and ∆Hm are respectively the enthalpies of recrystallization and melting. The melting
2.5. Fourier Transform Infrared Spectroscopy
enthalpy of 100% crystalline PPS (∆Hθ ) is 77.5 J/g [23].
Fourier transform infrared spectroscopy (FTIR) (Nicolet Nexus 670, Thermo Fisher Scientific,
2.5. FourierMA,
Waltham, Transform
USA)Infrared Spectroscopy
was performed for the 3D-printed PPS samples under different thermal
conditions
Fourier with a single-reflection
transform attenuated total
infrared spectroscopy (FTIR)reflectance (ATR) 670,
(Nicolet Nexus accessory.
Thermo ATR-FTIR spectra
Fisher Scientific,
were collected
Waltham, MA,at room
USA) wastemperature
performed over a scanning
for the range
3D-printed PPS of 4000–600
samples undercmdifferent
−1 with a spectral resolution
thermal conditions
of 4 cm
with a −1 . The surface ofattenuated
single-reflection FTIR test istotal
the cross sections
reflectance of 3D-printed
(ATR) accessory. samples
ATR-FTIR under different
spectra thermal
were collected
at room temperature over a scanning range of 4000–600 cm−1 with a spectral resolution of 4 cm−1 .
conditions.
The surface of FTIR test is the cross sections of 3D-printed samples under different thermal conditions.
3. Results and Discussion
3. Results and Discussion
3.1. FTIR Analysis
3.1. FTIR Analysis
Figure 4 shows the FTIR spectra recorded from 3D-printed PPS samples under different thermal
FigureAll
conditions. 4 shows the FTIRbands,
characteristic spectraincluding
recorded from
those3D-printed PPS samples
of the benzene ring andunder
C–H atdifferent
1571 andthermal
1076
−1
cm , are present. This indicates that PPS material maintains good stability after high-temperature,
conditions.
−1 All characteristic bands, including those of the benzene ring and C–H at 1571 and 1076 cm
are present.
treatment. Thisheat
After indicates that PPS
treatment, thematerial maintains
PPS samples showgood stability
obvious after high-temperature
characteristic peaks at 1904treatment.
and 1180
After heat treatment, the PPS samples show obvious characteristic peaks at 1904 and 1180 −1 that
cm−1 that should, respectively, be attributed to –C=O and –S=O stretching vibrations. Thiscmindicates
should,
that respectively,
the peaks be attributed
are formed to –C=O
by thermal and –S=O
oxidative stretching
crosslinking andvibrations. Thisreaction
an oxidation indicatesinthat
thethe peaks
printing
are formed by thermal oxidative crosslinking and an oxidation reaction in the printing PPS process.
PPS process. The thermal crosslinking of PPS depends on the temperature and time of exposure to
The thermal crosslinking of PPS depends on the temperature and time of exposure to air. In the printing
air. In the printing process, although PPS was heated to its melting point, it cooled in just a few
process, although PPS was heated to its melting point, it cooled in just a few seconds. There was no
seconds. There was no obvious oxidative crosslinking phenomenon for the 3D-printed PPS samples.
obvious oxidative crosslinking phenomenon for the 3D-printed PPS samples.

Figure4.
Figure FTIRspectra
4.FTIR spectraof
of 3D-printed
3D-printed PPS
PPS samples.
samples.

3.2.DSC
3.2. DSCAnalysis
Analysis
Figure 55 shows
Figure shows crystallization
crystallization and
and melting
melting thermograms
thermograms of of 3D-printed PPS samples under
different thermal
different thermalconditions.
conditions.Table
Table2 lists the quantitative
2 lists data ofdata
the quantitative the peak temperature
of the and enthalpies.
peak temperature and
It is seen that the PPS crystallization temperature range is 126.37–135.27 ◦ C. Furthermore, for both
enthalpies. It is seen that the PPS crystallization temperature range is 126.37–135.27 °C. Furthermore,
air-forced cooling and natural ◦ C.
for both air-forced cooling andcooling
naturalconditions, there is an
cooling conditions, obvious
there is anrecrystallization peak at 129
obvious recrystallization peak
When theWhen
samples ◦
at 129 °C. theare heatedare
samples to 130–240
heated toC, the recrystallization
130–240 peak diminishes
°C, the recrystallization or even disappears.
peak diminishes or even
This is mainly
disappears. Thisdue to the sufficient
is mainly due to the reordering
sufficient of the molecular
reordering of thechains in thechains
molecular sample, resulting
in the in
sample,
higher crystallinity
resulting and the establishment
in higher crystallinity of a tighter of
and the establishment polymer chain
a tighter network.
polymer chainWith an increase
network. in
With an
the heat in
increase treatment
the heattemperature, the melting peak
treatment temperature, widens, peak
the melting whichwidens,
is mainly due to
which is the thermal
mainly dueoxygen
to the
crosslinking reaction of the PPS molecules in the process of heat treatment and the greater number of
C–O bonds. The PPS molecular chain undergoing oxidation and crosslinking has reduced molecular
mobility during the cooling crystallization process that may not be sufficient to allow completion of
the crystallization process. When the temperature increases again, the molecular chains with different
thermal oxygen
Polymers 2018, crosslinking
10, x FOR reaction of the PPS molecules in the process of heat treatment and
PEER REVIEW 6 ofthe13
greater number of C–O bonds. The PPS molecular chain undergoing oxidation and crosslinking has
thermal molecular
reduced oxygen crosslinking reaction
mobility during theofcooling
the PPScrystallization
molecules in the process
process thatofmay
heatnot
treatment and the
be sufficient to
greater
allow number ofofC–O
completion bonds. The PPS
the crystallization molecular
process. Whenchain undergoing oxidation
the temperature and crosslinking
increases again, the molecular has
reduced
chains molecular
with
Polymers 2018,different
10, 875
mobility during
molecular the cooling
weights crystallization
have slightly process
different thatassociated
mobility may not be sufficient
with a6 wider
of 12
to
allow completion
melting peak and the of the crystallization
double process. When the temperature increases again, the molecular
melting peak.
chains with different molecular weights have slightly different mobility associated with a wider
molecular
melting peakweights
and thehave slightly
double different
melting peak. mobility associated with a wider melting peak and the
double melting peak.

Figure 5. DSC curves of 3D-printed PPS samples.

Figure
Table DSCproperties
5. DSC
2. Thermal
Figure 5. curves of
curves of 3D-printed PPS
of 3D-printed
3D-printed samples.
PPSPPS samples.
samples.

Table
Table
Sample ThermalEnthalpy
2. Thermal
2. properties
propertiesof
(J/g)3D-printed PPS
Crystallinity (%)
of 3D-printed PPSsamples.
samples.
ΔHc ΔHm Xc
Enthalpy
Air-forced cooling Enthalpy 20.03 (J/g)(J/g) 35.41 Crystallinity
19.13 (%)
Crystallinity (%)
Sample
Sample
Natural cooling 9.31
ΔH
∆Hc c 36.77
ΔH
∆Hm m 35.43
X c
Xc
130
Air-forced °C cooling
Air-forced cooling
2.96
20.03
20.03
36.15
35.41
35.41
42.28
19.13
19.13
150cooling
Natural
Natural °C
cooling --
9.31
9.31 33.31
36.77
36.77 42.75
35.43
35.43
130 ◦
130C
200 °C
°C 2.96--
2.96 36.15
39.16
36.15 42.28
50.04
42.28
150 ◦C – 33.31 42.75
150°C
240 °C ---- 49.67
33.31 64.08
42.75
200 ◦ C – 39.16 50.04
200
◦
240 C °C – -- 39.16
49.67 50.04
64.08
240 °C Condition on Temperature
3.3. Effect of the Thermal Processing -- 49.67
Profiles and64.08
the Accuracy of 3D-Printed
PPS3.3.Samples
Effect of the Thermal Processing Condition on Temperature Profiles and the Accuracy of 3D-Printed
3.3.
PPSEffect of the Thermal Processing Condition on Temperature Profiles and the Accuracy of 3D-Printed
Samples
Figure 6 shows 3D-printed PPS samples. It is seen that the color of the PPS 3D-printed sample
PPS Samples
under theFigure 6 shows cooling
air-forced 3D-printed PPS samples.
condition It istoseen
is close thethat theof
color color
the of thepellet,
PPS PPS 3D-printed
while thesample
color under
of heat-
theFigure
treated 6 shows
air-forced
samples 3D-printed
cooling
varies condition
from ivoryPPSto samples.
is close Itassociation
to theincolor
brown is seen
of thethat
PPS the color
pellet,
with of the
the while thePPS
increase 3D-printed
color
in theofheat sample
heat-treated
treatment
under
samplesthe
temperature. air-forced
varies from cooling
ivory to condition
brown in is close
association to the
with color
the of the
increase PPS
in pellet,
the heat while the
treatment color of heat-
temperature.
treated samples varies from ivory to brown in association with the increase in the heat treatment
temperature.

Figure 6. 3D-printed PPS samples: (a) Tensile samples; (b) Izod notched impact samples; (c) compact
tensile samples.
 Figure 6. 3D-printed PPS samples: (a) Tensile samples; (b) Izod notched impact samples; (c) compact
tensile samples.

Figure 7 shows the temperature profiles of the upper and lower surfaces of the 3D-printed PPS
samples and2018,
Polymers the10,warpage
875 of 3D-printed PPS samples. Figure 7a shows that the temperature 7 of 12at the
sample center rises rapidly to the nozzle temperature and then decreases rapidly with by the nozzle
leaving from measurement point. In the process of printing each layer, there are three peaks,
Figure 7 shows the temperature profiles of the upper and lower surfaces of the 3D-printed PPS
specifically two secondary peaks that appear to coincide with the process of printing contours and a
samples and the warpage of 3D-printed PPS samples. Figure 7a shows that the temperature at the
primary peak relating to the process of printing the infill pattern. Note that the primary peak reaches
sample center rises rapidly to the nozzle temperature and then decreases rapidly with by the nozzle
aboutleaving
300 °C, fromwhich is different
measurement point.from
In thethe actual
process nozzleeach
of printing temperature
layer, there of
are285
three°C. This
peaks, difference is
specifically
mainlytwodue to thepeaks
secondary measurement
that appear to being confounded
coincide by infrared
with the process of printing reflections
contours and from the nozzle.
a primary peak In
addition, emissivity
relating was of
to the process adopted
printing by employing
the infill pattern. aNote
semi-melted PPS peak
that the primary material,
reaches while
aboutthe ◦ C,
300 thermal
which iswas different from theby actual nozzlenozzle
temperature ◦
distribution dominated the brass whenofthe 285nozzle
C. Thismoved
difference
pastis the
mainly due to thepoint,
measuring
measurement
resulting being confounded
in the deviation by infrared reflections
of the measurement. For thefrom the nozzle.PPS
3D-printed In addition,
samplesemissivity was
under air-forced
adopted by employing a semi-melted PPS material, while the thermal
cooling, the peak temperature reduced rapidly and remained lower than Tc. For the 3D-printed distribution was dominated
by the brass nozzle when the nozzle moved past the measuring point, resulting in the deviation of
samples under the natural cooling condition, there was no adequate heat transfer in the envelope
the measurement. For the 3D-printed PPS samples under air-forced cooling, the peak temperature
region. Figure 7b,c clearly shows that the heat-affected zone under the natural cooling condition is
reduced rapidly and remained lower than Tc . For the 3D-printed samples under the natural cooling
largercondition,
than thatthere for was
the sample
no adequateunder the
heat air-forced
transfer in the cooling
envelopecondition. A comparison
region. Figure of the 3D-
7b,c clearly shows
printed PPS
that thesamples and 3D
heat-affected zone model
undershows that the
the natural maximum
cooling condition deviation
is largeristhan
+0.79/−0.89 mm
that for the under the
sample
air-forced
undercooling condition
the air-forced coolingand +0.89/−2.38
condition. mm underofthe
A comparison the natural
3D-printedcooling condition.
PPS samples It ismodel
and 3D seen that
the sample
showsunder
that the the condition
maximum of air-forced
deviation is +0.79/ −0.89 is
cooling mm ofunder
high precision andcooling
the air-forced the decrease of warpage
condition and
+0.89/ − 2.38 mm under the natural cooling condition. It is seen that the sample
due to residual thermal stress is attributed to the effective heat transfer through convection with the under the condition
of air-forced
environment. In cooling
summary, is of high
the precision
air-forced andcooling
the decrease
method of warpage due tocontrols
effectively residual thermal stress
the temperature
is attributed to the effective heat transfer through convection with the environment. In summary,
distribution of the 3D-printed PPS sample and improves the accuracy of the 3D-printed PPS sample
the air-forced cooling method effectively controls the temperature distribution of the 3D-printed PPS
in the FFF process.
sample and improves the accuracy of the 3D-printed PPS sample in the FFF process.

FigureFigure
7. Evolution of the
7. Evolution 3D-printed
of the 3D-printed PPS
PPStemperature:
temperature: (a) Temperature
Temperature profile
profile of the
of the upper
upper surface;
surface;
(b) temperature
(b) temperature profile
profile of the
of the lower
lower surface;(c)
surface; (c) infrared
infrared images
imagesshowing
showingthethe
evolution of the
evolution oflower
the lower
surface
surface temperature;
temperature; (d) (d) warpage
warpage ofof 3D-printed PPS
3D-printed PPS samples.
samples.
Polymers 2018, 10, 875 8 of 12

Polymers 2018, 10, x FOR PEER REVIEW 8 of 13

3.4. Tensile Properties of 3D-Printed PPS Samples

3.4. Tensile Properties of 3D-Printed PPS Samples
Figure 8 shows the tensile stress–strain curves and tensile strengths of 3D-printed PPS samples.
Figure 8 shows the tensile stress–strain curves and tensile strengths of 3D-printed PPS samples.
It is seen that the heat treatment process affects the tensile properties of 3D-printed PPS samples.
It is seen that the heat treatment process affects the tensile properties of 3D-printed PPS samples. The
The 3D-printed
3D-printed PPSPPS samples
samples without
without heatheat treatment
treatment showshow greater
greater breakbreak elongation.
elongation. The 3D-printed
The 3D-printed PPS
PPS samples without heat treatment have a ductile behavior with plastic
samples without heat treatment have a ductile behavior with plastic deformation. The samples deformation. The samples
show
show no obvious necking propagation ◦
no obvious necking propagation and and the fracture
the fracture is atisan
at an angle
angle of of
45°45to tothethe loadingdirection.
loading direction.
However,
However,the the samples
samples that that were
were heatheat treated
treated hadhad no no obvious
obvious plastic
plastic deformation
deformationand andnecking
necking
propagation. As the loading increased, the samples broke rapidly after
propagation. As the loading increased, the samples broke rapidly after reaching maximum stress. reaching maximum stress.
These results indicate that a ductile-brittle transition in 3D-printed PPS
These results indicate that a ductile-brittle transition in 3D-printed PPS samples occurred as the samples occurred as the
samples
sampleswere were heated
heated above
above the the crystallization temperatureTc.THeat
crystallizationtemperature c . Heat treatment
treatment is aisfeasible
a feasible
waywayto
toregulate
regulate the ratio of the crystalline region and amorphous region of
the ratio of the crystalline region and amorphous region of 3D-printed PPS samples, and the3D-printed PPS samples,
and
ratiothe
is ratio is a factor
a crucial crucialaffecting
factor affecting the mechanical
the mechanical properties. properties.
Figure 8bFigure
shows 8b shows
that that the
the tensile tensile
strength
strength of the atsample ◦ C was up to 108% higher than that of the sample subjected to air-forced
of the sample 240 °Catwas 240up to 108% higher than that of the sample subjected to air-forced cooling.
cooling. The strengths
The strengths and elastic
and elastic moduli moduli of 3D-printed
of 3D-printed samples
samples increased
increased withwith
an an increase
increase in in
thetheheat
heat
treatment
treatmenttemperature.
temperature.
Theimprovement
The improvementin inthe
thetensile
tensile strength and elastic
elastic modulus
modulusisisclosely
closelyrelated
relatedtotothethecrystallinity
crystallinity
ofofmaterials
materialsand andthe
thecrosslinking
crosslinkingof of molecular
molecular chains. Table Table 22 and
andFigure
Figure66reveal
revealthatthatwith
withananincrease
increase
ininheat
heat treatment
treatment temperature,
temperature, the crystallinity
the crystallinity rises19.13%
rises from from to 19.13%
64.08%toand 64.08%
oxygen and oxygen is
is continuously
continuously
introduced introduced
in the molecular in the molecular
chain. Without chain. Without considering
considering the effects ofthe theeffects
otherofprinting
the other printing
parameters
parameters on the forming sample, the heat treatment method improves
on the forming sample, the heat treatment method improves the tensile properties of 3D-printed the tensile properties of 3D-
printed
PPS samples. PPS samples.

Figure8.8.Tensile
Figure Tensileproperties
propertiesof
of3D-printed
3D-printed PPS samples: (a) (a)Stress–strain
Stress–straincurves
curvesofofthe
the3D-printed
3D-printedPPS
PPS
samples;(b)
samples; (b)elastic
elasticmodulus
modulusandand tensile
tensile strength
strength of the 3D-printed
3D-printed PPS
PPSsamples.
samples.

It is worth noting that the mechanical properties of 3D-printed samples are not only related to
It is worth noting that the mechanical properties of 3D-printed samples are not only related to the
the inherent properties of PPS materials but also depend on the macroscopic structure (i.e., voids
inherent properties of PPS materials but also depend on the macroscopic structure (i.e., voids between
between adjacent filaments, the directions of filaments and the diffusion degree at the interfaces of
adjacent filaments, the directions of filaments and the diffusion degree at the interfaces of adjacent
adjacent filaments) resulting from the complex printing trajectory. Figure 9 illustrates the fracture
filaments) resulting from the complex printing trajectory. Figure 9 illustrates the fracture morphology
morphology of 3D-printed PPS samples. Figure 9a,b show localized necking and diffusion
of 3D-printed PPS samples. Figure 9a,b show localized necking and diffusion accompanying the
accompanying the increase in loading at the end of a filament, indicated by a white arrow in Figure
increase in loading at the end of a filament, indicated by a white arrow in Figure 9a, and extensive
9a, and extensive crazing around the fracture. This is mainly because the semi-melted filament
crazing around the fracture. This is mainly because the semi-melted filament extruded from the nozzle
extruded from the nozzle produces a temperature gradient along the radial direction during
produces a temperature
solidification. The region gradient
closealong
to thethefilament
radial direction
surface during solidification.
has sufficient The region close
heat convection with to the
the
filament surfacewhile
environment, has sufficient heat convection
the main cooling process atwith
the the
coreenvironment,
of a filament while
is heatthe main by
transfer cooling process
conduction
atbetween
the coreadjacent
of a filament is heat transfer by conduction between adjacent filaments. The
filaments. The temperature gradient change results in a non-uniform crystallization temperature
gradient
region in change
whichresults
the outerin afilament
non-uniform crystallization
is disordered region
and loose andinthe
which
innerthe outer filament
filament is disordered
has stronger bonds
and loose and the inner filament has stronger bonds among molecular chains. As
among molecular chains. As the loading increases, the inner filament has better plastic deformation. the loading increases,
the inner
When filament
a critical has better
value plastic
is reached, deformation.
filament When
localized a critical
necking occurs,value is reached,
followed filament localized
by micro-crack growth
necking occurs, followed by micro-crack growth at the surface of the filament. Furthermore,
at the surface of the filament. Furthermore, diffusion between adjacent filaments results in a number diffusion
between
of cavitiesadjacent filaments results
and propagation in a number
associated of cavities
with increasing and propagation
loading associated
due to insufficient withunder
bonding increasing
the
Polymers 2018, 10, x FOR PEER REVIEW 9 of 13
Polymers 2018, 10, 875 9 of 12

air-forced cooling condition. Figure 9b–f show that cavities are effectively suppressed when PPS
loadingare
samples due to insufficient
built at a higher bonding under the
environmental air-forced cooling condition. Figure 9b–f show that
temperature.
cavities
Figure 9c,d show that the fracture contains a are
are effectively suppressed when PPS samples built
large at a higher
number environmental
of flake-like temperature.
structures and the
neckingFigure 9c,d showof
phenomenon that
thethe fracture contains
3D-printed a largedisappears.
PPS sample number of flake-like structures
The fracture and
surface the necking
roughness and
phenomenon of the 3D-printed PPS sample disappears. The fracture surface
the fracture extend in different directions at different levels [24]. With an increase in the heatroughness and the
fracture extend
treatment in different
temperature, directions
the void at different
size reduces and levels [24]. With
the diffusion an increase
between in the heat
the adjacent treatment
filaments and
temperature, the void size reduces and the diffusion between the adjacent filaments
interlayer increases. When the heat treatment temperature reaches 240 °C, the fracture surface is and interlayer
increases. When the direction
heat treatment ◦ C, the fracture surface is perpendicular
perpendicular to the of thetemperature
load, and the reaches
angle240
of 3D-printed samples heat treated at 130–
to the direction of the load, and the angle of 3D-printed samples heat treated at 130–200 ◦ C between
200 °C between the fracture surface and the loading direction remains about 45°. The fracture
the fracture surface and the loading direction remains about 45◦ . The fracture morphologies of the
morphologies of the 3D-printed PPS samples under heat treatment are covered with a fast-fracture
3D-printed PPS samples under heat treatment are covered with a fast-fracture zone and micro-ductile
zone and micro-ductile tearing, while the weak point of intercrystalline zones in the 3D-printed PPS
tearing, while the weak point of intercrystalline zones in the 3D-printed PPS samples under heat
samples under heat treatment at 240 °C is one reason for the fracture.
treatment at 240 ◦ C is one reason for the fracture.

Figure
Figure SEMmicrographs
9.9.SEM micrographsofofthe
thefracture
fracture of
of 3D-printed
3D-printed PPSPPS tensile
tensilesamples
samplesunder
underdifferent
differentthermal
thermal
conditions: (a) air-forced cooling; (b) natural cooling; (c) 130 ◦ C; (d) 150 ◦ C; (e) 200 ◦ C; (f) 240 ◦ C.
conditions: (a) air-forced cooling; (b) natural cooling; (c) 130 °C; (d) 150 °C; (e) 200 °C; (f) 240 °C.

Table
Table3 3gives
givesthe
thefilament
filamentdimensions
dimensions of 3D-printed
3D-printedPPSPPSsamples.
samples.The
Thedimensions
dimensions ofof a filament
a filament
(a (a and
and b)b)remain
remainconstant,
constant,while
whilethe
thediffusion
diffusion of the adjacent
adjacent filament
filament(H)
(H)and
andinterlayer
interlayer(c)(c)increase.
increase.
This is due to molecular motion being sufficient for the coalescence of cavities and
This is due to molecular motion being sufficient for the coalescence of cavities and the diffusion of the diffusion
of interfaces
interfaces when when
the the
heatheat treatment
treatment is isabove
abovethe the glass
glass transition
transition temperature.
temperature.The Theinternal
internal voids
voids
observed in Figure 9b are greatly reduced. It is therefore considered that the defects of the
observed in Figure 9b are greatly reduced. It is therefore considered that the defects of the 3D-printed 3D-printed
PPSPPS samplescan
samples canbe
beeffectively
effectivelysuppressed
suppressed through
throughheatheattreatment.
treatment.

Table 3. Measured filament dimensions of 3D-printed PPS samples.

Table 3. Measured filament dimensions of 3D-printed PPS samples.

Thermal
Thermal Condition
Condition HH(μm)
(µm) aa
(µm)
(μm) b (µm)
b (μm) c (µm) c (μm)
◦
130 °C ◦ C
130 87.6 ±
87.6 8.2
± 8.2 290.7
290.7± 10.7
± 10.7 ± 15.6± 15.6
306.7306.7 134.1 ±134.1
9.2 ± 9.2
150 C 108.8 ± 6.1 297.6 ± 12.1 380.8 ± 10.2 187.9 ± 10.5
150 °C
200 ◦ C 108.8
144.9 ±±10.5
6.1 297.6 ± 12.1
299.4 ± 13.1 380.8
364.7 ± 8.9 ± 10.2 187.9
240.8 ± 16.9 ± 10.5
240 ◦ C
200 °C 144.9 ± 10.5
204.9 ± 13.1 299.4
303.2 ± 13.1
± 11.2 370.8364.7
± 13.5 ± 8.9
248.5 ±240.8
19.8 ± 16.9
240 °C 204.9 ± 13.1 303.2 ± 11.2 370.8 ± 13.5 248.5 ± 19.8
Polymers 2018, 10, x FOR PEER REVIEW 10 of 13

Polymers 2018, 10, 875 10 of 12

3.5. Fracture Toughness of 3D-Printed PPS Samples
The fracture toughness of 3D-printed PPS samples is mainly attributed to interlayer bonding.
3.5. Fracture Toughness of 3D-Printed PPS Samples
Figure 10 shows the force–displacement curve and KIC. The sample had the best interlayer strength,
The fracture toughness of 3D-printed PPS samples is mainly attributed to interlayer bonding.
followed by the sample heated at 240 °C. The sample that was naturally cooled had lower fracture
Figure 10 shows the force–displacement curve and KIC . The sample had the best interlayer strength,
toughness than the other samples. The◦ samples under the natural cooling condition exhibit low
followed by the sample heated at 240 C. The sample that was naturally cooled had lower fracture
interlayer strength. This may be caused by the residual stress leading to layer delamination and
toughness than the other samples. The samples under the natural cooling condition exhibit low
dislocation.
interlayerFigures 8 and
strength. 9 show
This may bethat the by
caused samples that experienced
the residual stress leadingair-forced cooling have
to layer delamination andtypical
plastic deformation
dislocation. behaviors.
Figures In fracture
8 and 9 show that thetoughness tests,
samples that the samples
experienced undercooling
air-forced air-forced
havecooling
typical were
moreplastic
able todeformation
resist crackbehaviors.
extension,
In while
fracturethe samplestests,
toughness underthe heat treatment
samples exhibited
under air-forced brittlewere
cooling fracture.
more able to resist crack extension, while the samples under heat treatment exhibited
Table 3 shows that the width of the interlayer bonding increases from 134.06 to 248.54 μm with the brittle fracture.
Table
increase in3 heat
shows that the width
treatment of the interlayer
temperature. bonding increases
Heat treatment from 134.06method
is an applicable to 248.54of
µm with the the
improving
interlayer strength. The elimination of the interface between the semi-melt extrusion filamentthe
increase in heat treatment temperature. Heat treatment is an applicable method of improving and the
interlayer strength. The elimination of the interface between the semi-melt extrusion filament and the
solidified previous filament provides resistance to fracturing. The heat treatment method therefore
solidified previous filament provides resistance to fracturing. The heat treatment method therefore
provides an effective way to improve the interlayer strength.
provides an effective way to improve the interlayer strength.

FigureFigure 10. Fracture

10. Fracture toughness
toughness ofof 3D-printedPPS
3D-printed PPS compact
compact tension
tensionsamples: (a) (a)
samples: TheThe
displacement and and
displacement
force curves; (b) the stress intensity factor KIC .
force curves; (b) the stress intensity factor KI. Co
3.6. Izod Notched Impact Properties of 3D-Printed PPS Samples
3.6. Izod Notched Impact Properties of 3D-Printed PPS Samples
The impact strength is essentially an energy index that depends on the sum of various energies
The impactbystrength
consumed is essentially
the material an energy
in the process of impactindex that depends
fracture. Figure 11on the Izod
is the sumnotched
of various energies
impact
consumed
strengthbyofthe materialPPS
3D-printed in the process
samples. Theof impact
figure shows fracture.
that theFigure
impact 11 is theofIzod
strength notched
the PPS sample impact
strength
that of 3D-printed
experienced PPS samples.
air cooling The figure
is 17.04 kJ/m 2 , whichshows that the
is obviously impact
higher strength
than the impact of the PPS
strength sample
of the
that experienced air coolingheat
samples that underwent is 17.04 kJ/m2For
treatment. , which is obviously
the 3D-printed PPShigher
sample,than the impact
the impact strength
properties of theof the
sample
samples thatare affected byheat
underwent the strength
treatment.andFor
modulus of the sample,
the 3D-printed PPSthe crystallinity
sample, and crosslinking
the impact propertiesofof the
the material, the arrangement of the filaments, and the density of infill. The
sample are affected by the strength and modulus of the sample, the crystallinity and crosslinkingimpact test mainly relates of
to the comprehensive state of the strength and plasticity of the material under the test conditions,
the material, the arrangement of the filaments, and the density of infill. The impact test mainly relates
and an increase in the plasticity of the material greatly improves the impact resistance of the material.
to the comprehensive state of the strength and plasticity of the material under the test conditions, and
When the sample is printed under air cooling conditions, the crystallinity of the sample is low and
an increase in the plasticity of the material greatly improves the impact resistance of the material.
the amorphous region is larger. This leads to better ductility and greater toughness of the sample,
Whenand theultimately
sample is printed
strong impactunder air cooling
resistance. With the conditions,
increase of the
heatcrystallinity of the sample
treatment temperature, is low and
the samples
the amorphous region
exhibit a weaker is larger.
resistance This
to the leads
impact load to and
better ductility
lower strengthandduegreater toughness
to the increase of the sample,
of crystallinity.
and ultimately strong impact resistance. With the increase of heat treatment temperature, the samples
exhibit a weaker resistance to the impact load and lower strength due to the increase of crystallinity.
 Polymers
Polymers 10, x 10,
2018, 2018, FOR 875PEER REVIEW 11 of 12
11 of 13

Figure
Figure 11. 11.
IzodIzod notchedimpacted
notched impacted strength
strength ofof3D-printed
3D-printedPPS samples.
PPS samples.

4. Conclusions
4. Conclusions
It is important to analyze the effect of the thermal condition on the performance of 3D-printed PPS
Itsamples
is important to analyze the effect of the thermal condition on the performance of 3D-printed
as PPS is a semi-crystalline thermoplastic polymer sensitive to oxidation. The PPS material
PPS samples
undergoesasa PPS is a (drying,
four-step semi-crystalline thermoplastic
screw extrusion, polymer
3D printing and heatsensitive
treatment) to oxidation.
heating processThe PPS
material
fromundergoes a four-step
pellet to 3D-printed (drying,
sample. The screw
thermalextrusion, 3D printing
history strongly anddegree
affects the heat treatment)
of crystallinityheating
process
andfrom pellet to 3D-printed sample. The thermal history strongly affects the degree of
crosslinking.
crystallinity In the
andprinting process, air-forced cooling improves the precision of the 3D-printed sample.
crosslinking.
The maximum deviation
In the printing process, air-forced decreases from +0.89/
cooling −2.38 mm
improves theunder the natural
precision of the cooling
3D-printed condition to The
sample.
+0.79/−deviation
maximum 0.89 mm under the air-forced
decreases from cooling condition.
+0.89/−2.38 mmMost studies
under have
the focusedcooling
natural on improving the
condition to
environment temperature in an effort to restrain the non-uniform thermal gradients. We here propose
+0.79/−0.89 mm under the air-forced cooling condition. Most studies have focused on improving the
reducing crystallinity by increasing the cooling rate to improve the precision of the 3D-printed sample.
environment temperature in an effort to restrain the non-uniform thermal gradients. We here propose
The mechanical properties of 3D-printed samples are another important index. Heat treatment
reducing crystallinity
compensates for theby increasing
insufficient the cooling
strength of a sample ratethat
to has
improve the air
undergone precision
cooling. of the 3D-printed
A higher heat
sample.
treatment temperature benefits the tensile strength and fracture toughness. The tensile strength
The mechanical
increases from 27.7properties
to 57.3 MPaofand 3D-printed
the fracture samples
toughnessareofanother important
3D-printed PPS samples index. Heat treatment
increases from
1/2 . Meanwhile, the elastic modulus increasing from 1.45 to 3.21 GPa, which is too
compensates
1.29 to 1.74 forMPathe·minsufficient strength of a sample that has undergone air cooling. A higher heat
high, results
treatment in the sample
temperature being
benefits unable
the tensileto withstand
strengthaand greater impact toughness.
fracture strength. The tensile strength
The mechanical properties of 3D-printed samples depend not only
increases from 27.7 to 57.3 MPa and the fracture toughness of 3D-printed PPS samples increases on inherent material properties from
1.29 to 1.74 MPa·m1/2. Meanwhile, the elastic modulus increasing from 1.45 to 3.21 GPa, thermal
(i.e., crystallization and crosslinking) but also on the 3D printing parameters (e.g., the infill and
which is too
processing conditions). The tensile strength and impact strength are mainly dictated by the degree of
high, results in the sample being unable to withstand a greater impact strength.
crystallinity and crosslinking. The heat treatment method provides an effective way to improve the
The mechanical properties of 3D-printed samples depend not only on inherent material
interlayer strength. The diffusion of the interlayer, warpage and delamination depend on the thermal
properties
conditions(i.e., during
crystallization
printing. Theandproper
crosslinking)
selectionbut also onprocessing
of thermal the 3D printing
and heatparameters (e.g., the infill
treatment conditions
and thermal
will allow processing
the processingconditions). The tensile3D-printed
of high-performance strength and impact strength are mainly dictated by
PPS samples.
the degree of crystallinity and crosslinking. The heat treatment method provides an effective way to
Author Contributions: Formal Analysis, P.G. and Y.W.; Data Curation, G.L. and S.W.; Writing-Original Draft
improve the interlayer
Preparation, strength.
P.G. and B.W.; The diffusion
Supervision, J.Z.; Funding ofAcquisition,
the interlayer,
W.W. warpage and delamination depend
on the thermal conditions during printing. The proper selection of thermal processing and heat
Funding: This research is supported by National Natural Science Foundation of China (No. 51675226); a Key
treatment conditions
Scientific will allow
and Technological the Project
Research processing of high-performance
of Jilin Province 3D-printed
(No. 20180201055GX); PPS
a Project of the samples.
International
Science and Technology Cooperation of Jilin Province (No. 20170414043GH); and the Graduate Innovation Fund
of Jilin University (No. 2017143).
Author Contributions: Formal Analysis, P.G. and Y.W.; Data Curation, G.L. and S.W.; Writing-Original Draft
Conflicts of Interest: The authors declare no conflict of interest.
Preparation, P.G. and B.W.; Supervision, J.Z.; Funding Acquisition, W.W.

Funding: This research is supported by National Natural Science Foundation of China (No. 51675226); a Key
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