European Polymer Journal 114 (2019) 234–248

Contents lists available at ScienceDirect

European Polymer Journal

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

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

a,⁎ a b
Sunpreet Singh , Chander Prakash , Seeram Ramakrishna
a
School of Mechanical Engineering, Lovely Professional University, Phagwara, Punjab 144411, India
b
Center of Nanofibers & Nanotechnology, National University of Singapore, Singapore

A R T I C LE I N FO A B S T R A C T

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 complex shapes of the bones, scaffolds, and other medical devices.
Along with, the combination of excellent chemical and biological in-
The PEEK and its various co-polymers are nominated as some pro- ertness of PEEK, as well as its possible composites with hydroxyapatite,
mising alternative materials which do not only possess near-to-bone chitosan, and other bio-ceramics, helps to limit bone fixation as well as
mechanical properties but also good chemical resistance, and radi- enhances bone-implant integration [9–14]. Traditionally, PEEK has not
olucency [1–6]. PEEK (eC6H4eOC6H4eOeC6H4eCOe)n is basically a been used for the high production rates due to the associated processing
semi-crystalline polymer developed by English scientists in 1978 how- costs in comparison of other polymers [14].
ever, it reached at the doors of the industries and became an important However, on the other hand, researchers were always quite inter-
high strength polymer candidate in late 1990s [7]. The PEEK and its ested to use PEEK materials as a subordinating material for conven-
different varieties including PEEK-LT1, PEEK-LT2, and PEEK-LT3 have tional metallic implants in order to enhance their performances. Along
been used for different biomedical applications, for instance in spine with this, gradually, the PEEK became a potential candidate as an al-
treatment, orthopaedic tools and products, maxillofacial surgery, etc. ternative to precious metals. Therefore, various research activities have
[8]. Further, synthetically developed PEEK composites broaden the been performed where reinforced PEEK qualified, successfully, and the
physicochemical and mechanical characteristics of the products, obtained results opened new pathways as well as challenges. It has been
therefore, various methods to enhance the osteoinductive and anti- outlined that the carbon fiber reinforced (CFR) PEEK implants, both in
microbial capabilities are always attracted the researchers. Table 1 list a coated and uncoated states, presented desirable level of in-vivo os-
comprehensive description of different types of PEEK based bio-mate- seointegration when compared to titanium implants. there exists var-
rials used for various biomedical applications. Similarly, Table 2 shows ious classes of medical treatments, including bone replacement-max-
the comparison of different types of high performance thermoplastic illofacial and cranial implants, spine surgery and spinal cages,
materials as a popular choice for 3D printing applications. Basically, the orthopaedic surgery, dental prosthesis, intra-radicular posts, cardiac
repeated sterilization and shaping of PEEK through machining, thermal surgery-intracardiac pump, and heart valves, where PEEK and its
deforming, and thereby combinations enable the formation of highly 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

attachment, spreading, proliferation, and osteogenic differentiation

level of tolerances is itself a key problem that demands viable industrial

The resulting material is highly promising for spinal applications

BioHPP should not be considered as a substitute of conventional

The knitted composite bone plates showed higher deformability.

Bioactivity of the final product was significantly improved using
solutions.

Chitosan contributed antibacterial properties to the polymer

The nano-HA/PEEK composites were found to promote cell
Apart from this in [26], various methods of improving the bioac-

Silica coated PEEK obtained better mechanical properties

tivity of PEEK have been highlighted [27]. Current research studies
have highlighted the potential of PEEK composites as a load bearing

Apatite layer development on PEEK was very slow

materials and flexible implants which could be used for joint ar-
throplasty [28,29]. Furthermore, PEEK based composites can be en-

The material resulted in no complications.

gineered, effortlessly, into a broad range of custom specific physical,

The results encouraged the use of PEEK

mechanical, and surface properties. Specifically, today PEEK is suc-
cessfully being used for the fabrication of spinal implants [29,30],
Soaking did not affect PEEK 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-
metallic materials
nano-TiO2 filling
Remarks, if any

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
Interbody spinal fusion

Regenerative medicine

of biomedical and tissue engineering (BTE) application, hence, the

Maxillo-facial surgery
Orthopaedic implants

Orthopaedic fixations

Skull bone treatment

current trends are shifting towards such techniques which can create a
Bone substitution

Dental prosthesis

Dental prosthesis

Ophthalmology

controlled architecture of the porous structures, having high level of

Service Area

Orthopaedic

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),
Elastic modulus 4.6 MPa and compressive

layered manufacturing, rapid prototyping (RP), solid freeform fabrica-

Bending modulus 3.8 GPa and bending

tion (SFF), layered manufacturing (LM) represents a class of direct

fabrication wherein the part is produced through a layer-by-layer
Maximum average load 1790 N

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
Mechanical Properties

resonance imaging and computer tomography, in order to retrieve the

strength 160 MPa

14.5 ± 2.6 MPa

strength 93 MPa

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-
Temperature

trolled 3D inter-connected architecture [47]. In another work, they

Processing

suggested that 3D printed porous PEEK have promising compressive

400 °C

380 °C

400 °C

400 °C

380 °C

180 °C

properties with potential for both load bearing and non-load bearing
na
–

–
–

application [48]. Although, being a material of great industrial im-

portance, the 3D printing of PEEK has been some of the major issues in-
Micro-braiding yarn and hot moulding
Moulding and soaking with phosphate
Milling proceeded by acid etching air
Compression moulding and chemical

terms of the physical properties of the end products [1,49].

Compression moulding and NAOH

It has been cited by various researchers that the processing of PEEK

Powder mixing and compression

Powder mixing and compression

material with 3D printers is quite difficult and imparting critical bar-

abrasion and silica coating

riers for the widespread utility of the same for practical applications
Air plasma modification

[50]. Yang et al. outlined that the thermal processing conditions of 3D

Processing method

printers can instrument a significant impact, directly or indirectly, on

buffered saline
Wax moulding

the crystallinity and mechanical properties [51]. Having a high melting

CNC milling
List of PEEK based biomedical devices.

temperature, selective laser sintering (SLS) and fused deposition mod-

treatment
moulding

moulding

leaching

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

HAP embedded PEEK [18]

Knitted carbon/PEEK [21]

special high temperature FDM system in 2013 for processing PEEK

Type of PEEK material

Nano-TiO2/PEEK [15]

Nano-HAP/PEEK [16]

material [53], resulted in not much appreciable outcomes.

Chitosan/PEEK [22]

However, in case of SLS, processing temperature might not be the

PEEK blanks [19]

PEEK films [24]

PEEK PSIs [23]

major issue but the processing of PEEK powder at about 350 °C limits
BioHPP [17]

potential recycling of the non-fused PEEK powder that multiplies the

PEEK [20]

PEEK [25]

production expense [31]. Specifically, problems in controlling the

Table 1

temperature, occurrence of black specks, maintaining surface roughness

and dimensional accuracy, improper crystallization, and keeping PEEK

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S. Singh, et al. European Polymer Journal 114 (2019) 234–248

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 158 147 143

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

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

https://www.3dxtech.com/thermax-peek-
http://vshaper.com/en/3d-printers/med/

https://www.protiq.com/en/3d-printing/
https://www.eos.info/systems_solutions/

https://tractus3d.com/our-industrial-3d-
plastic/systems_equipment/eosint_p_800

https://www.aniwaa.com/best-peek-3d-
broad range of polymeric materials as also there possible composites.

https://apiumtec.com/en/apium-m-
Polycarbonate (PC), acrylonitrile butadiene styrene (ABS), poly-
phenylsulfone, PC-ABS blends, polyamide (PA), PC-medical grade,

series-medical-peek-3d-printing

https://www.intamsys.com/
https://www.kumovis.com/
polycaprolactone (PCL), high impact polystyrene (HIPS), etc. are the

printers/peek-3d-printer/
common materials for FDM based printing [69]. However, the in-

3d-printing-filament/
troduction of PEEK with FDM is comparatively new and full-proof

material/plastic-sls/
printer-pei-ultem/
theories and procedures are still awaited [69]. Rahman et al. developed
and studied numerous specimens to evaluate the parametric effect on
Reference

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
Apium M220 Series 3D printers are equipped with advanced temperature

Smart design for continuous production; high speed; high precision; and
It is already used to aid the creation of dental crowns, bone parts, blood

tensile properties of the printed PEEK parts, respectively.

To print advanced polymers it is essential to monitor and control the

management system enabling the temperature control of the printed

The PEEK 3D printers are perfect for printing objects extremely

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
The printing of this material can be done at 340–345 °C performance of the reinforced products in case of medical sector due as
World’s first printer for high performance polymers

the demands of reinforced products is expanding with time. Further, in

The printing of this material can be done at 350 °C

The printing of this material can be done at 372 °C

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
sensor assisted automatic levelling

cells in configuration closer to nature, and enhanced fixation of device

vessels and hip-joints prosthetics.

[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-
temperature process.

ficial muscles applications [76]. Zhao et al. conducted mechanical

medical device.

characterization and in vitro cytotoxicity evaluations of the FDM

printed PEEK specimens in order to explore the biomedical potential of
accurately
Speciality

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
Bed size 700 × 380 × 560 mm; scan speed 2 × 6 m/s; layer thickness

of FDM based PEEK structures are extremely difficult to establish.

temperature 450 °C; bed temperature 160 °C; resolution – 0.05 mm
Bed size- 250 × 250 × 175 mm; resolution – 0.05–0.3 mm; layer

Bed size- 420 × 420 × 400 mm; resolution – 0.05–0.3 mm; layer

2.2. Selective laser sintering

Dual extruder; bed size 305 × 305 × 406 mm; maximum

Build volume 300 diameter × 380 height × 405 center

This technology was developed and patented Carl Deckard as an

accuracy – 30 μm; maximum temperature – 420 °C

accuracy – 30 μm; maximum temperature – 420 °C

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
0.12 mm; building speed 7 mm/h

over the building platform by a cylindrical roller wherein fusion takes

place after the strike of an intensive and concentrated laser power [80].
Technical specifications

When a single slice of the decided geometry is fully sintered, the piston
controlling the vertical motion of the platform moves downward to
Technical descript of commercial PEEK printers and materials.

1.75 mm diameter

1.75 mm diameter

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-
NA

NA

NA

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
Continuous

Continuous
Type/form

sealed chamber which is maintained at a temperature below the

filament

filament
Powder

melting point of the feedstock [83]. The morphology, structure, and

FDM

FDM

FDM

FDM

FDM

FDM
SLS

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
KUMOVIS R1 Printer
Name of the Printer/

VSHAPER 270 MED

VSHAPER 450 MED

Apium M220 Series

FUNMAT PRO 410

characteristics are greatly influenced by various process parameters,

EOS P 800 Printer

ULTEM® Material

including laser beam features too [85–90].

T850P Printer

THERMAX™
Printer

Printer

Printer

Printer

SLS being useful for both polymeric and metallic materials has an
PEEK HP3
Material

edge over FDM as it can process a broad category of material including

Table 3

those with higher melting temperatures. Moreover, as per the require-

ment, the type of laser source can also be changed [80]. Therefore

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S. Singh, et al. European Polymer Journal 114 (2019) 234–248

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

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

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
Fig. 3. Multi-material cellular structure of Ti6Al4V/PEEK [82] (reused after produced. Fortunately, the Food and Drug Administration (FDA) of USA
permission]. issued the clearance certificate for the implication of SLS based printer

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S. Singh, et al. European Polymer Journal 114 (2019) 234–248

to process medical grade PEEK material [96]. In fact, OsteoFab is Ox- than thermoplastic composites, are particularly desired [106]. In both
ford Performance Materials’s brand name for 3D printed medical parts types of printer, as regards to PEEK processing, geometrical deforma-
and implants produced a co-polymer of PEEK [97]. A multi-material tion is highly complex because of the coupling of various parameters
Ti6Al4V-PEEK cellular structure, refer Fig. 3, was built by hybrid with each other [46]. Beyond the existing technical issues related to 3D
manufacturing system consisted of a powerful version of SLS and hot printing, its ramifications on strength, fatigue resistance, biocompat-
pressing [82]. ibility, and bone in-growth, etc., should be assessed with well accepted
Recent advances of SLS have been the ability to produce lower techniques addressed by FDA, USA. Further, 3D printing of PEEK im-
stiffness scaffolds and higher resolution features [98]. Wilmowsky et al. plants should sought for clearance certification in-terms of their safety
studied the individually shaped medical implant to evaluate the bio- and effectiveness [107].
logical behaviour of SLS processed PEEK implant indulged with osteo- Apart from the limitations from 3D printers’ part, PEEK material too
conductive bone materials in porcine bone defects. The obtained his- has certain issues as regards to medical applications. First, the viscosity
topathollogical evaluation revealed that the implant was majorly of this is high in comparison of other biocompatible materials such as
covered by connective tissue and there was no sign of inflammatory or PC, PCL, and others. Owing to this, the processing becomes tedious and
necroses [99]. However, after reviewing the boons and banes, it is the resulting product architecture is always undesirable. Secondly, the
worth mentioning that there is still a lot to understand about the bio- affinity of PEEK with the bio-ceramics (such as HAP and chitosan) is
compatibility of SLS based PEEK and bio-activity of SLS based PEEK week which affects the in-vivo and in-vitro performances of the bio-
composites. products. Thirdly, the processing temperature of PEEK is higher and as
a consequence various open source low capacity printers are unlikely to
3. Challenges with PEEK entertain it. Lastly, the cost of PEEK feedstock also restricts the wide-
spread use for general and sophisticated engineering applications.
3.1. Printing issues However, it has favourable characteristics including excellent me-
chanical, heat retardant, and bio-inertness features, which make it a
Although it has been more than 30 since the invention of 3D potential candidate for demanding applications.
printing technologies yet numerous issues such as material cost, in- For a good print, there should be required affection between the
vestment cost, and prolonged time for layer generation, manual work, printer and material so that excellent quality with minimal anisotropy
poor quality characteristics, and material constraints are unresolved, could be achieved. Therefore, in possible scenario, the part should be
specially, for processing novel materials such as PEEK. SLS is the first made in a way that the in-service stresses can be aligned with the
3D printing technology used for the development of production routes strongest orientation [108]. Similarly, the validation of the part’s
for PEEK [100]. But this printing technology is highly complicated characteristic should be carried out on the basis of standard test pro-
because of the variation in the size and shape of the powder particles cedures. There are various ASTM standards already available for some
[101]. Additionally, the principle cost of the SLS system is higher than testing, however, these are unable to capture complete picture
FDM costly and the use of gas sourced laser generates high magnitudes [61,109], for example, in the case of 3D scaffolds for BTE [110].
to waste [46,100]. This problem can be solved by using a compact Moreover, the trade-offs of various quality performances can be opti-
adaptation system into the SLS part bed, allowing the adaptor to mized by using chemical compounding of the polymeric system.
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- 3.2. Peek’s characteristics
terest of commercial and research community to use FDM, as alter-
native, to process PEEK. As yet, relatively few studies discuss FFF of Although, PEEK is a potential candidate for fabricating various
PEEK [39,46]. Wu et al. developed a PEEK 3D printing system and types of high standard biomedical implants owing to excellent tribo-
defined optimal heated bed and print head nozzle temperatures for logical, mechanical strength, and chemical resistance [111]. The main
FDM of PEEK [46]. While in FDM, the thermal gradient properties re- restriction of PEEK concerning biomedical applications, such as pros-
main a significant issue which can lead to limited mechanical perfor- theses and implants, is its relatively low integration to bone. Therefore,
mance when compared to moulded samples [103]. The filament during it has found limited practical usages as in comparison of prominent
the FDM printing fluctuates and alters the amount of melt during the metals, such as Ti, Co-Cr alloys, and stainless steel, mainly in-terms
printing, which introduced voids in the part and decreased the tensile accelerated wear and corrosion issues, as discussed below:
strength [4]. The comparison between the 3D printed and injection
moulded parts demonstrated that despite using a professional graded • Predominant wear rate
industrial FDM machine, the resulting parts did not outperform injec-
tion moulded parts [48]. Also, the anisotropic properties of the 3D It has been found that the wear rate of PEEK increases proportion-
printed parts are amongst the critical barriers [104]. Furthermore, full ally with the applied pressure [112], and considering demanding im-
medical certification of devices produced by the machine is the next plants, such as hip, knee, spine, and elbow, the failure rate of PEEK
step, dependent upon geometry and application. implants is high. However, the worn particles of PEEK have no cyto-
The mechanical strength of a thermoplastic typically increases with toxic effect on the surrounding cells [113]. As of today, there exists not
the molecular weight and degree of branching or side chains. even a single PEEK based total joint arthroplasties (TJAs) device has
Unfortunately this also results in an elevation of the melt viscosity and been cleared by the FDA for patient use because of predominant wear
melting point. The z-strength, or mechanical properties of the bond [114]. This is due to the fact of missing literature on the wear of PEEK
between adjacent layers, is formed by physically pushing the polymer against hard counter-faces in the presence of a bovine serum lubricant
melt into the previous layer. Therefore the resistance to melt flow is an [115]. But, PEEK composites have shown in-vitro wear properties
important parameter, and the extrusion of high strength thermoplastics comparable to metal-on-metal bearing couples [1,116] and are com-
requires elevated temperatures that aggravate thermal distortion. The monly used in trauma implants and spinal fixation devices [117]. The
melt pressure in FDM directly affects the surface morphology as a de- TJAs fail as a result of biologic responses to particles, it is imperative to
crease in it increase the surface defects [105]. Alternative materials for identify whether or not the wear debris produced by PEEK devices is
AM need to outperform thermoplastics in a number of critical areas, cytotoxic or immunologically reactive. In [118], authors reviewed 10
including mechanical properties (such as elastic modulus), chemical studies and found that the wear particles produced by PEEK-based
resistance, thermal stability, and overall durability. New materials that bearings were in almost all cases, in the phagocytozable size range
can be used in composite structures, and can attain higher performance 0.1–10 lm. A solution has been found in [119], highlighted the

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S. Singh, et al. European Polymer Journal 114 (2019) 234–248

reduction in friction coefficient and resulting wear rate through the printing, and their combination.
addition of carbon fibers (CF) in polymeric structures. The same has
also been verified in another research [120]. Nowadays, PEEK material 4.1. Scaffolding
is widely used as a veneering material for metallic in order to provide a
high mechanical strength, biocompatibility, and wear resistance in Various researchers have nominated 3D printing as one of the best
human body conditions [121]. Now, three contradicting questions are technologies to fabricate complex internal and external geometries of a
arising here: (i) Does PEEK really suffer from accelerated wear? (ii) If scaffold. In [92], the composite scaffolds developed by using various
yes, why it is still being considered as a veneering surface for metallic combinations of PEEK and HAP, through SLS showed great level of
implants? (iii) If no, why PEEK based materials are being nominated for interconnectivity with the scaffold. Further, the simulated body fluid
hard tissue engineering [122] and load bearing applications [123]? test demonstrated the cell adhesion with precipitation of bone-like
apatite in X-ray diffraction analysis. Vaezi et al. [151] proposed an
• Bioactivity innovative FDM based fabrication technique which can yield a bioac-
tive PEEK/HA composite scaffold with 100% interconnectivity, refer
Although PEEK is always physically and chemically stable, yet it Fig. 4(a) and (b), tailored pore size and distribution to facilitate greater
needs modifications in-terms of physical or chemical treatments [124]. cellular infiltration and biological integration. Fig. 4(c) and (d) showed
PEEK is biologically inert and often results in the improper fixation of the adherent of human bone marrow stromal cells on the surface of the
implants at defect sites and their loosening in severe cases [15]. For any developed composite scaffold. Roskies et al. customized PEEK scaffolds
of the potential replacement of bio-metals, it is mandatory that the in order to incorporate a trabecular microstructure using computer
replacement should have reasonably good cytocompatibility, especially designed program and to print via SLS. The developed structure was
in case of orthopaedic applications [125]. In order to inculcate the evaluated through SEM, refer Fig. 5, for the evaluation of the mor-
same, reinforcement of bioactive materials is frequently required to phology [152]. It can be seen that the cytocompatibility of the scaffolds
bring it at par with the requirements. It has been found that sulfonation to mesenchymal stem cells after 7–9 days were attached within the
of PEEK was occurred after its immersion in concentrated sulfuric acid, pores of In their study, graphene oxide was introduced as an interface
which caused geometrical distortions [126]. In [127], authors showed phase to improve the interfacial bonding between PEEK and HAP. It has
the rat osteoblast proliferation and the size and number of vinculin been found that with the help of conjugated structure of grapheme
adhesion plaques involved in cell spreading were comparable on PEEK, oxide strong π-π bonds could be formed. Fig. 5 shows proliferation of
titanium and cobalt chrome molybdenum alloy. However, in another the cells which attached to the overall surface of the scaffolds. In [38],
work, contradictory results questioned the interaction between PEEK authored outlined the benefits of PEEK composites. It has been men-
and osteoblastic differentiation [128]. For instance, in [129], PEEK tioned that the advanced technologies such as 3D printing enables
implants have comparable in-vitro bone forming capacity to that of greater control on distribution of bioactive phase, for instance HAP,
rough titanium. But, in [130], osteoblasts differentiate was reportedly within PEEK matrix. Moreover, the use of bioactive reinforcements
less in case of PEEK as compared to titanium surfaces. As the titanium- produces a 3D interconnected channel for further bone cells in-growth
PEEK composite indeed allowed the better osteoblastic differentiation and proliferation.
than PEEK, therefore, there is a probable existence of PEEK-Halo effect Overall, it can be concluded that the PEEK being bio-inert material
as discussed by [131]. Overall, the highlighted results on PEEK based may not offer desirable bio-characteristics which can affect its candi-
biomedical devices are contradicting in nature. Moreover, based on the dature in biomedical sector. Therefore, attempts to overcome this by
published literature, it is extremely hard to understand the realistic in- introducing osteoinductive factors, such as HAP, are the need of the
vivo and in-vitro characteristics of the PEEK material. hour. Also, the interactions of PEEK with bio-ceramics should be im-
proved by using supportive substrate materials and interface agents.
3.3. Improving the performance of PEEK
4.2. Orthopaedic implants
Despite aforementioned issues, extensive research efforts have been
made in order to bring PEEK components at par with their counter 3D printing of PEEK for the fabrication of orthopaedic implants and
metallic products. Followings are the primary issues with PEEK mate- load bearing devices, such as hip joints [154], is quite broad as com-
rial. Generally, mechanical, tribological, and biological properties of pared to the other biomedical applications. The main reason for the
the PEEK material can be modified by adopting two strategies including popularity of 3D printing is because it allows the creation of the cus-
physical and chemical. In comparison of physical modification tomized, patient specific, anatomic model and products to help the
methods, chemical modification does not hold significance as PEEK is surgeons in understanding and replacing the faulty bones & limbs, re-
chemically inert [132]. Coating, reinforcement, plasma treatment, spectively [155,156]. Moreover, severe orthopaedics problems related
surface modifications, etc. [133–136], are the commonly used methods such as spinal disorders, knee, elbow, hip, and bone fractures could also
which can enhance the performance standards of PEEK material. be treated easily through the use of 3D printing and high performance
Table 4 lists the various activities which can benefits PEEK based bio- materials [157–159]. In [160], the authored discussed the ways how
medical components. 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.
4. Potential medical applications [161] attempted to clearly define what 3D printing technologies have to
benefit orthopaedic surgeries. The history of implantable PEEK is not
Both 3D printing and PEEK has found utmost useful applications in new as the very first implant was introduced by London, United
the area of biomedical and tissue engineering applications including Kingdom-based Invibio Biomaterial Solutions in 1999. Further, ma-
development of orthopaedic implants, scaffolds, artificial organs, sur- chined and printed PEEK implants have already used for humans and
gical guides and templates, prostheses, and drug vessels. It is also true animals without major complications [162,163], respectively. How-
that manufacturing of the PEEK based aforementioned medical devices ever, the printed PEEK implants have not explored in detail. In
with conventional manufacturing technologies is very difficult due to [164,165], FDM and SLS sintered PEEK parts with graded porous parts,
the existence of patient specific parameters that generally demands for bone replacements, possessed excellent mechanical performance,
specificity. And, it is only possible with 3D printing as it enable cus- chemical stability and biocompatibility. To achieve further enhance-
tomization at any phase of the fabrication process. Therefore, this ment in the properties, especially bioactivity, numerous approaches,
section discusses the interesting biomedical application of PEEK, 3D such as spin coating, plasma gas teatment, plasma electron beam

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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
PEEK/β-TCP Biological [142]

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The proliferation rates of normal human osteoblast cells’ growth on β-TCP/PEEK were lower than
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]
adhesive strength of the polymer
8 Plasma immersion ion – Biological The experimented treatment is helpful in developing next generation orthopaedic implants [149]
deposition
9 Sterilization – Mechanical Steam treatment was found more efficient than other(s) [150]
European Polymer Journal 114 (2019) 234–248
S. Singh, et al. European Polymer Journal 114 (2019) 234–248

a b

HA PEEK

PEEK HA d

e f

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 improved osseointegration by maintaining the structural integrity.
considered [166]. Evans et al. [167] created a surface-porous PEEK Therefore, PEEK material can be used as a bearing surface in ar-
material with an average pore size of 279.9 ± 31.6 lm, strut spacing of throplasty wherein this can be processed on-site by using 3D printers to
186.8 ± 55.5 lm, porosity of 67.3 ± 3.1% and interconnectivity of get personalized implant geometry. This on-site or corporate based
99.9 ± 0.1%. Monotonic tensile tests conducted showed that the processing can be used to make a bearing surface that can live up to the
strength preserved by the material was 73.9% if compared to as-re- current implant standards set forth by ASTM and, obviously, the FDA
ceived moulded PEEK. Further, an osseointegration model in the rat [168]. Wang et al. studied the bacterial resistance of fabricated PEKK
revealed substantial bone formation within the pore layer at 6 and implant, comprised with nano-pillars with random inter pillar spacing
12 weeks by using a micro-CT technology and histological evaluation. and compared the same with its co-polymers. After 5 days test, it has
The overall results indicated that the produced material could provide been found that the PEEK has 37% higher Staphylococcus epidermidis

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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- Fig. 6. Possible replacement of cranioplasty and orbital rim implants of tita-
trusion–based 3D printing is still in its very early phase [4]. nium by 3D printed PEEK [180].

4.4. Miscellaneous medical applications

4.3. Dental and oral craniofacial/maxillofacial applications

Other than aforementioned applications, the 3D printing of the

In the past years, PEEK and its composites have furthermore har-
PEEK can also be explored, comprehensively, in the domains of drug
vested much interest in the clinical dentistry not just because of the
delivery, bone regeneration, and producing nano-scaled devices.
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 • Tan et al. [181] fabricated filaments of PEEK, for drug delivery
application, by using the hot melt extrusion technology that could
used dental materials such as titanium [173]. Considering mechanical
be used as feedstock of FDM at later stage; refer Fig. 7 for detailed
and physical properties similar to bone, PEEK can be used in many
set-up. It has been found that the bioactivity and solubility of the
areas of dentistry. However, improving the bioactivity of PEEK dental
drugs have been enhanced for the purposefully release of the drug
implants without compromising their mechanical properties is a major
over a prolonged period of time. Interestingly, many researchers
challenge [174]. Moreover, PEEK does not cause any toxicity, muta-
have also designed and fabricated novel scaffolds which can also
genic effects, and significant inflammation [175,176]. However, being
deliver required drugs in a well-controlled manner. Here, FDM and
small in size, fabrication of dental and maxillofacial devices is a chal-
SLS are playing tremendous roles [172–187]. Further, it is outlined
lenging task and should be comprehended to completely understand the
that the future utility of 3D printing of soft materials, particularly
available useful technologies. Here, CAD/CAM assisted 3D printers can
for lipid-based drug delivery systems, will offers appreciable bene-
have a notable advantage as these have negligible effect of the me-
fits to potentially support patient compliance [188]. This demands
chanical properties of the PEEK, therefore, can maintain the desirable
the extensive explorations of bioprinters/bioplotters.
specification [177]. Thus, considering 3D printing of PEEK in order to
develop dental implants, denture prostheses, and crowns is an efficient • Similarly, low temperature 3D printing systems hold acknowledge-
able promises for fabricating synthetic bone graft substitutes with
way. Moreover, crowns and fixed dental prostheses (FDPs) are gen-
enhanced performance over traditional techniques [189].
erally made of ceramic or composite resin, and here the application of
PEEK is still amateur [178]. Msallem et al. followed a hybrid manu- • Gittard and Narayan [190] reviewed the fabrication of micro and
nano structured devices through 3D printing. A wide variety of
facturing route consisted of FDM and silicon moulding processes. In
medical devices, such as prostheses, drug delivery devices, bio-
their work, sterilization of a patient-specific mold was done first and
sensors, stents and tissue scaffolds were highlighted in this work.
then used intra-operatively to produce an implant. They did a huge cost
Further, in [191], author discussed a 3D printing assisted procedure;
cutting because the procedure adopted was very simple, basic, and
refer Fig. 8, to solve complex medical problems. Additionally, var-
convenient [179].
ious others suggested the potential of this revolutionary technology
Roskies et al. attempted to combine and improve after the two
to aid vascular networks [192], bandages [193], bones [194], ears
methods by altering the internal geometry into a trabecular network
[195], and exoskeleton issues [196].
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 5. Concluding remarks
[152]. The results of the study showed that unreinforced SLS printed
PEEK supported both BMSC and ADSC cell growth and integration; 3D printing and PEEK material both are well integrated with the
however, ADSCs differentiated into osteoblasts much more reliably medical devices for many years. It has been reported by various re-
when co-cultured with the structured. Some clinical researches dis- searchers that PEEK and its composites have a bright future in biome-
cussed the practicality of 3D printing to create PEEK based max- dical industry owing to their near to bone mechanical characteristics.
illofacial implants, refer Fig. 6 [180]. However, the manufacturing of the complex biomedical geometries is
Overall, it is worth to recapitulate by stating that the different not too easy through conventionally available technologies; therefore,
benefits of 3D printing of PEEK for making dentistry, maxillofacial, or 3D printing is currently being explored to overcome the existing man-
craniofacial devices help the practitioners to fabricate strong and ufacturing hurdles. Admittedly, through 3D printing, it is feasible to
lightweight products to provide comfortable experience to the patients. construct patient specific controlled architectures with optimized

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Fig. 7. Hybrid hot melt extrusion and FDM systems for continuous fabrication of drug delivery vessels [181].

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.

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