European Polymer Journal 114 (2019) 234-248

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European Polymer Journal

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3D printing of polyether-ether-ketone for biomedical applications

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Sunpreet Singh3’*, Chander Prakash3, Seeram Ramakrishna1’
a
School of Mechanical Engineering, Lovely Professional University, Phagwara, Punjab 144411, India
b
Center of Nanofibers & Nanotechnology, National University of Singapore, Singapore

ARTICLE INFO ABSTRACT

Keywords: Despite the rapid progress of several three-dimensional (3D) printing technologies, there exists a critical barrier
3D printing in-term of processability of high performance materials. Polyether-ether-ketone (PEEK) is known for its higher
Biomedical engineering mechanical properties, chemical stability, biological stability and biocompatibility suitable for certain biome¬
Drug dical applications. Examining a growing body of scientific literature on 3D printing of biomedical polymers
Fused deposition modelling
indicates that most of the studies are conducted using biomedical polymers such as poly-carpolactone, poly¬
Orthopaedics
Polyether-ether-ketone
lactic acid, poly-glycolic acid, polyethylene and polyurethanes. However, studies on 3D Printing of PEEK is
Scaffold sparse owing to the higher temperatures needed for melting, lacking of availability of suitable feedstock, con¬
Selective laser sintering cerns over poor adhesion between layers, and time consuming and uneconomical processing steps. Given the
Tissue engineering unique nature of PEEK class of polymers, this manuscript closely examines 3D printability of PEEK for a range of
biomedical applications. This manuscript also presents ideas, feasible solutions and enabling scientific me¬
chanisms to improve the 3D printability of PEEK. This article will help the research community to strengthen the
conceptual knowledge and insights on the 3D printing of PEEK based medical devices and tools, and future
possibilities.

1. Introduction
The PEEK and its various co-polymers are nominated as some pro¬
mising alternative materials which do not only possess near-to-bone
mechanical properties but also good chemical resistance, and radi-
olucency [1-6]. PEEK (— C6H4—0C6H4— O— C6H4— CO— )n is basically a
semi-crystalline polymer developed by English scientists in 1978 how¬
ever, it reached at the doors of the industries and became an important
high strength polymer candidate in late 1990s [7]. The PEEK and its
different varieties including PEEK-LT1, PEEK-LT2, and PEEK-LT3 have
been used for different biomedical applications, for instance in spine
treatment, orthopaedic tools and products, maxillofacial surgery, etc.
[8]. Further, synthetically developed PEEK composites broaden the
physicochemical and mechanical characteristics of the products,
therefore, various methods to enhance the osteoinductive and anti¬
microbial capabilities are always attracted the researchers. Table 1 list a
comprehensive description of different types of PEEK based bio-mate-
rials used for various biomedical applications. Similarly, Table 2 shows
the comparison of different types of high performance thermoplastic
materials as a popular choice for 3D printing applications. Basically, the
repeated sterilization and shaping of PEEK through machining, thermal
deforming, and thereby combinations enable the formation of highly
complex shapes of the bones, scaffolds, and other medical devices.
Along with, the combination of excellent chemical and biological in¬
ertness of PEEK, as well as its possible composites with hydroxyapatite,
chitosan, and other bio-ceramics, helps to limit bone fixation as well as
enhances bone-implant integration [9-14]. Traditionally, PEEK has not
been used for the high production rates due to the associated processing
costs in comparison of other polymers [14],
However, on the other hand, researchers were always quite inter¬
ested to use PEEK materials as a subordinating material for conven¬
tional metallic implants in order to enhance their performances. Along
with this, gradually, the PEEK became a potential candidate as an al¬
ternative to precious metals. Therefore, various research activities have
been performed where reinforced PEEK qualified, successfully, and the
obtained results opened new pathways as well as challenges. It has been
outlined that the carbon fiber reinforced (CFR) PEEK implants, both in
coated and uncoated states, presented desirable level of in-vivo os-
seointegration when compared to titanium implants, there exists var¬
ious classes of medical treatments, including bone replacement-max¬
illofacial and cranial implants, spine surgery and spinal cages,
orthopaedic surgery, dental prosthesis, intra-radicular posts, cardiac
surgery-intracardiac pump, and heart valves, where PEEK and its
composites can be employed for satisfied services. However,

• Corresponding author.
E-mail address: snprt.singh@gmail.com (S. Singh).

https://doi.Org/10.1016/j.eurpolymj.2019.02.035
Received 20 January 2019; Received in revised form 19 February 2019; Accepted 22 February 2019
Available online 26 February 2019
0014-3057/ © 2019 Elsevier Ltd. All rights reserved.
S. Singh, et aL European Polymer Journal 114 (2019) 234-248

manufacturing of such critical and intricate shapes with almost zero

level of tolerances is itself a key problem that demands viable industrial
solutions.
Apart from this in [26], various methods of improving the bioac¬
tivity of PEEK have been highlighted [27]. Current research studies
have highlighted the potential of PEEK composites as a load bearing
materials and flexible implants which could be used for joint ar¬
throplasty [28,29], Furthermore, PEEK based composites can be en¬
gineered, effortlessly, into a broad range of custom specific physical,
mechanical, and surface properties. Specifically, today PEEK is suc¬
cessfully being used for the fabrication of spinal implants [29,30],
trauma implants [31], femoral stems [32], anthroplastry bearings [33],
scaffoldings [34], drug vessels [35], etc. The main credit for widespread
industrial utilization of PEEK goes to the availability of numerous sui¬
table commercial technologies, including machining, powder me¬
tallurgy, extrusion, shot blasting, injection moulding anodic oxidation,
alkali treatment, and acid-etching [36]. Fortunately, the PEEK can be
manufactured using conventional thermoplastic machines without the
need for a tempering process and in-process use of additives [37,38].
Since the use of a porous structure plays a vital role in almost all types
of biomedical and tissue engineering (BTE) application, hence, the
current trends are shifting towards such techniques which can create a
controlled architecture of the porous structures, having high level of
pore precision.
In this, three-dimensional (3D) printing is playing a prominent role
as one of the most advanced manufacturing processes [39,40]. Basi¬
cally, 3D printing is also known as additive manufacturing (AM),
layered manufacturing, rapid prototyping (RP), solid freeform fabrica¬
tion (SFF), layered manufacturing (LM) represents a class of direct
fabrication wherein the part is produced through a layer-by-layer
fashion, centrally controlled by a numeric controlled mechanism
[41,42]. Moreover, the 3D printing technologies can be collaborated
with the medical devices and scanning instruments, such as magnetic
resonance imaging and computer tomography, in order to retrieve the
first hand patient specific information, refer Fig. 1 [43,44]. Further, the
inherent feature of the 3D printing technologies automatically enables
the fabrication of controllable porous products [45],
Nowadays, this special feature of 3D printing system helps the re¬
searchers to meet with the requirement of porous structures which can
help in the initiation in the cell attachment, osseintegration, and
thereby, tissue growth [46]. Vaezi and Yang used extrusion based 3D
printing technology and created a PEEK based composite with con¬
trolled 3D inter-connected architecture [47], In another work, they
suggested that 3D printed porous PEEK have promising compressive
properties with potential for both load bearing and non-load bearing
application [48]. Although, being a material of great industrial im¬
portance, the 3D printing of PEEK has been some of the major issues in¬
terms of the physical properties of the end products [1,49].
It has been cited by various researchers that the processing of PEEK
material with 3D printers is quite difficult and imparting critical bar¬
riers for the widespread utility of the same for practical applications
[50] . Yang et al. outlined that the thermal processing conditions of 3D
printers can instrument a significant impact, directly or indirectly, on
the crystallinity and mechanical properties [51]. Having a high melting
temperature, selective laser sintering (SLS) and fused deposition mod¬
elling (FDM) are the only nominated 3D printing methods, whereas,
FDM has an additional benefit in-terms of process expenditures when
compared to the earlier [52]. Moreover, Valentan et al. developed a
special high temperature FDM system in 2013 for processing PEEK
material [53], resulted in not much appreciable outcomes.
However, in case of SLS, processing temperature might not be the
major issue but the processing of PEEK powder at about 350 °C limits
potential recycling of the non-fused PEEK powder that multiplies the
production expense [31], Specifically, problems in controlling the
temperature, occurrence of black specks, maintaining surface roughness
and dimensional accuracy, improper crystallization, and keeping PEEK

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Table 2
Comparison between different types of high performance thermoplastics.
Properties Poly-ether-ketone-ketone (PEKK) Poly-aryl-ether-ketone (PAEK) PEEK

Chemical structure

Glass transition 158 143

temperature (°C)
Processing temperature (°C) 380 330-360 385
Tensile Strength (MPa) 145 149 152
Youngs’ modulus (GPa) 5.2 4.1 5.2
Bio-compatibility Yes Yes Yes
Processability Medium Medium Easy
Key applications Aerospace, automotive, and chemical industries Bearings, piston parts, pumps, valve, etc. Similar to PEKK and PAEK along with biomedical
components applications

material dry are demanding practical solutions. Despite all, the recent
years have witnessed the significant efforts made on the 3D printing of
PEEK [54,55], and many others are motived to come up with optimized
procedures in order to reduce the defect formation during the printing
of PEEK [56] . Therefore, this paper is aimed to provide a state of the art
literature review on the 3D printing of PEEK for BTE application. This
paper will highlight the suitable 3D printer for processing PEEK mate¬
rial in different forms, such as filament and powder, current printing
barriers, and potential applications of 3D printing of PEEK in medical
industry.
2. 3D printers for PEEK
Being a polymeric material, PEEK could be printed with different
types of 3D printers which can process feedstock either available in
powder or filament form. However, the available literature outlines
only the extensive use of FDM and SLS technologies for handling a high
performance material like this [31,52], while some sources review the
on-going development of specialized printers [57,58], All types of 3D
printer, irrespective of their working principles, can take inputs from
CAD software, MRI/CT scan, and reverse engineering tool. The current
section deals with a comprehensive review of both FDM and SLS
technologies for processing PEEK material. Apart from this, an effort
has been made to summarize the 3D printers other than these which can
provide new and emerging horizons to the interested community.
Table 3 highlights the technological aspects of existing commercial
PEEK printers and materials. However, there are numerous upcoming
too.
2.1. Fused deposition modelling
Also known as fused filament fabrication [59], this technology ba¬
sically utilized a continuous filament feedstock of required diameter or
powder, generally depends on the machine model, that is heated in the
liquefier to a temperature nearby melting point and finally the fused
material is deposited on a fixtureless platform [60,61]. The liquefier
head and fixtureless platform follow a predefined numerically con¬
trolled machine path to build a 3D geometry. However, for a complex
geometry, support material is normally utilized to support overhanging
parts [62]. After heating, the subsequent cooling processes leads the
semi-molten filament to re-assume a solid state are characterized by
high thermal gradients inducing residual stresses on the printed com¬
ponent [63]. There exist two different sorts of FDM systems, such as
syringe based and filament based as shown in Fig. 2(a) [64] . There are
two variants of FDM machines available in the market such as RepRap,
an open-source project developed in 2007, and FabLabs, to support
education [65]. There are number of process parameters which are
widely researched in the last decade and the importance of the same is
well documented in-terms of strength, surface roughness, and dimen¬
sional accuracy [66-68].

Physical patient
specific devices

3D Printing
Fig. 1. Illustration of 3D printing digitization in biomedical sector.

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S. Singh, et aL European Polymer Journal 114 (2019) 234-248

The biggest advantage of FDM technology is its compatibility with a

broad range of polymeric materials as also there possible composites.
Polycarbonate (PC), acrylonitrile butadiene styrene (ABS), poly¬
phenylsulfone, PC-ABS blends, polyamide (PA), PC-medical grade,
polycaprolactone (PCL), high impact polystyrene (HIPS), etc. are the
common materials for FDM based printing [69]. However, the in¬
troduction of PEEK with FDM is comparatively new and full-proof
theories and procedures are still awaited [69]. Rahman et al. developed
and studied numerous specimens to evaluate the parametric effect on
the mechanical properties of the obtained PEEK samples. It has been
found that the fracture mechanics could be controlled by raster angle to
an appropriate setting [70]. Vaezi et al. [63] and Yang et al. [71] stu¬
died the mechanical properties, thermal processing conditions, and
tensile properties of the printed PEEK parts, respectively.
In a study conducted on rheological prospective of PEEK, it was
outlined the viscous stability of PEEK, in air, when heated is higher for
unreinforced condition than reinforced [72,73]. This can affect the
performance of the reinforced products in case of medical sector due as
the demands of reinforced products is expanding with time. Further, in
case of In the case of PEEK based medical devices reinforced with bio¬
ceramics, the biological efficacies can be compromised due to the lack
of physical bonding between the duo [74]. 3D printed porous PEEK
architecture can replicate the natural tissue and allow orientation of
cells in configuration closer to nature, and enhanced fixation of device
[75]. Despite limitations, recently, researchers have developed a carbon
fiber reinforced PEEK structure, based on a modified FDM setup that
could be used for biomimetic sensors, actuators, transducers, and arti¬
ficial muscles applications [76]. Zhao et al. conducted mechanical
characterization and in vitro cytotoxicity evaluations of the FDM
printed PEEK specimens in order to explore the biomedical potential of
the material. Interestingly, in-vitro cytotoxicity test outlined that no
toxic substances were introduced during the printing process [77].
However, with these limited reports, the biological performance indices
of FDM based PEEK structures are extremely difficult to establish.

2.2. Selective laser sintering

This technology was developed and patented Carl Deckard as an

experimental setup for his master’s thesis at the University of Texas in
1989 [78]. The schematic of the process is described in Fig. 2(b) [79],
In this process, a beam of laser is stroked over the building surface
where a tightly packed powder of thermoplastic material is available.
As shown in Fig. 2(b), the powder is moved and brought in right place
over the building platform by a cylindrical roller wherein fusion takes
place after the strike of an intensive and concentrated laser power [80].
When a single slice of the decided geometry is fully sintered, the piston
controlling the vertical motion of the platform moves downward to
accommodate the next slice above. The excess of powder particles that
surround the model object act as supporting structures during the
building process [81]. However, these supports often get heated due to
the heat and result into waste. A study conducted on the physico-che¬
mical behaviours of SLS processed PEEK material showed that inspite of
the fact that laser power causes degradation in the supports, the reuse
of PEEK powder in laser is still possible with a minor compromise on
mechanical performance [82], The whole fabrication takes place in a
sealed chamber which is maintained at a temperature below the
melting point of the feedstock [83], The morphology, structure, and
granulometry of the powder are highly crucial parameters in SLS [84].
For SLS products also, mechanical properties, dimensional shrinkage,
structural characteristics, surface roughness, and other materialistic
characteristics are greatly influenced by various process parameters,
including laser beam features too [85-90].
SLS being useful for both polymeric and metallic materials has an
edge over FDM as it can process a broad category of material including
those with higher melting temperatures. Moreover, as per the require¬
ment, the type of laser source can also be changed 180], Therefore

237
S. Singh, et aL European Polymer Journal 114 (2019) 234-248

(0
Fig. 2. Schematic of FDM: syringe-based (a) and fllament-based (b) and SLS (c) (reused after permission).

considering PEEK material, SLS is more suitable technology in com¬

Fig. 3. Multi-material cellular structure of T16A14V/PEEK [82] (reused after
permission].
parison of FDM, however, the cost is a primarily dominant factor as¬
sociated here. Also, the in-vitro and in-vivo efficacy of the medical parts
made with SLS technology is far better than FDM as in later the use of
organic solvent during post-fabrication processes cause toxicity [91],
While, one other source highlighted that owing to the larger pore size in
SLS, cells fall through the pores during the seeding process [92]. SLS, in
medical industry, has been used for making objects such as anatomical,
cutting and drilling guides, dental models, and scaffolds with materials
like PEEK [93-95]. Tan et al. explored the potential of SLS for fabri¬
cating solvent-free porous PEEK/HAP composites scaffolds and found
that the scaffold library approach used in the fabrication can result in
controlled microarchitecture and higher consistency [91]. Therefore, by
integrating computational design methods and SLS the anatomical
shaped external architectures and porous interior structure can be
produced. Fortunately, the Food and Drug Administration (FDA) of USA
issued the clearance certificate for the implication of SLS based printer

238
S. Singh, et aL
to process medical grade PEEK material [96] . In fact, OsteoFab is Ox¬
ford Performance Materials’s brand name for 3D printed medical parts
and implants produced a co-polymer of PEEK [97]. A multi-material
Ti6A14V-PEEK cellular structure, refer Fig. 3, was built by hybrid
manufacturing system consisted of a powerful version of SLS and hot
pressing [82],
Recent advances of SLS have been the ability to produce lower
stiffness scaffolds and higher resolution features [98]. Wilmowsky et al.
studied the individually shaped medical implant to evaluate the bio¬
logical behaviour of SLS processed PEEK implant indulged with osteo-
conductive bone materials in porcine bone defects. The obtained his-
topathollogical evaluation revealed that the implant was majorly
covered by connective tissue and there was no sign of inflammatory or
necroses [99]. However, after reviewing the boons and banes, it is
worth mentioning that there is still a lot to understand about the bio¬
compatibility of SLS based PEEK and bio-activity of SLS based PEEK
composites.
3. Challenges with PEEK
3.1. Printing issues
Although it has been more than 30 since the invention of 3D
printing technologies yet numerous issues such as material cost, in¬
vestment cost, and prolonged time for layer generation, manual work,
poor quality characteristics, and material constraints are unresolved,
specially, for processing novel materials such as PEEK. SLS is the first
3D printing technology used for the development of production routes
for PEEK [100]. But this printing technology is highly complicated
because of the variation in the size and shape of the powder particles
[101]. Additionally, the principle cost of the SLS system is higher than
FDM costly and the use of gas sourced laser generates high magnitudes
to waste [46,100], This problem can be solved by using a compact
adaptation system into the SLS part bed, allowing the adaptor to
transfer the motion of the SLS part bed onto its own small part bed
[102], However, the different limitations of SLS have fuelled the in¬
terest of commercial and research community to use FDM, as alter¬
native, to process PEEK. As yet, relatively few studies discuss FFF of
PEEK [39,46]. Wu et al. developed a PEEK 3D printing system and
defined optimal heated bed and print head nozzle temperatures for
FDM of PEEK [46]. While in FDM, the thermal gradient properties re¬
main a significant issue which can lead to limited mechanical perfor¬
mance when compared to moulded samples [103]. The filament during
the FDM printing fluctuates and alters the amount of melt during the
printing, which introduced voids in the part and decreased the tensile
strength [4]. The comparison between the 3D printed and injection
moulded parts demonstrated that despite using a professional graded
industrial FDM machine, the resulting parts did not outperform injec¬
tion moulded parts [48]. Also, the anisotropic properties of the 3D
printed parts are amongst the critical barriers [104]. Furthermore, full
medical certification of devices produced by the machine is the next
step, dependent upon geometry and application.
The mechanical strength of a thermoplastic typically increases with
the molecular weight and degree of branching or side chains.
Unfortunately this also results in an elevation of the melt viscosity and
melting point. The z-strength, or mechanical properties of the bond
between adjacent layers, is formed by physically pushing the polymer
melt into the previous layer. Therefore the resistance to melt flow is an
important parameter, and the extrusion of high strength thermoplastics
requires elevated temperatures that aggravate thermal distortion. The
melt pressure in FDM directly affects the surface morphology as a de¬
crease in it increase the surface defects [105]. Alternative materials for
AM need to outperform thermoplastics in a number of critical areas,
including mechanical properties (such as elastic modulus), chemical
resistance, thermal stability, and overall durability. New materials that
can be used in composite structures, and can attain higher performance
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European Polymer Journal 114 (2019) 234-248
than thermoplastic composites, are particularly desired [106]. In both
types of printer, as regards to PEEK processing, geometrical deforma¬
tion is highly complex because of the coupling of various parameters
with each other [46]. Beyond the existing technical issues related to 3D
printing, its ramifications on strength, fatigue resistance, biocompat¬
ibility, and bone in-growth, etc., should be assessed with well accepted
techniques addressed by FDA, USA. Further, 3D printing of PEEK im¬
plants should sought for clearance certification in-terms of their safety
and effectiveness [107].
Apart from the limitations from 3D printers’ part, PEEK material too
has certain issues as regards to medical applications. First, the viscosity
of this is high in comparison of other biocompatible materials such as
PC, PCL, and others. Owing to this, the processing becomes tedious and
the resulting product architecture is always undesirable. Secondly, the
affinity of PEEK with the bio-ceramics (such as HAP and chitosan) is
week which affects the in-vivo and in-vitro performances of the bio¬
products. Thirdly, the processing temperature of PEEK is higher and as
a consequence various open source low capacity printers are unlikely to
entertain it. Lastly, the cost of PEEK feedstock also restricts the wide¬
spread use for general and sophisticated engineering applications.
However, it has favourable characteristics including excellent me¬
chanical, heat retardant, and bio-inertness features, which make it a
potential candidate for demanding applications.
For a good print, there should be required affection between the
printer and material so that excellent quality with minimal anisotropy
could be achieved. Therefore, in possible scenario, the part should be
made in a way that the in-service stresses can be aligned with the
strongest orientation [108]. Similarly, the validation of the part's
characteristic should be carried out on the basis of standard test pro¬
cedures. There are various ASTM standards already available for some
testing, however, these are unable to capture complete picture
[61,109], for example, in the case of 3D scaffolds for BTE [110].
Moreover, the trade-offs of various quality performances can be opti¬
mized by using chemical compounding of the polymeric system.
3.2. Peek’s characteristics
Although, PEEK is a potential candidate for fabricating various
types of high standard biomedical implants owing to excellent tribo¬
logical, mechanical strength, and chemical resistance [111]. The main
restriction of PEEK concerning biomedical applications, such as pros-
theses and implants, is its relatively low integration to bone. Therefore,
it has found limited practical usages as in comparison of prominent
metals, such as Ti, Co-Cr alloys, and stainless steel, mainly in-terms
accelerated wear and corrosion issues, as discussed below:
• Predominant wear rate
It has been found that the wear rate of PEEK increases proportion¬
ally with the applied pressure [112], and considering demanding im¬
plants, such as hip, knee, spine, and elbow, the failure rate of PEEK
implants is high. However, the worn particles of PEEK have no cyto¬
toxic effect on the surrounding cells [113], As of today, there exists not
even a single PEEK based total joint arthroplasties (TJAs) device has
been cleared by the FDA for patient use because of predominant wear
[114], This is due to the fact of missing literature on the wear of PEEK
against hard counter-faces in the presence of a bovine serum lubricant
[115]. But, PEEK composites have shown in-vitro wear properties
comparable to metal-on-metal bearing couples [1,116] and are com¬
monly used in trauma implants and spinal fixation devices [117]. The
TJAs fail as a result of biologic responses to particles, it is imperative to
identify whether or not the wear debris produced by PEEK devices is
cytotoxic or immunologically reactive. In [118], authors reviewed 10
studies and found that the wear particles produced by PEEK-based
bearings were in almost all cases, in the phagocytozable size range
0.1-101m. A solution has been found in [1191, highlighted the
S. Singh, et aL
reduction in friction coefficient and resulting wear rate through the
addition of carbon fibers (CF) in polymeric structures. The same has
also been verified in another research [120]. Nowadays, PEEK material
is widely used as a veneering material for metallic in order to provide a
high mechanical strength, biocompatibility, and wear resistance in
human body conditions [121], Now, three contradicting questions are
arising here: (i) Does PEEK really suffer from accelerated wear? (ii) If
yes, why it is still being considered as a veneering surface for metallic
implants? (iii) If no, why PEEK based materials are being nominated for
hard tissue engineering [122] and load bearing applications [123]?
• Bioactivity
Although PEEK is always physically and chemically stable, yet it
needs modifications in-terms of physical or chemical treatments [124].
PEEK is biologically inert and often results in the improper fixation of
implants at defect sites and their loosening in severe cases [15]. For any
of the potential replacement of bio-metals, it is mandatory that the
replacement should have reasonably good cytocompatibility, especially
in case of orthopaedic applications [125], In order to inculcate the
same, reinforcement of bioactive materials is frequently required to
bring it at par with the requirements. It has been found that sulfonation
of PEEK was occurred after its immersion in concentrated sulfuric acid,
which caused geometrical distortions [126], In [127], authors showed
the rat osteoblast proliferation and the size and number of vinculin
adhesion plaques involved in cell spreading were comparable on PEEK,
titanium and cobalt chrome molybdenum alloy. However, in another
work, contradictory results questioned the interaction between PEEK
and osteoblastic differentiation [128]. For instance, in [129], PEEK
implants have comparable in-vitro bone forming capacity to that of
rough titanium. But, in [130|, osteoblasts differentiate was reportedly
less in case of PEEK as compared to titanium surfaces. As the titanium-
PEEK composite indeed allowed the better osteoblastic differentiation
than PEEK, therefore, there is a probable existence of PEEK-Halo effect
as discussed by [131]. Overall, the highlighted results on PEEK based
biomedical devices are contradicting in nature. Moreover, based on the
published literature, it is extremely hard to understand the realistic in-
vivo and in-vitro characteristics of the PEEK material.
3.3. Improving the performance of PEEK
Despite aforementioned issues, extensive research efforts have been
made in order to bring PEEK components at par with their counter
metallic products. Followings are the primary issues with PEEK mate¬
rial. Generally, mechanical, tribological, and biological properties of
the PEEK material can be modified by adopting two strategies including
physical and chemical. In comparison of physical modification
methods, chemical modification does not hold significance as PEEK is
chemically inert [132]. Coating, reinforcement, plasma treatment,
surface modifications, etc. [133-1361, are the commonly used methods
which can enhance the performance standards of PEEK material.
Table 4 lists the various activities which can benefits PEEK based bio¬
medical components.
4. Potential medical applications
Both 3D printing and PEEK has found utmost useful applications in
the area of biomedical and tissue engineering applications including
development of orthopaedic implants, scaffolds, artificial organs, sur¬
gical guides and templates, prostheses, and drug vessels. It is also true
that manufacturing of the PEEK based aforementioned medical devices
with conventional manufacturing technologies is very difficult due to
the existence of patient specific parameters that generally demands
specificity. And, it is only possible with 3D printing as it enable cus¬
tomization at any phase of the fabrication process. Therefore, this
section discusses the interesting biomedical application of PEEK, 3D
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European Polymer Journal 114 (2019) 234-248
printing, and their combination.
4.1. Scaffolding
Various researchers have nominated 3D printing as one of the best
technologies to fabricate complex internal and external geometries of a
scaffold. In [92], the composite scaffolds developed by using various
combinations of PEEK and HAP, through SLS showed great level of
interconnectivity with the scaffold. Further, the simulated body fluid
test demonstrated the cell adhesion with precipitation of bone-like
apatite in X-ray diffraction analysis. Vaezi et al. [151] proposed an
innovative FDM based fabrication technique which can yield a bioac¬
tive PEEK/HA composite scaffold with 100% interconnectivity, refer
Fig. 4(a) and (b), tailored pore size and distribution to facilitate greater
cellular infiltration and biological integration. Fig. 4(c) and (d) showed
the adherent of human bone marrow stromal cells on the surface of the
developed composite scaffold. Roskies et al. customized PEEK scaffolds
in order to incorporate a trabecular microstructure using computer
designed program and to print via SLS. The developed structure was
evaluated through SEM, refer Fig. 5, for the evaluation of the mor¬
phology [152]. It can be seen that the cytocompatibility of the scaffolds
to mesenchymal stem cells after 7-9 days were attached within the
pores of In their study, graphene oxide was introduced as an interface
phase to improve the interfacial bonding between PEEK and HAP. It has
been found that with the help of conjugated structure of grapheme
oxide strong rt-it bonds could be formed. Fig. 5 shows proliferation of
the cells which attached to the overall surface of the scaffolds. In [38],
authored outlined the benefits of PEEK composites. It has been men¬
tioned that the advanced technologies such as 3D printing enables
greater control on distribution of bioactive phase, for instance HAP,
within PEEK matrix. Moreover, the use of bioactive reinforcements
produces a 3D interconnected channel for further bone cells in-growth
and proliferation.
Overall, it can be concluded that the PEEK being bio-inert material
may not offer desirable bio-characteristics which can affect its candi¬
dature in biomedical sector. Therefore, attempts to overcome this by
introducing osteoinductive factors, such as HAP, are the need of the
hour. Also, the interactions of PEEK with bio-ceramics should be im¬
proved by using supportive substrate materials and interface agents.
4.2. Orthopaedic implants
3D printing of PEEK for the fabrication of orthopaedic implants and
load bearing devices, such as hip joints [154], is quite broad as com¬
pared to the other biomedical applications. The main reason for the
popularity of 3D printing is because it allows the creation of the cus¬
tomized, patient specific, anatomic model and products to help the
surgeons in understanding and replacing the faulty bones & limbs, re¬
spectively [155,156]. Moreover, severe orthopaedics problems related
such as spinal disorders, knee, elbow, hip, and bone fractures could also
be treated easily through the use of 3D printing and high performance
materials [157-159]. In [160], the authored discussed the ways how
pre-surgical planning could be done by using a custom printed models
to minimize the surgery time and blood loos of the patient. Gibbs et al.
[161] attempted to clearly define what 3D printing technologies have to
benefit orthopaedic surgeries. The history of implantable PEEK is not
new as the very first implant was introduced by London, United
Kingdom-based Invibio Biomaterial Solutions in 1999. Further, ma¬
chined and printed PEEK implants have already used for humans and
animals without major complications [162,163], respectively. How¬
ever, the printed PEEK implants have not explored in detail. In
[164,165], FDM and SLS sintered PEEK parts with graded porous parts,
for bone replacements, possessed excellent mechanical performance,
chemical stability and biocompatibility. To achieve further enhance¬
ment in the properties, especially bioactivity, numerous approaches,
such as spin coating, plasma gas teatment, plasma electron beam
 S.

Singh,
et
aL

Table 4
Methods of improving PEEK’S quality characteristics.
S. No. Method(s) Material system(s) Affected property Major outcome(s) Ref.

1 Composite fabrication PEEK/Alumina Mechanical The use of alumina reinforcement, 60 wt%, has increased the dynamic strength of the resulting [137]
composite by 78%
PEEK, Carbon fibers and nano-ZrO2 Mechanical and tribological The use of nano-ZrO2 reinforcement has reduced the stress concentration on the carbon fibers [138]
interface and the shear stress between sliding surfaces
PEEK/HAP Mechanical The tensile strength of the resulting composite was increased due to good interactivity between [139]
HAP and PEEK
PEEK/Inorganic tungsten disulfide- nanoparticles Mechanical and The hardness of the product was increased by 60% [140]
microscopical
PEEK/Carbon nano-tubes Mechanical and crystalline The use of the reinforcement enhanced the mechanical properties as well as reduced the [141]
crystallization rate of PEEK
241 PEEK/p-TCP Biological The proliferation rates of normal human osteoblast cells’ growth on P-TCP/PEEK were lower than [142]
PEEK
2 Blending PEEK/Polytetrafluoroethylene Tribological With the use of polytetrafluoroethylene in PEEK, the resulting coefficient of friction was reduced [143]
3 Processing temperature Injection moulding process Mechanical and tribological The hardness of the material increased with processing temperature and reduced the coefficient of [144]
friction
4 Use of additives Polyetherimide Mechanical The use of additive benefitted the mechanical and thermal processing of the PEEK based products [145]
5 Electron beam deposition Titanium Biological In-vivo tests showed that the coating of titanium on PEEK implants resulted in enhanced bone in¬ [146]
contact ratio
6 Pre-treatment of PEEK Piranha solution etching and abrasion followed by chemical Chemical Airborne particle abrasion in combination with piranha solution etching improved the adhesive [147]
treatment, and properties of PEEK
7 Plasma treatment - Chemical Plasma treatment of PEEK at atmospheric pressure worked remarkably in the improvement of [148]

8 Plasma immersion ion
deposition
9 Sterilization
—
adhesive strength of the polymer
Biological The experimented treatment is helpful in developing next generation orthopaedic implants [149]
- Mechanical Steam treatment was found more efficient than other(s) [150]

European
Polymer
Journal
114
(2019)
234- 8
S. Singh, et aL
Fig- 4. (a) Scanning electron microscopic image of 3D printed PEEK/HAP scaffold, (b) interface of PEEK and HAP, (c, d) cell adhesion on the developed PEEK/HAP
scaffolds [157], and (e, f) cell adhesion for PEEK scaffold [152],
deposition, plasma ion immersion, or the use of HAP/TiO2 could be
considered 1166]. Evans et al. [167] created a surface-porous PEEK
material with an average pore size of 279.9 ± 31.6 Im, strut spacing of
186.8 ± 55.51m, porosity of 67.3 ± 3.1% and interconnectivity of
99.9 ± 0.1%. Monotonic tensile tests conducted showed that the
strength preserved by the material was 73.9% if compared to as-re¬
ceived moulded PEEK. Further, an osseointegration model in the rat
revealed substantial bone formation within the pore layer at 6 and
12 weeks by using a micro-CT technology and histological evaluation.
The overall results indicated that the produced material could provide
242
European Polymer Journal 114 (2019) 234-248
improved osseointegration by maintaining the structural integrity.
Therefore, PEEK material can be used as a bearing surface in ar¬
throplasty wherein this can be processed on-site by using 3D printers to
get personalized implant geometry. This on-site or corporate based
processing can be used to make a bearing surface that can live up to the
current implant standards set forth by ASTM and, obviously, the FDA
[168], Wang et al. studied the bacterial resistance of fabricated PEKK
implant, comprised with nano-pillars with random inter pillar spacing
and compared the same with its co-polymers. After 5 days test, it has
been found that the PEEK has 37% higher Staphylococcus epidermidis
S. Singh, et at
Fig. 5. MG-63 cell attachment and proliferation on the PEEK-HAP/GO [153].
as compared to its co-polymer [169]. Although, a couple of test con¬
ducted on SLS based PEEK implants presented a positive clinical impact
[170,171], however, currently, due to the lack of efforts, ex¬
trusion-based 3D printing is still in its very early phase [4].
4.3. Dental and oral craniofacial/maxillofacial applications
In the past years, PEEK and its composites have furthermore har¬
vested much interest in the clinical dentistry not just because of the
attainable aesthetics but due to its incredible bio-mechanical properties
[172], It has been proposed by the researchers that this material can
showcase less stress-shielding effects in comparison of conventionally
used dental materials such as titanium [173]. Considering mechanical
and physical properties similar to bone, PEEK can be used in many
areas of dentistry. However, improving the bioactivity of PEEK dental
implants without compromising their mechanical properties is a major
challenge [174]. Moreover, PEEK does not cause any toxicity, muta¬
genic effects, and significant inflammation [175,176]. However, being
small in size, fabrication of dental and maxillofacial devices is a chal¬
lenging task and should be comprehended to completely understand the
available useful technologies. Here, CAD/CAM assisted 3D printers can
have a notable advantage as these have negligible effect of the me¬
chanical properties of the PEEK, therefore, can maintain the desirable
specification [177] . Thus, considering 3D printing of PEEK in order to
develop dental implants, denture prostheses, and crowns is an efficient
way. Moreover, crowns and fixed dental prostheses (FDPs) are gen¬
erally made of ceramic or composite resin, and here the application of
PEEK is still amateur [178]. Msallem et al. followed a hybrid manu¬
facturing route consisted of FDM and silicon moulding processes. In
their work, sterilization of a patient-specific mold was done first and
then used intra-operatively to produce an implant. They did a huge cost
cutting because the procedure adopted was very simple, basic, and
convenient [179].
Roskies et al. attempted to combine and improve after the two
methods by altering the internal geometry into a trabecular network
and to impregnate PEEK with mesenchymal stem cells. In this work,
they compared the newly developed craniofacial structures through its
interaction with bone-derived (BMSC) and adipose (ADSC) stem cells
[152], The results of the study showed that unreinforced SLS printed
PEEK supported both BMSC and ADSC cell growth and integration;
however, ADSCs differentiated into osteoblasts much more reliably
when co-cultured with the structured. Some clinical researches dis¬
cussed the practicality of 3D printing to create PEEK based max¬
illofacial implants, refer Fig. 6 [180],
Overall, it is worth to recapitulate by stating that the different
benefits of 3D printing of PEEK for making dentistry, maxillofacial, or
craniofacial devices help the practitioners to fabricate strong and
lightweight products to provide comfortable experience to the patients.
243
European Polymer Journal 114 (2019) 234-248
Fig. 6. Possible replacement of cranioplasty and orbital rim implants of tita¬
nium by 3D printed PEEK [180].
4.4. Miscellaneous medical applications
Other than aforementioned applications, the 3D printing of the
PEEK can also be explored, comprehensively, in the domains of drug
delivery, bone regeneration, and producing nano-scaled devices.
• Tan et al. [181] fabricated filaments of PEEK, for drug delivery
application, by using the hot melt extrusion technology that could
be used as feedstock of FDM at later stage; refer Fig. 7 for detailed
set-up. It has been found that the bioactivity and solubility of the
drugs have been enhanced for the purposefully release of the drug
over a prolonged period of time. Interestingly, many researchers
have also designed and fabricated novel scaffolds which can also
deliver required drugs in a well-controlled manner. Here, FDM and
SLS are playing tremendous roles [172-187]. Further, it is outlined
that the future utility of 3D printing of soft materials, particularly
for lipid-based drug delivery systems, will offers appreciable bene¬
fits to potentially support patient compliance [188], This demands
the extensive explorations of bioprinters/bioplotters.
• Similarly, low temperature 3D printing systems hold acknowledge¬
able promises for fabricating synthetic bone graft substitutes with
enhanced performance over traditional techniques [189],
• Gittard and Narayan [190] reviewed the fabrication of micro and
nano structured devices through 3D printing. A wide variety of
medical devices, such as prostheses, drug delivery devices, bio¬
sensors, stents and tissue scaffolds were highlighted in this work.
Further, in [191], author discussed a 3D printing assisted procedure;
refer Fig. 8, to solve complex medical problems. Additionally, var¬
ious others suggested the potential of this revolutionary technology
to aid vascular networks [192], bandages [193], bones [194], ears
[195], and exoskeleton issues [196],
5. Concluding remarks
3D printing and PEEK material both are well integrated with the
medical devices for many years. It has been reported by various re¬
searchers that PEEK and its composites have a bright future in biome¬
dical industry owing to their near to bone mechanical characteristics.
However, the manufacturing of the complex biomedical geometries is
not too easy through conventionally available technologies; therefore,
3D printing is currently being explored to overcome the existing man¬
ufacturing hurdles. Admittedly, through 3D printing, it is feasible to
construct patient specific controlled architectures with optimized
S. Singh, et aL European Polymer Journal 114 (2019) 234-248

DESIGN

HOT-MELT EXTRUSION PROCESS

PRINTING
DOSAGE FROM 3D PRINTING
OUTPUT AS DESIGNED
Fig. 7. Hybrid hot melt extrusion and FDM systems for continuous fabrication of drug delivery vessels 1181].

Fig. 8. Schematic illustrating the 3D reconstruction process flow (A) 3D diseased aorta model; (B) virtual testing; (C) FEA analysis; (D) determining rupture potential;
(E) averaged idealized aneurysm; (F) customized aneurysm; and (G) healthy aorta.

244
S. Singh, et al
process contributors.
Although, both potential printers, namely FDM and SLS, are strug¬
gling with their inherent manufacturing issues, as regards to PEEK and
its composites. FDM based PEEK products suffer from thermal, me¬
chanical, and dimensional shocks because of the unfriendly processing
conditions, particularly fusion temperature. Whereas, SLS printer’s in¬
itial cost as well as the generation of the waste during manufacturing
are inclining the overall expenditures. Furthermore, the poor interac¬
tion of the bio-ceramics and PEEK material leads to drop down the
performance indices of bio-products, however, it could be resolved by
using an interfacing agent or coupler, as suggested in [153].
Furthermore, the availability of standards for testing and validating
the 3D printed biomedical tools and devices is insufficient, restricting
the widespread utilization of the technology and associated materials.
Therefore, the future research efforts should not only focus the possible
innovations to dropdown the manufacturing cost of the biomedical
devices but also to provide acceptable testing standards to encourage
the commercialization of the processed products. With these only, the
actual use of the "3D printing of PEEK” could be validated for the in¬
terest of the community.
Acknowledgement
There is no conflict of interest.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.eurpolymj.2019.02.035.
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Further Reading
[1] R. Sonntag, J. Reinders, J.P. Kretzer, What’s next? Alternative materials for articu¬
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site polyetheretherketone/Bioglass® coatings deposited on Ti-6Al-7Nb alloy for
medical applications, Appl. Surf. Sci. 15 (273) (2013) 62-67.
[3] A. Wang, R. Lin, C. Stark, J.H. Dumbleton, Suitability and limitations of carbon fiber
reinforced PEEK composites as bearing surfaces for total joint replacements, Wear 1
(225) (1999) 724-727.
[4] S. Scholes, A. Unsworth, Wear studies on the likely performance of CFR-PEEK/
-
CoCrMo for use as artificial joint bearing materials, J. Mater. Sci. Mater. Med. 20
(2009) 163-170.
[5] F.P. Koch, D. Weng, S. Kramer, S. Biesterfeld, A. Jahn-Eimermacher, W. Wagner,
Osseointegration of one-piece zirconia implants compared with a titanium implant of
identical design: a histomorphometric study in the dog, Clin. Oral Implants Res. 21
(2010) 350-356.
[6] LV. Panayotov, V. Orti, F. Cuisinier, J. Yachouh, Polyetheretherketone (PEEK) for
-
medical applications, J. Mater. Sci. Mater. Med. 27 (7) (2016) 118.