Chapter 2

Synthesis and Processing of PEEK for

Surgical Implants
Steven M. Kurtz Ph.D.

2.1 Introduction PEEK used in biomedical applications. Readers with

an interest in PEEK composites may wish to skip
Polyaryletheretherketone (PEEK) is a challenge to ahead to Chapter 3, which covers blending of PEEK
synthesize and convert into surgical implants. The with additives.
polymer is chemically inert and insoluble in all
conventional solvents at room temperature. Indeed,
PEEK can only be completely dissolved using fairly 2.2 Synthesis of PAEKs
esoteric solvents, such as diaryl sulfones [1].
As noted previously, the polymerization of aryl-
Although inertness and insolubility are desirable for
etherketones is a complex and challenging process
a biomaterial, these attributes constrain the synthesis
due to the insolubility of PAEKs in typical solvents.
and manufacture of PEEK.
Furthermore, the solvents and high temperatures
Fabrication techniques for polyaryletherketone
necessary to carry out successful polymerization of
(PAEK) polymers have undergone constant refine-
PEEK, such as benzophenone or diphenylsulfone
ment since the preparation of polyetherketoneketone
above 300
C, necessitate dedicated plant facilities
(PEKK) was first described in the 1960s [1e3].
with rigorous safety procedures (Fig. 2.1). Because
Although many of the details associated with
of the precautions necessary to carry out safe poly-
synthesis and processing of PAEKs are proprietary to
merization, the reactions are typically carried out in
resin and stock material suppliers, it is important to
batches, as opposed to in a continuous process. All
understand the steps used in the manufacture of raw
these challenges contribute to the higher cost in
materials, because these techniques can substantially
producing PAEK polymers, when compared with
impact the properties and quality of the stock shapes
other thermoplastics.
and molded implant components [4]. Consequently,
Historically there are two main routes involved in
this chapter summarizes the principal steps used to
the production of PAEKs. The first method involves
synthesize and fabricate PEEK implant components.
linking aromatic ether species through ketone
Early studies on PEEK processing tend to
groups, whereas a second method involves linking
emphasize the fabrication of PEEK composites,
aromatic ketones by an ether bond. The first method
using carbon and glass fibers [4]. This chapter is
involves an electrophilic reaction and Friedel Crafts
focused on the synthesis and processing of neat,
acylation chemistry, and the second route involves
unfilled PEEK polymer. We begin by outlining the
a nucleophilic displacement reaction.
two main synthesis routes for contemporary
PEEK. As a high-temperature thermoplastic, PEEK 2.2.1 Electrophilic Routes to PAEK
can be processed using a variety of commercial
techniques, including injection molding, extrusion, Polymers
and compression molding. This chapter provides an The inherent solvent resistance and propensity to
overview of the methods for processing unfilled reach high crystallinity levels prevents PAEK

PEEK Biomaterials Handbook. DOI: 10.1016/B978-1-4377-4463-7.10002-8

Copyright Ó 2012 Elsevier Inc. All rights reserved. 9
10 PEEK B IOMATERIALS H ANDBOOK

Figure 2.1 PEEK production facility, Thornton-Cleveleys, United Kingdom. Source: Victrex.

polymers from being synthesized in common organic
solvents. Early attempts to synthesize PEEK in
methylene chloride or nitrobenzene produced only
low-molecular-weight variants.
Work by DuPont using a combination of anhy-
drous hydrogen fluoride/boron trifluoride succeeded
in protonating the carbonyl groups and meant that
high-molecular-weight polyetherketone (PEK)
became a possibility (Scheme 2.1) [5].
Raychem also reported the synthesis of PAEK
polymers using similar reaction conditions in the
presence of alkylthiochloroformates.
Another electrophilic process exemplified by
Ueda and Oda uses methanesulfonic acid (MSA)/
phosphorus pentoxide (P2O5) at low temperatures
[6]. Although PEEK produced by this method has
acid to form PEEK. This route has only remained of
academic interest due to the extremely high cost and
corrosive nature of the solvent used (Scheme 2.2).
The electrophilic synthesis of PAEK polymers
produces materials with reactive end groups such as
benzoic acids. Such polymers cannot be processed,
without endcapping, due to their high thermal
O
O C Cl
HF / BF3

a less branched structure than AlCl3-catalyzed

systems, it also suffers from high temperature insta- O
bility and hence cannot be molded or extruded
without extensive cross-linking and degradation. * O C *
Colquhoun and Lewis [7] have described the
Friedel Crafts polycondensation of 4-(40 -phenoxy-
phenoxybenzoic acid) in trifluoromethanesulfonic Scheme 2.1
2: S YNTHESIS AND P ROCESSING OF PEEK
n O
* O
instability. When the reactive end group materials are
subjected to high-temperature processing, the poly-
mer immediately cross-links, producing gels, which
cannot be shaped into desired articles. Therefore,
PEEK production by electrophilic processes as
described earlier has historically had limited
commercial success.
More recently, a modification to the electrophilic
process for manufacturing PAEK polymers has been
described. This again involves the polycondensation
of 4-(40 -phenoxyphenoxybenzoic acid). However,
methanesulfonic acid was used as the reaction
solvent in the absence of phosphorus pentoxide, and
1,40 -diphenoxybenzene was used as an endcapping
agent [8]. This route permits the manufacture of
thermally stable PAEK polymers and has been used
in industrial processes (Scheme 2.3).
It should be noted that to ensure thermal stability,
significant quantities of the endcapping agent are
used and as a result may be present in significant
n O
CH3SO3H
* O
C6H6-O-C6H6
End Capping Agent
O C
FOR S URGICAL I MPLANTS 11
O Scheme 2.2
O C OH
CF3SO3H
O C *
quantities in the finished polymer. The choice of the
endcapping agent may therefore significantly alter
the leachable and biocompatibility profile of the
material.
2.2.2 Nucleophilic Routes to PAEK
Polymers
The nucleophilic route to PAEK polymers
provides a straightforward pathway to polymers such
as PEEK. Initial attempts to form high-molecular-
weight PAEKs from the reaction of a dihalobenzo-
phenone and an equivalent bisphenate failed due to
the polymer product crystallizing from the sulfolane
solvent (Scheme 2.4).
Owing to the poor solubility of PEEK, the selec-
tion of the synthesis solvent is crucial. Suitable
solvents should be thermally stable and inert to
phenoxide species. It became apparent that solvents
such as benzophenone or diphenylsulfone could be
O Scheme 2.3
O C OH
O C *
O
12
O O
F C F +
Sulfolane
* O
Scheme 2.4
F C
* O
Scheme 2.5
used in the synthesis of PAEK polymers [3]. The
inherent instability of bisphenates to oxidation was
overcome by the use of hydroquinone and sodium or
potassium carbonate to form the bisphenate in situ.
Very high temperatures (>300
C) are required
to reach high molecular masses, the molecular
weight being controlled by a slight excess of di-
fluorobenzophenone, leading to fluorine-terminated
chains (Scheme 2.5).
This process was patented in 1977 by ICI and sold
under the brand “Victrex PEEK,” and this route
provided the majority of PEEK polymer used in
industrial applications.
The establishment of the nucleophilic route to
PAEK polymers permitted the investigation of
polymer variants by the use of different bisphenols to
produce PAEK polymers with various properties, as
reported by Attwood et al. [1]. The family of PAEK
polymers grew to contain variants such as PEK,
PEEK, PEKK, PEKEKK, and so on, with a range of
glass transition temperatures (143e160
C) and high
crystalline melt temperatures (335e441
C). As the
dominant member of the PAEK family of polymers,
PEEK is in its “glassy” state at room temperature, as
its glass transition temperature occurs about 143
C,
PEEK B IOMATERIALS H ANDBOOK
KO C OK
C *
F + HO OH
Diphenylsulfone
K2CO3
O C *
whereas the crystalline melt transition temperature
(Tm) occurs around 343
C.
2.3 Nomenclature
The literature on PAEK resin is a maze of trade
names and producers, which have changed over the
years, complicating interpretation of reported data
for today’s materials. For researchers interested in
deciphering the historical polymer science literature,
we provide here a brief primer on the nomenclature
of PAEK resins used for industrial purposes as well
as for biomaterials (Table 2.1). Resin, when used in
this context, refers to the neat, unfilled powder that is
created by polymerization, whereas grades are typi-
cally characterized by flow characteristics (e.g., for
injection molding or compression molding) or based
on their filler content (e.g., glass fiber or carbon
fiber). Because PAEK polymers are converted using
standard thermoplastic processing techniques, such
as injection molding, they are generally available as
pellets, although powder resin is also available. Stock
shapes, such as rods, are also available from
producers.
2: S YNTHESIS AND P ROCESSING OF PEEK FOR S URGICAL I MPLANTS 13

Table 2.1 Summary of PAEK Materials Related to Implant Use

Polymer Trade Name Producer Comments

PEEK OPTIMA Invibio (subsidiary of Victrex), Manufacturer and supplier of long-

(Biomaterial) Thornton-Cleveleys, United term implantable PEEK in CE and
Kingdom Food and Drug Administration-
approved devices since 1998
PEK Invibio (subsidiary of Victrex), Available only in experimental
Thornton-Cleveleys, United quantities (see Chapter 13)
Kingdom
PEEK Victrex Victrex, Thornton-Cleveleys, Provides PEEK for blood/tissue
United Kingdom contact less than 24 h
PEEK Gatone Gharda, India No record of supplier implantation
studies. Discontinued for medical
use when acquired by Solvay in
December 2005
PEEK Keta-Spire Solvay Advanced Polymers, Not available for implant use
LLC
PEEK Zeniva Solvay Advanced Polymers, Implantable grade available
LLC
PEEK VESTAKEEP I Evonik Implantable grade available
PEKK PEKK DuPont, Wilmington, DE Discontinued for medical use by
DuPont
PEKK OXPEKK OPM, Enfield, CT Implantable grade available. Base
resins supplied by Cytec [9]
PEKEKK Ultrapek BASF, the United States Discontinued in December 1995

Historically, PAEK materials, including PEEK,
have been produced primarily as niche polymers for
industrial use, because their cost even today is at least
two orders of magnitude more expensive than low-
temperature thermoplastics such as polyethylene.
When ICI launched Victrex PEEK in 1987, the
primary application targets were not medical.
However, Victrex PEEK was used, if not yet sup-
ported, for implant applications. The Victrex PEEK
business was sold by ICI in 1993, and in 1998, Victrex
launched PEEK-OPTIMAÒ for long-term implant-
able applications. The offering of PEEK-OPTIMA
provided a higher specification product and was
aimed at addressing the previous failings of PAEK
polymers by offering long-term supply assurance
agreements in addition to a policy of no change con-
cerning the main characteristics of polymer proper-
ties. PEEK-OPTIMA was supported by drug and
device masterfiles and manufactured in compliance
with Good Manufacturing Practice. In 2001, Victrex
established Invibio Biomaterial Solutions to specifi-
cally provide grades of PEEK suitable for long-term
implantation. In reviewing the historical PEEK liter-
ature, whether for industrial or biomedical applica-
tions, the reader should keep in mind that polymers
from ICI, Victrex, and Invibio were all produced at
the same plant location, although the name of the
company has changed since that time. Similarly, the
nomenclature for the resin grades has changed over
time, but the polymerization technology has remained
fundamentally similar (Table 2.2). Today, PEEK
biomaterials are designated by the OPTIMA trade
name based on their molecular weight, which governs
their flow properties in the melt (Table 2.2). The same
range of molecular weight of PEEK polymers was
also previously available from Victrex.
14
Table 2.2 Contemporary and Historical Nomenclature for Medical Grades of PEEK
Property General-Purpose Grade
Historical Victrex 450
nomenclature
Invibio nomenclature OPTIMA LT1
Melt flow index 3.4
Molecular weight (Mn) 115,000
LT1 Standard grade
LT2 Optimized grade for melt strength and melt
viscositydrecommended for tubing
LT3 High-flow grade for injection molding thin-
walled parts
The most commonly used grade for PEEK is
OPTIMA LT1, which has flow properties similar to
450. Victrex grades are also designated as PF (fine
powder), P (powder), or G (granulated). Powder
grades are recommended for compounding, whereas
granulated resin is preferred for injection molding.
Although powder grades are produced for industrial
applications, there are no powder grades commer-
cially available for implantable grade PEEK-
OPTIMA, only granules. PEEK-OPTIMA undergoes
a melt filtration step as a quality control measure to
ensure cleanliness and biocompatibility. Following
melt filtration, the polymer is granulated into cylin-
drical pellets (Fig. 2.2). Thus, to obtain powder from
PEEK-OPTIMA, it is necessary to mill or grind the
granules to obtain the desired particle size.
Recently, two new resin manufacturers entered the
medical PEEK market. In 2007, Solvay announced
an implantable grade of PEEK marketed under the
Zeniva trade name. In 2009, Evonik began marketing
an implantable grade of PEEK under the VESTA-
KEEP trade name. However, no reports have been
published describing these resins in scientific studies
or how they are used in long-term implants. Publi-
cation of further details about the performance of
Solvay and Evonik materials is anticipated.
PAEK alternatives to PEEK are available from
Invibio and Oxford Performance Materials (OPM).
PEK has been made available by Invibio in experi-
mental quantities as a candidate biomaterial for
PEEK B IOMATERIALS H ANDBOOK
Medium-Flow Grade Easy-Flow Grade
381 150
OPTIMA LT2 OPTIMA LT3
4.5 36.4
108,000 83,000
tribological testing (see Chapter 13). However,
PEK has not been commercialized for implant
manufacture.
PEKK resins are produced by OPM (Enfield, CT)
and have been marketed under the OXPEKK trade
name since the company was founded in 2000. Both
medical grades and implantable grades of OXPEKK
are available. OPM was acquired by Arkema
(Colombes Cedex, France) in 2009.
Sustainability of biomaterial supply has been
a concern with PAEK resins in the 1980s and 1990s.
With the exception of PEEK-OPTIMA, which can
trace its origins back to 1998, many industrial PAEK
materials have been withdrawn from the market,
either out of concern for liability, patent infringe-
ment, and concerns about viability of a niche market
or due to technical difficulties (Table 2.1). Nonethe-
less, to the extent that biomaterials history is not fully
reflected in the literature, Table 2.1 provides some
guidance as to the current availability of PAEK
materials for industrial and implant use.
2.4 Quality Systems for Medical
Grade Resin Production
PEEK-OPTIMAÒ biomaterials are manufactured
under a Quality Management System certified to ISO
9001:2000 and ISO 13485:2003. Only fully approved
raw materials are used at the production stages
together with extensive supervision and checks at key
production stages. The recording of key parameters is
performed at all stages.
PEEK-OPTIMA biomaterials are manufactured on
a campaign basis, thus enabling the employment of
contamination risk reduction procedures. Invibio
embraces Good Manufacturing Practice in relation to
2: S YNTHESIS AND P ROCESSING OF PEEK FOR S URGICAL I MPLANTS 15

(A)

(B)

Figure 2.3 Clean room production environment for MG

PEEK. Photo courtesy of Invibio.

Enhanced Quality Control procedures and stan-

dards, together with extensive testing and product
release control, ensure a tight product specification for
(C) PEEK-OPTIMA. Test results are verified by dual
testing at an independent UKAS-accredited labora-
tory. Invibio has a “no-change” agreement for the long-
term supply of PEEK-OPTIMA biomaterials to assure
its specification and production methods over time.

2.5 Processing of Medical Grade

Figure 2.2 High-resolution optical micrographs of
PEEK-OPTIMA LT1 granules (A, B) and representative
scanning electron micrograph (C). SEM image courtesy
of Josa Hanzlik, Drexel University.
the manufacture of PEEK-OPTIMA biomaterials,
including clean room conditions for processing
(Fig. 2.3). Process documentation is archived to
provide long-term batch and raw material traceability.
PEEK
Despite the exceptional properties of medical
grade PEEK polymers, these materials are processed
by traditional plastic processing methods (Table 2.3).
medical grade PEEK-based materials exhibit melting
temperatures of around 340
C; however, PEEK
polymers demonstrate good melt stability and remain
workable with most conventional process equipment
between 360 and 400
C. Commercial manufacturers
of implantable grade PEEK provide detailed guid-
ance and support for all processing techniques.
However, for students and researchers, a brief
summary of the main techniques is discussed in the
16
Table 2.3 Traditional Plastic Processing Methods
and Applicability to PEEK
Processing Method Applicable
Injection molding Yes
Extrusion (profiles, sheet, and Yes
monofilament)
Compression molding Yes
Powder coating Yes
following. A comparative plot of melt viscosity
versus temperature for a range of conventional
polymers in comparison with PEEK-OPTIMA LT1 is
shown in Fig. 2.4.
Although commercial PEEK materials are
supplied nominally dry, the pellet form of the mate-
rial typically absorbs 0.5% w/w atmospheric mois-
ture. It is therefore recommended that for processing
operations such as injection molding, the polymers
should be dried to less than 0.02% w/w moisture.
Typically, suitable drying of PEEK pellets can be
achieved by 3 h of exposure in an air-circulating oven
at 150
C. If the oven is only capable of lower
temperatures, a longer drying time will be necessary
(e.g., 12 h of exposure at 120
C).
PEEK-OPTIMA materials are provided in a range
of viscosities in relation to the processing technique
Figure 2.4 Shear viscosity versus
temperature for a range of
thermoplastics. Source: Invibio.
PEEK B IOMATERIALS H ANDBOOK
used. As mentioned previously in this chapter, PEEK-
OPTIMA LT1 is recommended for the majority of
machining and injection molding of medical device
components. PEEK-OPTIMA LT2 demonstrates
good melt strength with reduced viscosity and is
therefore recommended for the extrusion of thin-
walled parts such as tubing. PEEK-OPTIMA LT3 is
especially preferred for the injection molding of
thin-walled parts. The problem of machine wear is
common to all engineering plastics, and it is therefore
recommended that screws, dies, and barrels should
be hardened to minimize wear, especially when pro-
cessing fiber-reinforced materials.
2.5.1 Injection Molding
Injection molding is an attractive manufacturing
technique suitable for mass projection of PEEK
implant components (Fig. 2.5). Injection molding is
typically performed using pellets or granules, which
are poured in a hopper in the machine. The pellets are
then automatically introduced into a heated screw
assembly that melts and pressurizes the molten
polymer, so that it flows into a heated mold. Once the
PEEK component has consolidated, it is automati-
cally ejected from the mold, so that a new cycle can
take place.
Injection molds are optimized and specially
designed for each part, taking into account the details
of the part geometry and flow and pressure capabil-
ities of the molten polymer injection system.
2: S YNTHESIS AND P ROCESSING OF PEEK FOR S URGICAL I MPLANTS 17

Figure 2.5 Representative injection molding system for PEEK. Picture supplied with kind permission of Krauss Maffei
Technologies.

Consequently, the cost of the designing and fabri-

cating mold itself represents a significant financial
investment for this process. However, after this
investment has been made, multiple PEEK parts can
be manufactured in their near-final shape with cycle
times of the order of minutes. Figure 2.6 shows a tree
of tensile test specimens immediately after injection
molding. The cylindrical sprue, radial runners, and
any extra flashing are trimmed to complete the part
manufacturing process. Because of the up-front cost
of a suitable mold, injection molding techniques are
not suitable for prototyping or low-volume PEEK
part production.
Most standard reciprocating screw injection
molding machines are capable of molding natural IG
PEEK materials and also carbon fiber-reinforced
PEEK materials (Fig. 2.5). Furthermore, specialized
injection molders with extensive experience in
manufacturing PEEK-based medical devices exist in
Europe and the United States. Injection molding of
PEEK typically requires barrel and nozzle temper-
atures in the region of 400
C. The recommended Figure 2.6 Injection-molded test specimens, joined by
sprue and runners. Injection molding allows multiple
mold surface temperature for PEEK lies in the range
PEEK components to be fabricated in near-final shape.
of 175e205
C, and this is extremely important to High up-front tooling costs are the main drawback of
ensure that molded parts demonstrate uniform levels injection molding. Photo courtesy of David Jaekel,
of crystallinity. Failure to achieve the minimum Drexel University.
18
Figure 2.7 Amorphous regions within an injection-
molded part as a result of low mold tool temperatures.
Photo courtesy of Invibio.
mold temperature results in rapid cooling of the part,
with insufficient time for crystallization, as demon-
strated in Fig. 2.7. Additional detailed guidelines
for injection molding and mold design for PEEK
implants can be obtained from raw material
suppliers [10].
It is possible to increase crystallinity by annealing
amorphous or low-crystallinity PEEK moldings
(Fig. 2.8). However, the process of crystallization
may lead to distortion and dimensional changes.
Figure 2.8 Effect of annealing after processing on
injection-molded test specimens. The amorphous
sample was created by heating to 400
C and then
immersed in liquid nitrogen. Image courtesy of David
Jaekel, Drexel University.
PEEK B IOMATERIALS H ANDBOOK
Component design should also take into account the
shrinkage that occurs as crystalline regions form within
the cooling polymer melt. Shrinkage is therefore
dependent on the level of crystallinity and therefore the
mold and polymer melt temperature. If operating
under recommended injection molding conditions,
commercial grades such as PEEK-OPTIMA can
produce consistent parts with dimensional tolerances
as low as 0.05%. Commercial manufacturers of
implantable PEEK materials provide full guidelines
and technical support for molding PEEK medical
components.
2.5.2 Extrusion
Extrusion is a manufacturing process for
producing long stock shapes, such as rods, sheets,
and monofilament fibers (Fig. 2.9). PEEK pellets or
granules are typically the starting, raw material for
extrusion. Similar to injection molding, the pellets
are poured into a hopper that feeds into a heated
screw assembly that melts and pressurizes the molten
polymer. The molten, pressurized polymer is then
forced through a heated die and slowly cools to room
temperature along an extrusion line.
The extrusion of PEEK can be accomplished
using conventional extrusion equipment and dies at
similar temperatures as those described for injection
molding. The drive motor typically requires a power
output of 0.25 HP/kg h. This power requirement
is similar to that required for polycarbonate,
poly(ethersulfone) (PES), or high-molecular-weight
polyolefins.
PEEK is a very stable polymer and as such is not
sensitive to prolonged exposure (up to 2 h) to
temperatures above its melting point. However, for
optimal results, residence times should be of the
order of 5e10 min. Dead spots, areas of material
hold within the barrel, should be avoided. Therefore,
careful design of the screw and barrel is necessary.
The extrusion of PEEK-OPTIMA stock shapes
followed by machining remains the predominant
method of manufacturing medical device compo-
nents. PEEK-OPTIMA can be purchased in rod or
plate form ranging from 6 to 150 mm in diameter for
rod and 40 mm in plate thickness (Fig. 2.10). In
addition to this, thin-walled implantable PEEK
tubing is also available from commercial suppliers.
The thermal processes involved in extrusion and
annealing of stock shapes also result in slight
mechanical property variances when compared with
2: S YNTHESIS AND P ROCESSING OF PEEK FOR S URGICAL I MPLANTS 19

Figure 2.9 PEEK polymer extruder. Photo kindly supplied by Coperion GmbH, Stuttgart.

two heated platens. The lower platen contains

Figure 2.10 PEEK-OPTIMA rod stock, pellets, and
powder.
injection-molded components. This is highlighted
graphically in Fig. 2.11.
2.5.3 Compression Molding
Compression molding is a manufacturing process
for stock shapes, such as plates or thick sheets
(Fig. 2.12). A compression molding press consists of
a recess for the plate or sheet that is charged with
resin powder or granules. The platens are then
pressed together and heated to consolidate the resin.
Compression molding is typically used for low-
volume production, prototyping, and evaluation work
or in the production of industrial components with
very thick sections. Compared with injection
molding, it is a relatively inexpensive process, but
cycle times are long and as such it is not suited to
high-volume production.
The process involves the heating and cooling
down of the melt and tooling. Pressure is applied
to the melt and maintained during the cool-down
phase. This is a time-consuming process, particu-
larly when section thicknesses are large. Compres-
sion molding of PEEK requires a heated press, an
oven, and the tool, which can be low-grade steel/
metal due to the levels of stresses, shear, and forces
involved. There is generally a preference for fine
powder grade of PEEK polymer for compression
20 PEEK B IOMATERIALS H ANDBOOK

Figure 2.11 Graphical representation of the differences between injection-molded and machined PEEK components.
Source: Invibio.

molding to avoid granular boundary parts in molded

parts. These boundary points may also represent
weak points in the components. If controlled
cooling over long time periods is practiced, then
compression-molded parts typically have higher
crystallinity and tensile strength than injection-
molded components. Although, in theory, milled
fibers or fillers could be compounded into PEEK for
compression molding, this is rarely practiced
because of the difficulty in ensuring a uniform fiber
distribution and therefore uniform properties in the
final component.

2.5.4 Film and Fiber Production

Figure 2.12 PEEK polymer compression molding. The
figure shows a 20-ton compression molding press
(Rondol Kompress 20 T).
The use of implantable grade PEEK in fiber and
film form is a growing area of interest in medical
devices because of mechanical performance and
inherent purity. The industrial applications of PEEK
in these forms have been established for a number of
years. Thin sections of PEEK film are produced
by extruding polymer using a suitable die and
haul-off equipment, which controllably handles and
stores the film for secondary operations. PEEK film
can be produced in either crystalline or amorphous
forms by controlling the temperature of the casting
drums in the haul-off equipment. However, as
the thickness of the film increases, the production
2: S YNTHESIS AND P ROCESSING OF PEEK FOR S URGICAL I MPLANTS 21

2.6 Machining
Table 2.4 Properties of a 0.5-mm PEEK
Monofilament Often for prototype designs or short production
runs, it is not economically viable to manufacture an
Typical
injection molding tool. Under such circumstances, it
Material Property Value
is common to use compression molding or to
machine PEEK-OPTIMA polymer materials to form
Energy to break 1.24 J
components. PEEK-OPTIMA polymer may be
Tensile load at 2% elongation 1.18 kg machined and finished using the same techniques
Tensile load at 5% elongation 1.77 kg and equipment as for other engineering thermo-
plastics. However, because of the excellent physical
Tensile load at 10% elongation 2.66 kg properties and wear characteristics of these mate-
Tensile load at break 5.81 kg rials, it is advisable to use carbide or diamond tipped
tools and bits. Machining and finishing operations
Elongation at break 22.0%
on polymeric materials are prone to propagating
Knot strength 2.42 kg molded-in or residual stresses. Before machining, it
is recommended that components formed from
PEEK are annealed to relieve stress. During
of fully amorphous PEEK films becomes more machining or finishing, further stresses may be built
challenging. up within the material by localized heating at the
PEEK monofilament can be produced by extrusion cutting point. Therefore, if a large amount of
followed by drawing of the PEEK extrudate. machining and finishing is to be carried out on
Drawing the polymer provides orientation within the a component, a second annealing procedure may be
fiber prior to heat setting. The resultant monofilament required.
is tough, highly oriented, and has a controlled The thermal conductivity of all polymeric mate-
diameter, which will retain its set form above the rials is lower than that of metals; hence, heat build-up
glass transition temperature of the material. Typical during machining is rapid. It is advisable that
properties of a PEEK monofilament are shown in a cooling fluid is used to remove some of the heat
Table 2.4. PEEK monofilaments are distributed as generated by working the material. Water or air jet
multifilament yarns (Fig. 2.13) and can be woven into cooling is generally recommended for medical grade
more complex three-dimensional shapes. PEEK polymer-based materials. A summary of the
suggested machining conditions for PEEK-OPTIMA
has been provided by Invibio [10].

2.7 Summary
As detailed in this chapter, there are various
synthetic routes involved in the production of
polyketone-based materials. These routes have been
developed to overcome the initial challenges in
relation to polyketone manufacturing, resulting in the
consistent production of polymers for medical
applications. It should be noted that the synthetic
chemistry used in PAEK manufacture has a major
influence on the thermal stability of the polymer in
processing operations and on the leachable and
volatile content of these polymers. Therefore, the
manufacturing route has the potential to alter the
biocompatibility of PAEK materials. The progress in
Figure 2.13 Spool of technical grade, multifilament manufacturing has been extended to processing
PEEK yarn. where established methods have been developed to
22
allow the production of reproducible components
from a range of production techniques such as
injection molding or machining of stock shapes. The
relatively recent addition of a biomedical focus to
manufacturing and supply offers device companies
an opportunity to use these PEEK-based materials, in
implants, with confidence in the quality and security
of supply. In the following chapter, we turn to the
combination of PEEK with additives to form polymer
matrix composites.
Acknowledgments
Special thanks to David Jaekel, Drexel Univer-
sity, for editorial assistance and to Chris Espinosa,
Exponent, for assistance with figures. This chapter
would not have been possible without helpful
discussions and insights provided by John Devine,
Ph.D., and Craig Valentine, Ph.D., from Invibio.
[10] P.E.E.K. Unfilled, Optima Processing Guide:
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