Materials Research Innovations

ISSN: 1432-8917 (Print) 1433-075X (Online) Journal homepage: https://www.tandfonline.com/loi/ymri20

Manufacture and thermal deformation analysis of

semicrystalline polymer polyether ether ketone by
3D printing

W. Z. Wu, P. Geng, J. Zhao, Y. Zhang, D. W. Rosen & H. B. Zhang

To cite this article: W. Z. Wu, P. Geng, J. Zhao, Y. Zhang, D. W. Rosen & H. B. Zhang
(2014) Manufacture and thermal deformation analysis of semicrystalline polymer polyether
ether ketone by 3D printing, Materials Research Innovations, 18:sup5, S5-12-S5-16, DOI:
10.1179/1432891714Z.000000000898

To link to this article: https://doi.org/10.1179/1432891714Z.000000000898

Published online: 21 Aug 2014.

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 Manufacture and thermal deformation
analysis of semicrystalline polymer polyether
ether ketone by 3D printing
W. Z. Wu1, P. Geng1, J. Zhao1, Y. Zhang1, D. W. Rosen2 and H. B. Zhang*3
This study developed a polyether ether ketone (PEEK) three-dimensional (3D) printing system.
Three-dimensional printing chamber is designed for researching and solving the thermal
deformation problem of the fabricating high melting point biomaterial PEEK process through 3D
printing. A multi-parameter single factor experiments were carried out to analyse the effect of
chamber temperature T1, nozzle temperature T2 on deformation of PEEK 3D printing samples. The
results prove that the warping deformation is minimal with the chamber temperature at 130uC, the
nozzle temperature at 350uC. The PEEK parts were printed successfully through the optimal
parameters determined by the experiment. The results of this study demonstrate the feasibility of
manufacturing personalised small batch PEEK function parts in industrial and medical fields.
Keywords: Crystalline polymer, PEEK, 3D printing, Thermal deformation analysis, Biomaterial

Introduction comparative analysis of the PEEK samples is also

Polyether ether ketone (PEEK) is a super high
performance special engineering plastic. Its melting
point is 334uC, the glass transition temperature is
143uC, and can be used for a long time at a high
temperature of 250uC and for a short time at 300uC.1
PEEK has the advantages of temperature resistance, and
excellent mechanical properties including high strength,
elastic modulus and fracture toughness. PEEK also
exhibits excellent biocompatibility. PEEK interacts well
with the live tissue cells after being implanted into
animals.2
3D printing technology is an advanced manufacturing
technology based on the principle of layered manufacturing.3
Because of process limitations, current commercial 3D
printers can only print certain materials. Schmidt et al.
have formed PEEK by selective laser sintering. PEEK has
been commercialised by both 3D Systems and EOS in
their SLS machines. But this method has some significant
limitations for industrial applications and the equipment
cost is very high.4
In this study, high viscosity and hard formed PEEK is
produced by 3D printing with a custom-made PEEK
material extrusion 3D printing system, and the effect of
reaction parameters on deformation of PEEK 3D-printed
parts is investigated through the method of multi-
parameter single factor experiment. The deformation
1
School of Mechanical Science and Engineering, Jilin University, Renmin
Street 5988, Changchun 130025, China
2
George W. Woodruff School of Mechanical Engineering, Georgia Institute
of Technology, Atlanta, GA 30332, USA
3
Alan G. MacDiarmid Institute, College of Chemistry, Jilin University,
Qianjin Street 10#, Changchun 130012, China
*Corresponding author, email zhanghaib@jlu.edu.cn
performed. Compared with SLS, our method does not
generate waste gas or pollution generated by the laser
sintering powder materials. Moreover, the expensive laser
device is not employed to form the materials, and greatly
reduces energy consumption.
Methods and materials
In this research, a custom-made PEEK 3D printing
system is employed, as shown in Fig. 1. This system
includes a 3D printing platform that can move along the
X and Y axes directions. A 0?2 mm thick PEEK film is
coated on the surface of the platform and a 3D printing
chamber with a heating equipment installed on it. This
chamber can control the PEEK 3D printing tempera-
ture. Temperature control systems include ones for the
nozzle, chamber and printing platform.
The PEEK used in this research is purchased from
Changchun Jilin University Special Plastic Engineering
Research Co., Ltd. Its melting point is 334uC, the glass
transition temperature is 143uC and the melt index is
44 g/10 min. A 2062063 mm 3D digital model is
the PEEK printing sample. To remove moisture from
the PEEK and to prevent bubbles in the 3D printed
samples, a PEEK filament with a diameter of 1?6 mm
was dried in an oven at a temperature of 130uC for 8 h
firstly. Then the chamber temperature T1 was increased
to 90–130uC, the nozzle temperature T2 was increased to
340–360uC, the platform temperature T3 was increased
to 150uC by the PEEK 3D printing temperature control
system. The system temperature was held at these values
for 5–10 min. Finally, we placed PEEK filament into the
pre-heated nozzle at a constant speed through the wire
feed system. The 3D printing nozzle moves along a
certain path on the stratified surface of the sample and

ß W. S. Maney & Son Ltd. 2014

Received 3 March 2014; accepted 6 May 2014
S5-12 DOI 10.1179/1432891714Z.000000000898 Materials Research Innovations 2014 VOL 18 SUPPL 5
 Wu et al.
1: chamber temperature controller; 2: nozzle temperature controller; 3 PEEK; 4 nozzle; 5 chamber
1 PEEK 3D printing device
prints the first layer of the PEEK sample, then the nozzle
moves up a layer along the Z axis after finishing the first
layer and continues to print the second layer. The first
and second layers are bonded together firmly through
the adhesive force of melted PEEK. Subsequent layers
are printed until the PEEK 3D sample is complete. To
reduce the stratification and deformation of PEEK
caused by crystallisation shrinkage during the printing
process, it is necessary to maintain the chamber
temperature for 20–30 min after finishing printing.
Then, we gradually cooled T1 to room temperature at
a rate of 5uC min21. The simple variable method is
adopted to research the influence of chamber tempera-
ture T1 and nozzle temperature T2 on forming quality.
We selected five levels from each factors to print PEEK
samples. Table 1 is the single factor experiment design of
3D printing samples, group A parameters is chamber
temperature T1, group B parameters is nozzle tempera-
ture T2. The layer thickness is 300 mm.
Then, a non-contact 3D scanner-Shining3D EaScan-T
Scanner (Hangzhou Shining 3D Tech Co., Ltd) was
employed to scan the PEEK samples printed in single
factor experiments. The point cloud data of 3D printing
sample is obtained and compared with the 3D data
models of the samples for analysing the samples warping
deformation.
Results and discussion
The PEEK samples are printed at room temperature
to 90uC, the large temperature difference between the
underlying and processing layer results in different
cooling speeds when 3D printing. Samples exhibited
serious warping, delamination, cracking or even inabil-
ity to print. Therefore, this paper investigates PEEK 3D
printing single factor experiment above 90uC.
Chamber temperature
Group A variables are chamber temperature T1 in the
single factor experiment. Figure 2 shows the PEEK
Table 1 Designing experiment of single factor
A B
Group no. 1 2 3 4
Chamber temperature/uC 90 100 110 120
Nozzle temperature/uC 350 350 350 350
Manufacture and analysis of semicrystalline polymer polyether ether ketone
samples printed by the custom-made PEEK 3D printing
system under the chamber temperature at 90, 100, 110,
120 and 130uC respectively. Figure 3 is a comparative
analysis on deformation between sample point clouds
and three 3D models at different chamber temperatures.
In the single factor experiment of the chamber
temperature, as the chamber temperature increases from
90 to 130uC, the sample warping deformation reduces
from 1?93 mm to 0?65 mm, the difference value of the
two points is 1?28 mm. When the chamber temperature
rises from 90 to 100uC, the sample warping deformation
reduces 1?93 mm to 1?10 mm. The sample warping
distortion is significant. It is mainly caused by the PEEK
cooling too quickly, resulting in uneven crystallisation
within this range of temperature, the internal stress is
large which brings significant deformation. When the
chamber temperature rises from 100 to 130uC, the
sample warping deformation reduces from 1?10 mm to
0?65 mm. This indicates that with the increasing 3D
chamber temperature, the cooling rate slows down,
which makes the PEEK more fully crystallised and
internal stress to be small, as shown in Fig. 4.
Nozzle temperature
Group B variables are nozzle temperature T2 in the
single factor experiment. Figure 5 shows the PEEK
samples printed by the custom-made PEEK 3D printing
system under the nozzle temperature at 340, 345, 350,
355 and 360uC respectively. A comparative analysis is
performed on deformation between sample point clouds
and 3D digital models at different nozzle temperatures.
In the single factor experiment of the nozzle tempera-
ture, as the nozzle temperature increases from 340 to
350uC, the amount of the sample warping deformation
reduces from 1?26 mm to 0?65 mm, the difference value
of the two points is 0?61 mm. With the nozzle
temperature rising to 360uC, the amount of the sample
warping deformation reaches 1?35 mm, the difference
value of the two points is 0?7 mm. Compared to the
5 6 7 8 9 10
130 130 130 130 130 130
350 340 345 350 355 360
Materials Research Innovations 2014 VOL 18 SUPPL 5 S5-13
Wu et al. Manufacture and analysis of semicrystalline polymer polyether ether ketone

a T1590uC; b T15100uC; c T15110uC; d T15120uC;

e T15130uC
2 3D printing samples of PEEK

influence of the chamber temperature, and the nozzle

temperature has a little impact on the warp of the
sample.
The warping deformation of sample is minimal with
the nozzle temperature of 350uC, as shown in Fig. 6.
Suitable nozzle temperature can guarantee the sufficient
time of heating the PEEK filament. If the nozzle
temperature is too low, the PEEK filament has not
melted completely, which leads to plug nozzle because of
the larger viscosity. If the nozzle temperature is too high,
crosslinking reaction will occur, and PEEK may even
burn.
The optimum conditions were obtained through the
two factors of PEEK 3D printing single factor experi-
ment and comparative analysis, including the chamber
temperature T1 at 130uC and the nozzle temperature T2
at 350uC. The chamber temperature has more influence
on the warping deformation of PEEK samples than the
nozzle temperature does. When the 3D printing tem-
perature and other factors are selected appropriately,
high quality PEEK parts can be printed successfully.
Figure 7 shows a high quality 3D printed PEEK nut.
4 Influence of chamber temperature on warp deformation
Through comparing SEM images of the PEEK materials
before print, filiform PEEK after 3D print and PEEK
3D print part (Fig. 8), the form of organisation is the
same, the physical appearance of PEEK part do not
have significant changes after 3D printing.
Conclusions
This study realised a semicrystalline polymer material
PEEK forming by 3D printing. The effect of forming
factors on the quality of PEEK 3D printed samples was
researched. The 3D digital model based on reversed
engineering was established for deformation analysis
comparison with the original one. The experimental
results showed that the warping deformation of PEEK
sample is minimal when the chamber temperature T1 is
at 130uC and the nozzle temperature T2 at 350uC. The
chamber temperature has more influence on the warping

a T1590uC; b T15100uC; c T15110uC; d T15120uC; e T15130uC

3 Matching between surface point cloud data of PEEK samples and its CAD model

S5-14 Materials Research Innovations 2014 VOL 18 SUPPL 5

 Wu et al. Manufacture and analysis of semicrystalline polymer polyether ether ketone

a T25340uC; b T25345uC; c T25350uC; d T25355uC;

e T25360uC
5 3D printing samples of PEEK

6 Influence of nozzle temperature on warp deformation

a PEEK before print; b filiform PEEK after 3D print; c

7 3D printing part of PEEK PEEK 3D print part
8 Images of scanning electron microscope

deformation of PEEK samples than the nozzle tempera-
ture does.
In the process of manufacturing PEEK by 3D printing,
deformation is very complex because of many parameters
with coupled interaction between each other. For the
PEEK materials used in this study, warping deformation
of sample can be effectively controlled by the appropriate
parameters. Semicrystalline polymer PEEK has excellent
mechanical properties, chemical stability and biocompat-
ibility. The manufacturing of PEEK by 3D printing will
enable small batch production of industrial function
parts, personalised PEEK artificial bones, PEEK medical
apparatus and instruments in industrial and medical
fields.
Acknowledgements
This research is supported by National Natural Science
Foundation of China (No. 51205163), ‘SRFDP’ (No. 2012
0061120030), Young Research Fund of Jilin Province
Science and Technology Development Plan (No. 20
140520124JH).

Materials Research Innovations 2014 VOL 18 SUPPL 5 S5-15

Wu et al. Manufacture and analysis of semicrystalline polymer polyether ether ketone

2. R. Hosemann: ‘Crystalline and paracrystalline order in high

References
1. C. Wang and C. T. Sun: ‘Experimental characterization of
constitutive models for PEEK thermoplastic composite at heating
stage during forming’, J. Compos. Mater., 1997, 31, (15), 1480–
1506.
polymers’, J. Appl. Phys., 2004, 34, (1), 25–41.
3. M. Pawlyn and M. Braungart: ‘Push the limits Of 3D printing’,
Nature, 2013, 494, (7436), 174–174.
4. M. Schmidt, D. Pohle and T. Rechtenwald: ‘Selective laser sintering
of PEEK’, CIRP Ann.-Manuf. Technol., 2007, 56, (1), 205–208.

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