Technological University of the Philippines Taguig Campus

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CHEMICAL ENGINEERING TECHNOLOGY

Individual Polymer
Polyether ether ketone
(PEEK)

Submitted By:
Dela Cruz Bryan Jesher S.
3B1
CHEMICAL ENGINEERING TECHNOLOGY

Submitted To:
ENGR. EMERITA H. HINOJALES

TABLE OF CONTENTS
I.

Historical Development
I.1 Chronological Events of Early Studies and Discoveries of PEEK

II.

CLASSIFICATIONS

III.

Structure
III.1 Structural Representation of PEEK
Properties
IV.1 PEEK Vs. Metal
IV.2 PEEk Vs Stainless Steel and Other Polymers
IV.3 PEEK Grades

IV.

V.
VI.

Applications
Manufacturing
VI.1 The manufacturing process of PEEK
VII. Fabrication of PEEK
VIII. PEEK Testing / Analysis
IX. Property Modification of PEEK
X.

Environmental Impact and Related Issues

XI. Material Degradation

XII. Advancement
XIII. REFERENCES

I. HISTORICAL DEVELOPMENT

1920- The First Preparation of completely aromatic polyether ketones was reported by Bonner of Du Pont (i) , who
obtained polymers of low molecular weight by the polyaroylation reactions (3) using both isophthaloyl and
terephthaloyl chlorides as monomers withNitrobenzene as solvent and aluminum chloride as the catalyst.

Figure 1: Preparation of completely aromatic polyether ketones with isophthaloy and terephthaloyl chlorides in
Nitrobenzene eith aluminum chloride as catalyst
1925 - In ICI, Imperial chemistry Industry, Goodman et al, performed similar experiments and were the first to report
a polymer structure which they made by the reaction (4) using aluminum chloride as catalyst and methylene chloride
as solvent. This polymer apeared not to melt at 350 deg C and had a reduced viscosity, RV, of 0.57.
1930-A Polymer of the same structure was prepared via reaction (5) by Iwakura (4) who noted that the polymer was
insoluble in all the usual organic solvents and used polyphosphoric acid as the solvent / catalyst for his reactions.

Figure 2: (4) Reaction which increased the property of the polymer (Higher Melting point) by Goodman et al.
(5) A reaction performed by Iwakura who noted that the plymer was insoluble to common solvents used for most of
the polymers.

1935- A much more effective acidic system was devised by Marks , working for du Pont, who found that liquid
hydrogen fluoride was a good solvent for polyaryl ether ketones .
1960 du Pont disagreed to tie a knot with the ICI which is a former partner developing other polymers which is
commercialized and monopolized to gain huge money.
1960 - John Rose (a chemist working for ICI Platics) decided to investigate high temperature materials. He wanted to
find a material that would have a high melting point and also be resistant to oxidation.
1978 The ICI Patented the reaction, producing polyaryl ether ketones.
1978 through further dedication, ICI discovered the Polyether ether ketone (PEEK) from the family of Polyaryl
ether ketone. As a revenge, they denied du Pont from being a company partner to commercialized the newly
discovered polymer PEEK.

1982 The U.S. granted the ICI for patenting the polymer, PEEK
1990 Polyether ether ketones were commercialized.
1990- PEEK became an important high-performance thermoplastic candidate for replacing metal implant
components, especially in orthopedic and traumatic applications
1993 - Victrex formed following a management buyout from ICI. Sales of 17 million and less than 60 employees,
focused primarily on the industrial market.
1999 - Victrex acquires upstream assets through the purchase of our DFDPM manufacturing site at Rotherham, UK
(part of the process for manufacturing BDF, the key raw material to make PEEK)
2005 - Victrex acquires the Seal Sands site on Teesside, UK, part of the process for manufacturing BDF, the key raw
material for PEEK. Rotherham and Seal Sands together provide a long term supply of raw materials and superior
process in manufacturing BDF, the key raw material for PEEK

II. CLASSIFICATIONS
A. Classification based on sources:
Polyether ether ketone is classified as a synthetic polymer, hence, it is a manmade polymer. It is made
by the dialkylation reaction of bisphenolate salts.
Being a synthetic polymer, it has an advantage, interms of manufacturability which balances the
supply over growing
number of demands.

Figure 3: PEEK resin produced through laboratory

synthesis (by Solvay)

B. Classification based on structure:

Polyether ether ketone is classified as a Linear Polymer. Poly(ether ether ketone), PEEK, is a linear
aromatic polymer with a repeat unit of three benzene rings separated by two ether bonds and one
carbonyl bond as shown in figure 4.
The chains when heated can flow easily . Although properties often associated with this type of
chain are a weak material, ductile with a low density and melting point, Polyether ether ketones have
high melting point, stronger and stiffer than other linear polymer.
As, a member of the polyaryletherketone family, it has an aromatic molecular backbone, with
combinations of ketone and ether functional groups between the aryl rings. This special chemical
structure makes PEEK exhibit stable chemical and physical properties :it is wear-resistant and stable
at high temperatures ; it is resistant to attack by all substances apart from concentrated sulfuric acid ; it
remains stable in sterilization processes .

Figure 4: Structure of Polyether ether ketone

C. Classification based on molecular forces:

PEEK is a semicrystalline thermoplastic, the polymer chains associate through intermolecular forces,
which weaken rapidly with increased temperature, yielding a viscous liquid. Thus, Polyether ether ketone
may be reshaped by heating and are typically used to produce parts by various polymer processing
techniques such as injection molding, compression molding, calendering, and extrusion.

D. Classification based on mode of polymerisation:

PEEK polymers are obtained by step-growth polymerization by the dialkylation of bisphenolate salts.
Typical is the reaction of 4,4'-difluorobenzophenone with the disodium salt of hydroquinone, which is
generated in situ by deprotonation with sodium carbonate. The reaction is conducted around 300 C in
polar aprotic solvents - such as diphenyl sulphone.
Step-growth polymerization refers to a type of polymerization mechanism in which bi-functional or
multifunctional monomers react to form first dimers, then trimers, longer oligomers and eventually
long chain polymers.
Due to the nature of the polymerization mechanism, a high extent of reaction is required to achieve
high molecular weight. The easiest way to visualize the mechanism of a step-growth polymerization is
a group of people reaching out to hold their hands to form a human chain each person has two

hands (= reactive sites).

Figure 5: Synthesis of Polyether ether ketone via Stepgrowth polymerization

III. STRUCTURE
PAEK is a family of high-performance thermoplastic polymers, consisting of an aromatic backbone
molecular chain, interconnected by a ketone and ether functional groups. Thus, PEEK belongs to a larger
family of PAEK polymers, Sometimes refered to as Poly ether ketones (PEK) or more simply as
Polyketones.
The chemical Formula of PEEK is shown in Figure 6 . Other members of PAEK family that are
considered for implants include PEK and Polyether ketoneketones (PEKK), whith chemical structures
depicted in Figure7. PEEK is the dominant member of the PAEK family for implant applications.
The chemical structure of PEEK,similar to its PAEK cousins,confers stability at high temperatures
(exceeding 300 deg C), resistance to chemical and radiation damage, compatibility with many reinforcing
agents ( such as glass and carbon fibers) and greater strength (On a per mass basis) than many metals,
making it highly attractive in industrial applications, such as aircraft and turbine blades. It stability,
biocompatibility, radiolucency, and mechanical properties make PEEK a suitable biomaterial for
orthopaedic and spine implants.

Unfilled neat PEEK is available as tanpellets or powder ( Figure 8) which can be converted into implant
parts by standard polymer processing techniques such as injection molding.

IV. Properties

Table 1 : Key Properties of PEEK

Table 2: Specific Properties of Polyether ether ketones

PEEK is a semicrystalline thermoplastic with excellent mechanical and chemical resistance

properties that are retained to high temperatures. The processing conditions used to mold PEEK can influence the
crystallinity, and hence the mechanical properties.
The Young's modulus is 3.6 GPa and its tensile strength 90 to 100 MPa. PEEK has a glass transition
temperature of around 143 C (289 F) and melts around 343 C (662 F). Some grades have a useful operating
temperature of up to 250 C (482 F) . The thermal conductivity increases nearly linearly versus temperature
between room temperature and solidus temperature. It is highly resistant to thermal degradation as well as attack
by both organic and aqueous environments. It is attacked by halogens and strong Bronsted and Lewis acids as well
as some halogenated compounds and aliphatic hydrocarbons at high temperatures. It is soluble in concentrated
sulfuric acid at room temperature, although dissolution can take a very long time unless the polymer is in a high
surface area to volume form such as a fine powder or thin film.
Shown in both tables ( Table 1, and Table 2 ) , It has an Excellent chemical resistance Very low
moisture absorption Inherently good wear and abrasion resistance and Unaffected by continuous exposure to
hot water or steam.

A. PEEK VS METALS
PEEK is an ideal replacement for stainless steel, other types of metal tubing, and even glass, for weight reduction,
comparable strength/mass, chemical resistance, hardness, and low extractables. PEEK most of all is comparable in
strength, yet lighter and more cost effective than stainless steel. PEEK is polymer tubing, so the risk of corrosion,
outgassing, or leaching (which can cause contamination) is minimal. PEEK is chemically resistant and inert with
most acids and bases. PEEK with thin walls can also be made more flexible than stainless steel or titanium tubing,
and can easily be cut to length with a razor blade. PEEK is weldable, machinable, and can be used with your existing
stainless steel or polymer fittings. PEEK can be bonded with epoxies, cyanoacrylates, polyurethanes, or silicones.

Table 3: Contrast of The thermoplastic, Polyether ether

Ketones, against Metals, such as Steel,Bronze, and
Besides weight reduction, we can see three more major benefits: enhanced performance, greater design freedom,
Aluminum

and lower total system cost. Enhanced performance benefits include everything from extending lifetime by
eliminating corrosion, increasing fuel efficiency with lower friction, and handling higher loads/speeds to operating
in more extreme chemical environments.

B. PEEK Vs. Stainless Steel and Other Polymers

Table 4: Properties of Polyether ether ketaone vs. Stainless

steel and other common polymers

As shown in table 4, in terms of its Temperature performance, Gama radiation, its resistance to chemicals, and
prevention of dimensional changes, Polyether ether ketone does very well, than to most of the polymer, and even
to the most commercially produced and highly demanded metal material, stainless steel, without sacrificing the
specific weight , which is desirable to aerospace application and clinical applications.
It is, however, very costly to produce, like PTFE, which will be discussed later on, in Manufacturing.

C. PEEK Grades
c.1. PEEK (Unfilled)

This general purpose grade is unreinforced and offers the highest elongation and toughness of all PEEK
grades. Unfilled PEEK is available in sheet and rod forms in natural (a very light brown or tan) color (shown
in Figure 9) and is also available in black . Black PEEK is ideal for instrument components where aesthetics
are important, as well as for seal components where ductility and inertness are important. All unfilled PEEK
grades comply with FDA regulation 21 CFR 177.2415 for repeated food contact.
NOTE: Boedeker Plastics now carries Virgin PEEK 450G Tube Stock.

Figure 9: Virgin ( Unfilled ) Polyether ether ketone

c.2. PEEK (30% Glass Filled)

The addition of glass fibers significantly reduces the expansion rate and increases the flexural modulus of
PEEK. This grade is ideal for structural applications that require improved strength, stiffness, or stability,
especially at temperatures above 300F (150C). Glass-filled PEEK is light brown or tan in color.

Figure 10: 30% Glass Filled - Polyether ether ketone

c.3. PEEK (30% Carbon Filled)

The addition of carbon fibers enhances the compressive strength and stiffness of PEEK, and dramatically
lowers its expansion rate. It offers designers optimum wear resistance and load carrying capability in a PEEKbased product. This grade provides 3 times higher thermal conductivity than unreinforced PEEK -dissipating heat from the bearing surface faster. Carbon-filled PEEK is black in color.

Figure 11: 30% Carbon Filled - Polyether ether

ketone

c.4. PEEK (Bearing Grade, Ketron HPV)

This grade of PEEK, containing carbon fiber reinforced with graphite and PTFE lubricants, offers the lowest
coefficient of friction and the best machinability for all PEEK grades. Bearing grade PEEK has an excellent
combination of low friction, low wear, high limiting PV, low mating part wear, and easy machining. Bearing
grade PEEK is black or dark grey in color.

Figure 12: 30% Carbon Filled - Polyether ether

ketone

Table 5: Properties of Polyether ether ketone Grdaes

In the table 5 shown above, of all the three grades of Polyether ether ketone, including also, the unfilled, virgin
Polyether ether ketone, the PEEK grade that possesses the highest unit of properties,is PEEk filled with 30% carbon.
It is because of the change in Molecular weight.

D. Influence of molecular weight on the properties of Polyether ether ketone

Variations in molecular weight of poly(ether ether ketone) significantly alter its processing behavior, product properties,
and performance.

We used molecular weights (measured by size-exclusion chromatography) of 23,000, 27,000, and 37,000g/mol,
corresponding to 80, 94, and 129 repeat units (designated PEEK80, PEEK94, and PEEK129, respectively). We
characterized the thermal behavior of these different polymer grades using differential-scanning-calorimetric
analysis. Both isothermal and nonisothermal crystallization processes resulted in a crystallization index for all three
grades of approximately 3.0, indicating a tendency for all to form spherulitic crystals. The material's melting
temperature and crystallinity decreased slightly with increased molecular weight, while the crystallization
temperature decreased dramatically. We determined isothermal crystallization-activation energies of 565, 553, and
408kJ/mol for PEEK80, PEEK94, and PEEK129, respectively. We obtained comparable values from our
nonisothermal crystallization-activation study. This data suggests that, compared to commodity polyolefin resins,
PEEK has a much faster rate of crystallization.2 However, the rate greatly decreases with increasing molecular
weight. These molecular-weight-dependent relationships should be considered when determining how to process
PEEK to obtain the most desirable product.
The performance of PEEK-based products depends on the polymer's mechanical and thermomechanical behavior. We
conducted dynamic-mechanical thermal analysis, in addition to tensile and impact tests, to assess the effects of
molecular-weight variations on these properties. In the low-temperature region, the storage moduli for all three
grades of PEEK were comparable, while high-molecular-weight PEEK demonstrated a slightly smaller flexural
modulus than the low-molecular-weight polymers. In the glassy region and in the rubbery phase above the glasstransition region, the storage moduli significantly decreased with increasing polymer molecular weight. In addition,
as molecular weight increased, the tensile strength at yield decreased, while that at break increased. As molecular
weight of PEEK increased, the tensile moduli decreased slightly, while the tensile strain increased greatly (see Figure
13).
Figure
13

Many aspects of PEEK processing and performance behavior are related to its relaxation characteristics, which have
not previously been reported. Our relaxation study of PEEK, using a parallel-plate rheometer, demonstrated that a
slight increase in molecular weight can significantly increase the relaxation time: PEEK129 exhibited relatively
linear behavior, analogous to rubber-type relaxation (see Figure 14). However, PEEK80 and PEEK94 have at least
two different relaxation regions.
Figure
14

We conducted rheological studies using a capillary rheometer in steady shear mode and a parallel-plate rheometer in
both steady and dynamic modes. The broad range of shear rates from these experiments encompassed conditions
relevant to PEEK melt processing, secondary operations, and stress relaxation. In the entire shear-rate region studied,
the shear viscosity increased dramatically with increased molecular weight (see Figure 15). Additionally, doubleshear-thinning behavior, analogous to that of liquid-crystalline polymers, distinguishes PEEK from many other
polymers. We determined the double-melt shear-thinning regions of PEEK. In low-frequency regions, it can be
assigned to molecular relaxation at crystalline interfaces and is related to the double-melt-peak phenomenon of
PEEK.

Figure
15

In summary, understanding the influence of molecular weight on the PEEK thermal, mechanical, and rheological
behavior, and product performance will be useful for optimization of product development. Additionally, both
primary and secondary conversion processes (such as injection molding and extrusion on the one hand and annealing
and post-processing on the other) will benefit from this work. This represents one direction in our continuing efforts
to better understand engineering and high-performance polymers. Ultimately, the design of high-performance PEEK
composites will be optimized because of an understanding of these molecular-weight/performance trends.

E. Crystallinity
The molecular chain of PEEK may be visualized as a tangled strand of spaghetti that is hundreds of meters
long. The molecular chain is not static but vibrates and rotates due to thermal energy or in response o externally
applied deformation. The PEEK molecule is relatively stiff because of the presence of the aromatic (benzene
rings) along its backbones (Fig 4) however, does have the freedom to rotate axially about the ether (-O-) bonds
and ketone-carbon bonds (-CO-). When cooled slowly from the molten state, the molecular chain can rotate upon
itself to form chain folds and to organize into ordered domains, known as crystals. PEEK crystals are embedded
within amorphous (disordred Regions) and form a two phase microstructure (fig. 16)

Figure

PEEK conforms well to the conceptual world of a two phase semi-crystalline polymer, consisting of an
amorphous phase and crystalline phase. Similar to semi-crystalline polymersincluding utra high molecular weight
polyethylene (UHMWPE), the crystalline content of PEEK variesdepending upon its thermal processing history.
The crystallinity of injection molded PEEK in implants typically ranges from 30% to 35%, by adjusting the
cooling rate during fabrication offilms, crystallization of PEEK can be greatly reduced, resulting a nearly
completely amorphous material.

V.

Applications
A. HPLC Application

PEEK has become the gold standard for HPLC analytical science applications due to its purity, high burst
pressure, and chemical inertness and resistance. It is also resistant to organic and inorganic solvents.
Chromatographers value PEEK for its strength, flexibility, and ease of cutting.
Property of PEEK essential for this application:
Purity
High burst pressure
Chemical resistance
PEEK (poly ether ether ketone) tubing has become a standard item in the operation of many HPLC systems. It is
convenient, inexpensive, and easy to identify the internal diameter. However, some care needs to be taken to avoid
problems associated with PEEK tubing .
Most reversed-phase HPLC applications with systems running at conventional pressures (Another advantage of
PEEK is that it is easily cut to any desired length with a small guillotine-like cutter containing a razor blade. But be
careful not to cut the tubing by slicing through it like you would with a pair of scissors this can block the lumen of
the tubing. Rather, pinch the cutter and rotate it around the tubing until a groove is cut all the way around the tubing.
The tubing then can be snapped at the cut, leaving the lumen open. As with SS tubing, it is wise to run a few
milliliters of solvent through the tubing to purge any particulate matter left from the cutting process. Just connect the
up-stream end of the tubing to the HPLC system and turn on the pump for a minute or so.
An advantage about PEEK tubing is that it is easily identified. Most manufacturers colour-code the tubing, as is
shown in Figure 17. The brand shown uses red to code the 0.005-in. (0.125-mm) and yellow for the 0.007-in. (0.175-

mm) i.d. tubing. Others would probably worried about the colour leaching out and causing UV interferences. But
some chemists laboratory did extensive testing and did not find any evidence of problems with extracted pigments.

Figure 17: PEEK tubing can be purchased in bulk for convenient cutting in the laboratory. Color coding
makes it easy to keep track of the internal diameter.
However, not all HPLC solvents are compatible with PEEK tubing. Aqueous buffers and salts are fine, as is
acetonitrile (ACN), methanol (MeOH), and other alcohols. But tetrahydrofuran (THF) and the chlorinated solvents
are not recommended for PEEK tubing. These solvents weaken the tubing and cause it to become brittle. I have
found no evidence of UV interferences when these solvents are used, but be careful if you are using LC-MS. Others
have seen background problems created when THF was used with PEEK tubing in LC-MS applications, and it may
be a problem with other detectors, as well. The best practice is to avoid the use of THF and chlorinated solvents
when PEEK tubing is present.
You might be a bit puzzled, though, when PEEK tubing instructions cautioned against the use of THF and
chlorinated solvents, but I did not see similar warnings for PEEK injector rotors or other PEEK parts. So I asked an
expert in PEEK chemistry, and learned that the solvent compatibility problem with PEEK is a result of the processing
techniques. Tubing is extruded during manufacturing and needs some kind of a lubricant in the process. Rather than
using plasticizers, which would be sure to contaminate an HPLC system, a small amount of the PEEK monomer is
mixed into the polymer blend as a lubricant. It is this monomer that gets extracted out of the tubing and causes the
brittleness and lower burst strengths. PEEK injector rotors and other machined or cast PEEK parts do not need the
lubricant, so the monomer is not added, and a more solvent-stable product is achieved.
Speaking of burst strengths, most PEEK tubing can be used up to the upper pressure limits of conventional HPLC
equipment (6000 psi = 400 bar), but cannot be used at higher pressures with U-HPLC type applications. The smaller
internal diameters should have higher burst strengths because of the greater wall thickness, but it is wise to check the
specific tubing specifications if you expect to expect to operate routinely at >4000 psi (275 bar) with PEEK tubing.
Another nice characteristic of PEEK tubing is that it can be connected with finger-tightened PEEK fittings. These
allow tool-free assembly for convenient connections. Because the connection is less secure than a SS fitting on SS
tubing, proper assembly is mandatory. With the pump off, push the tubing to the bottom of the fitting port, then
tighten the nut. If the fitting leaks, turn the pump off, loosen the nut, reseat the tubing, and tighten the nut.
Attempting to tighten the nut with the pump on can cause the connection to slip, creating leaks or internal voids.

Also, although you can use PEEK fittings with SS tubing, dont try the reverse. SS ferrules can pinch PEEK tubing
closed or if over-tightened, can cut off the tip of the tubing

B. Aerospace
PEEK is particularly useful in the aerospace field for its weight. In an application where two grams can make a
difference and where weight is directly correlated to fuel cost, lightweight PEEK tubing is superior to stainless steel.
PEEK matches aluminum in mechanical properties, and is more resistant to fluids such as hydraulic fluids. Thinwall
PEEK is more flexible and kink resistant than aluminum tubing. PEEK convoluted tubing is alsoused for its abrasion
resistance properties, to protect vulnerable wires located in areas where they could be crushed or severed. PEEKs
strength, weight, and heat resistance are ideal for this application.

Property of PEEK essential for this application:

Lightweight
Strength
Chemical resistance

Aerospace engineers require lightweight materials that provide processing

flexibility, reduce manufacturing costs, and provide durability in harsh
environments.PEEK polymers have successfully displaced metals, traditional
composites and other plastics in a growing number of aerospace applications
because they are exceptionally strong, inert, and inherently flame retardant,
and can be easily fabricated into tight tolerance parts. VICTREX PEEK polymers
have been officially qualified by many aircraft manufacturers and can also be
supplied to the military specification MIL-P-46183.

PERFORMANCE
Stability at Elevated Temperatures
Many aerospace components must endure continuous long term exposure to elevated
temperatures. PEEK polymer is extremely stable when tested against other commonly known high
heat thermoplastics.
Figure

Several new PEEK polymer grades and compounds are available to maximize
mechanical properties and improve moldability.

High Temperature Resistance

Due to the semi-crystalline structure of VICTREX PEEK polymer mechanical
properties are maintained well past the glass transition temperature.

Figure 19: Yield Strength as a Function of Temperature for

PEEK Polymers

Flammability
VICTREX PEEK polymer performs exceptionally well in respect to flammability.
VICTREX PEEK 450G is UL94 V-0 rated
at 1.5 mm and has a Limiting Oxygen Index of 35% at 3.2 mm thickness and 24% at
0.4 mm thickness. These flammability characteristics are inherent in the material and
are achieved without the inclusion of any flame retardant materials such as halogenbased additives. In tests to measure smoke produced by the combustion of plastic
materials, the data shows that unfilled VICTREX PEEK polymer has the lowest value
of specific optical density of all the materials tested
8

Toxic Gas Emission

VICTREX PEEK polymer produces very little toxic gases when combusted. It
produces mainly carbon dioxide and carbon monoxide upon pyrolysis. VICTREX
PEEK 450G has a toxicity index of 0.22 (MOD NES 713) with no acid gases detected.

Coefficient of Thermal Expansion

The inclusion of fillers into VICTREX PEEK polymer results in a reduction in the
coefficient of expansion to a level where it is comparable to metals, thus allowing
direct replacement of metal components with polymer-based components without
any risks arising due to differential expansion.

Figure 21: Coefficient of Linear Expansion in Flow Direction of VICTREX PEEK PolymerBased Materials in Comparison with Other Common Aerospace Materials

Strength
VICTREX PEEK polymer has high specific strength compared to metals. Reinforcing
with chopped glass or carbon fibers yields strength-to-weight ratios that meet or
exceed those of common aerospace materials. Continuous fiber reinforced
composites made with a VICTREX PEEK polymer matrix have significantly higher
strength and stiffness
Figure 23: Specific Strength of VICTREX PEEK Polymer-Based
Materials in Comparison with Other Common Aerospace Materials

1
0

Chemical Resistance
PEEK polymer has exceptional resistance to a wide range of acids, bases and
hydrocarbons including jet fuel and hydraulic fluid. Soaking PEEK compounds
in
70C (158F) hydraulic fluid for 1,000 hours led to less than a 5% change in
nominal properties of tensile strength, tensile modulus and tensile elongation.

ELECTRIC WIRE BUNDLE AND TUBING CLAMPS

PEEK polymer has been coupled with a proprietary silicone overmolding process to
produce a range of wiring, tubing clamps and stand-offs that deliver significant
weight and cost savings on the new Boeing 787 aircraft.
Advantage:

Weight is reduced versus aluminium

Part count is reduced by consolidation
Material is completely non-corrosive and non-conductive for use throughout
un-pressurized zones.

Figure 24: Wiring and table clamps made from PEEK

Polymer
1
1

IMPELLER BLADES
VICTREX PEEK polymer has been used to replace metal propellers and impellers in a
variety of aerospace devices including oil cooling systems and ventilation system
fans used for low pressure air delivery in helicopters. They can be designed to weigh
much less than metal components, have less inertia and reduce the horsepower
requirements of the motors used to spin the blades.

Figure 25: Environmental control system made from PEEK

Polymer

Air craft door handles

Weight reduction was paramount when developing the
Airbus A380. This included door handle systems. PEEK polymer was the only
material to survive the Airbustest program for door handles. Components are
injection molded and have complex geometries with numerous ribbing and long
flow paths

Figure 26: Door Handles in Airplane

made from PEEK Polymer

Cable Ties
Used for bundling and securing wires and cables to the airframe. Low moisture
absorption of VICTREX PEEK polymer ensures the dimensional integrity of the ties so
they will not swell and damage wire insulation.
1
2

Figure 27: Cable Ties made from PEEK

Polymer

C. Chemical Processing
In the chemical processing industry, PEEK is chosen because it is inherently pure and has
outstanding chemical resistance. Unlike most metals, such as stainless steel or aluminum, PEEK
can be used in long continuous service applications with virtually no levels of contamination
introduced to the chemicals being processed. PEEK has been shown to outperform fluoropolymers
with its excellent fatigue resistance and general mechanical properties.

Property of PEEK essential for this application:

Inherently pure
Chemical resistance
High continuous service temperature (500F/260C)
D. Medical Application

PEEK can be used in the medical field as a rigid tube in minimally invasive surgery, such as stent
delivery. PEEK is also useful in medical applications because of its low coefficient of friction,
which does not allow heat to build up, reducing downtime and speeding time-sensitive procedures.
For medical devices which require repeated sterilization, PEEK tubing can withstand 3000+
autoclave sterilization cycles. PEEK maintain
s high mechanical strength, resists stress cracking, and hydrolytic stability in hot
water, steam, solvents, and chemicals.

Property of PEEK essential for this application:

Biocompatibility
Mechanical strength
Resistant to stress cracking

1
3

Hip Arthroplasty
This durable material addresses the need for new, longer-lasting designs for younger and more
active patients. Excellent wear resistance and exceptional structural strength make it an ideal
choice for hip cups that support bone-conserving concepts.
PEEK-OPTIMA Wear Performance offers an alternative load-bearing material to metal designed
to address metal ion concerns. It features a modulus similar to human bone, which reduces stress
shielding and leads to improved physiological loading.
PEEK-OPTIMA Wear Performance accommodates both standard and new implant fixation
technologies. It is radiolucent and compatible with common imaging technologies. This allows
improved visualisation for placement and post-operative follow up in the months and years after
surgery.

Screening tests and hip and knee simulator tests indicate that extremely low wear can be
achieved against metal and ceramic counterfaces. 1

An acetabular cup bearing against a 54mm ceramic head showed a wear rate of
approximately 1mm3/million cycles; unicondylar knee testing reported a 70% reduction in
wear compared with literature values for similar UHMWPE-base prostheses 1 & 2

Implantation in a clinical trial as an a acetabular liner produced no adverse reports of wear

biocompatibility. 3

Use as a very thin acetabular bearing provides anatomical stress distributions; fixation has
been achieved by titanium and/or hydroxyapatite coatings 4

1
4

Figure 28: a.) Hip implant made from

polymer(left) b.) Hip Arthroplasty by PEEK
Implant

Knee Arthroplasty

In 2010 more than 90,000 knee revision surgeries were performed in the US and Europe. This
indicates that some 8% of all knee implant procedures result from failure of the initial knee
implant. A contributing factor to these failures is dislocation, whereby the rotational axis slips out
of its guide, requiring total replacement of the implant.
Hinge constructs made from PEEK-OPTIMA Reinforced and PEEK-OPTIMA Wear Performance
offer superior cold-flow resistance as well as dimensional stability during the device lifetime (>15
years) compared to traditional hinge mechanisms that use UHMWPE, which resists dislocation. In
addition, the PEEK-OPTIMA polymer has a flexural strength similar to the cortical bone, thus
reducing stress shielding and improving patient comfort. Its proven biocompatibility and
biostability in implantable devices worldwide provides safety, longevity and reassurance to
patients and surgeons alike.

1
5

Figure 29: a.) knee implant made from

polymer(left) b.) knee Arthroplasty by PEEK
Implant

Shoulder Arthroscopy

PEEK-OPTIMA Natural features mechanical properties that allow reliable suture retention for
knotless suture anchors. Commonly used in the lateral row of a double-row rotator cuff or in the
Glenoid for SLAP and Bankart repairs, knotless suture anchors allow surgeons to perform
procedures faster and reduce the time patient are under anesthesia.

The natural mechanical strength of PEEK-OPTIMA polymers has shown remarkable

performance in load-to failure strength (F. A. Barber, M.A. Herbert, C. Beavis, F. Orro; J.
of Arthroscopic and Related Surgery; Vol. 24, No 8; 2008). This is why the material is
commonly used for high-strength anchors.

PEEK-OPTIMA polymers allow for simple post-operative implant assessment with no

image artifacts using X-ray, CT, and MRI imaging methods.

Completely bio-inert PEEK-OPTIMA polymers reduce the possible risk of patient reaction
to a device implanted in the body.

PEEK-OPTIMA Natural allows for greater design and production flexibility for injection
molding and machining processes, enabling development of smaller implantable devices.

1
6

a.)

b.)

Figure 29: a.) Shoulder implant made from

polymer b.) Shoulder Arthroplasty by PEEK
Implant

VI. Manufacturing
Poly(arylene ether ketone)s (PAEKs), such as PEK, PEKK and PEEK are an important
class of high performance engineering thermoplastics displaying a unique combination of thermal
stability, chemical and solvent resistance, good mechanical properties over a wide temperature
range, good fire resistance and good electrical performance.

1
7

These polymers can be fabricated by conventional techniques, such as extrusion and

compression molding, and can be applied as matrix resins for high performance reinforced
composites. The Tg and Tm values are usually amorphous polymers and subject to attack by
solvents, PAEKs are semicrystalline polymers and therefore resistant to solvents, which is a
critical factor in an aerospace environment. However, because of their crystallinity and the
resulting insolubility, together with melting points generally above 300 deg C, these polymers
are also difficult to prepare with sufficiently high molecular weight unless extreme reaction
conditions are used.

1
8

PAEKs are generally synthesized by an aromatic nucleophilic substitution reaction of activated aryl
dihalides with aromatic diphenolates in a dipolar aprotic solvent, or by electrophilic (FriedelCrafts) acylation of aryl ethers.
1.2

Synthesis of Poly(arylene ether ketone)s

1.2.1 Electrophilic Routes
8

In 1962, Bonner at DuPont was the first one who reported the synthesis of wholly
aromatic poly(ether ketone ketone)s (PEKK) by Friedel-Crafts acylation.

Isophthaloyl

chloride or terephthaloyl chloride was condensed with diphenyl ether using nitrobenzene as
solvent and aluminum trichloride as a catalyst (Scheme 1.2). However, only low molecular
weight polymers (inherent viscosity, IV ~ 0.18 dL/g) were obtained.

In 1964, Goodman at

ICI reported the successful synthesis of poly(ether ketone) (reduced viscosity, RV ~ 0.5 dL/g) by
the self-condensation of p-phenoxybenzoyl chloride under similar conditions using methylene
chloride as solvent.

Aluminum chloride catalyzed polycondensation of diphenyl ether with mixtures of terephthaloyl

chloride and isophthaloyl chloride is a low cost route to poly(ether ketone ketone)s. The
1
9

reactions are carried out in the presence of an excess of aluminum chloride in non-basic solvents
such as 1,2-dichloroethane, dichloromethene, or o-chlorobenzene. The insolubility of the polymers
in these solvents limits the formation of high molecular weight polymers. Special treatment is
usually required to improve the melt stability. In some cases, ortho-acylation and alkylation of
aromatic polymer chains also occur.
The low cost acid chlorides, such as terephthaloyl chloride and isophthaloyl chloride,are weaker
base than 4,4-oxybisbenzoyl chloride and more difficult to activate by AlCl3. The resulting
carbocationic intermediates are more reactive and less selective to aromatic sites, which leads to
increased ortho-acylation during polymerization.
Polymerizations in the presence of a large excess of AlCl3 complexed with a Lewis
base, such as DMF, LiCl, dimethyl sulfone, pyridine or N-methylpyridinium chloride, were
reported by Jansons et al. to produce cleaner and higher molecular weight polymers at or below
room temperature.

12,13

The Lewis base can complex with AlCl3 to keep excess AlCl3 in the

solution. The complex adducts can be dissolved in a non-basic solvent, such as CH2Cl2 or
1,2-dichloroethane. The polar complex solutions also increase the solubility of polymer
complexes that lead to high molecular weight polymers. Most of the work in this area was
submitted for patents. One of the examples in literature publications was reported by Fukawa
and Tanabe. p-Phenoxybenzoyl chloride was polymerized in the presence of excess AlCl3 and
phenyl ether capping agent in a solution of DMF in methylene chloride to give PEK with
1.37 dL/g inherent viscosity.
Alternatively, PEKK can be obtained by condensation of isophthaloyl chloride and/or
terephthaloyl chloride with isolated intermediates such as 4,4-diphenoxytere- phthaloylphenone
and 4,4-diphenoxyisophthoylphenone. These polymerizations yield cleaner polymers, especially
in the presence of AlCl3 complexed with a basic co-agent.
by Gay and Brunette

15

The copolymer was prepared

at DuPont from the isolated intermediates,

2
0

1,3-bis(p-phenoxybenzoyl)benzene with terephthaloyl chloride, and 1,4-bis(p-phenoxybenzoyl)benzene with isophthaloyl chloride (Scheme 1.3).
This perfectly alternating
copolymer of meta and ortho phenylene group has high Tg (166 C) and low Tm (332 C),
which is desirable for facile processing and high heat deformation resistance.

Polyphosphoric acid can be used as a solvent to produce high molecular weight poly(ether
ketone ketone)s.

Previously, Iwakura

16

reported the synthesis of PEK with inherent

viscosity of 0.5 dL/g by self-condensation of p-phenoxybenzoic acid using polyphosphoric acid

as the solvent and catalyst.

Later, diphenyl ether was also used to condense with diacids

or diacid chlorides in the presence of AlCl3 or SnCl4 to produce high molecular weight
poly(ether ketone)s.

17

One of the reasons for the formation of high molecular weight

polymers is polyphosphoric acid dissolves the polymers probably by protonation of the carbonyl
groups.
Mark developed a more effective solvent/catalyst (HF/BF3) system to synthesize high
molecular weight PEK.

Under well-controlled reaction conditions, high molecular weight

2
1

PEK with an inherent viscosity of 1.33 dL/g was prepared in HF/BF3 solvent system. Large
excesses of solvent and catalyst have to be used to obtain high molecular weight polymers.
Another strong acid system, trifluoromethanesulfonic acid, was reported by Rose to catalyze
the condensation of carboxylic acid with activated phenyl ether (Scheme 1.4). High molecular
weight polymers were synthesized using this solvent system. For semi-crystalline PAEKs,
replacement of CF3SO3H with the less expensive CH3SO3H failed to yield high molecular
weight polymers.

These two strong acid systems are not very attractive for industrial

applications due to the harsh reaction conditions and cost factors.

2
2

1.2.2 Nucleophilic Routes

The nucleophilic aromatic substitution reaction involves use of activated aromatic dihalides and
aromatic diphenolates. The general reaction is shown in Scheme 1.5. In general, a strong
electron withdrawing group such as carbonyl, sulfone or phosphine oxide is necessary to activate
the aromatic dihalides. The reactivity of the halogens are in the order of F>>Cl>Br. Typically
19
potassium carbonate is used as base to avoid the side reaction of alkali metal hydroxides and
dipolar aprotic solvents such as DMSO, DMAc and NMP are utilized.

Johnson et al. reported the first attempt to synthesize PEEK by polycondensation of

bisphenolate with activated dihalides using DMSO as a solvent and NaOH as a base. High
molecular weight polymers were difficult to obtain due to the crystallinity and the resulting
insolubility of polymers in DMSO.
22

Rose

To circumvent the solubility problem, Attwood

21

and

used diphenyl sulfone as a solvent to obtain high molecular PEEK (Scheme 1.6). The

polymerization was carried out near the melting point of the polymer to maintain solubility.
Victrex PEEK was commercialized by ICI in 1982 using this method. At high temperatures, side
reactions such as ether exchange and cleavage became important.
high molecular weight poly(ether ketone)s can be obtained.

2
3

Under careful optimization,

One of the major drawbacks for this synthetic route is the expense of fluoro monomers. For
dihalides activated with carbonyl groups, less reactive chloro monomers fail to produce high
molecular weight polymers. Side reactions such as single electron transfer reaction were observed
during polymerization of dichlorides.
To develop a low cost route to PAEKs, expensive fluoro monomers are being replaced
with activated chloro monomers.
Dichloro monomers were also polymerized with bisphenols in the presence of fluorides as
promoting agents.

26

The fluoride ions promote the displacement of the chloride sites to form

more reactive fluoride sites, which react with phenoxide anion to form high molecular weight
polymers. The nucleophilicity and solubility of phenoxide anion increased by adding 5-10 mol %
27

phase transfer catalysts such as N-alkyl-4-(dialkylamino)pyridium chlorides.

The reaction time

to obtain the same molecular weight was reduced up to 5 fold compared to the uncatalyzed
reaction.
Kricheldorf and coworkers used trimethylsilylated phenols to react with activated difluoro
monomers, such as 4,4-difluorobenzophenone, in the presence of CsF to prepare poly(ether
ketone)s. The polymers were prepared in the melt without the use of base and solvent. The
volatile side product, trimethylsilyl fluoride, can be removed at high temperature.

1.2.3 Soluble PrecursorApproaches

Despite the success of electrophilic and nucleophilic routes, harsh reaction conditions are usually
required to obtain high molecular weight poly(ether ketone)s. To address the solubility problems, several
soluble precursor approaches were reported to initially produce high molecular weight, soluble precursors,
which could then be chemically modified to remove the solubilizing groups. McGrath and later Sogah
independently reported the synthesis of soluble highmolecular weight PEEK containing pendent t-butyl
groups in the polymer backbone (Scheme 1.9).

t-Butylhydroquinone was polymerized with 4,4-

difluorobenzophone in DMSO at relatively low temperature (170 C). Polymers with inherent viscosity
up to 2.7 dL/g(in H2SO4) were obtained. Retro Friedel-Crafts alkylation in the presence of Lewis acid
catalysts such as CF3SO3H removed the t-butyl substituents to produce high molecular PEEK.

32

Kelsey et al. used the cyclic ketal of 4,4-dihydroxybenzophenone to polymerize with

4,4-difluorobenzophenone in DMAc at 150 C (Scheme 1.10). The polymerization
produced soluble amorphous polyketal, which was quantitatively converted to PEK by acid
catalyzed hydrolysis. Since the polymerization is carried out at lower temperatures, PEK
with minimal defect structures can be obtained by this process. Compared to PEEK
prepared under the usual high temperature conditions (diphenyl sulfone as solvent), PEK
produced by this approach displayed excellent physical properties, especially the high
degree of crystallinity and higher Tg, which indicate a uniform linear backbone structure.

In 1993, Pandya, Yang and Gibson developed a new polyketone synthesis based on the
nucleophilic substitution of bis( -aminonitrile) derivatives with activated aromatic
dihalides. Bis( -aminonitrile)s were prepared from aromatic dialdehydes in high yield by
Strecker synthesis. The conjugate bases of the

-aminonitriles are powerful and selective

nucleophiles, which can react with activated aromatic dihalides to form a carbon-carbon bond.
Polymerization of isophthalaminonitrile with 4,4-difluorophenyl sulfone in anhydrous DMF at
room temperature using NaH as base gives a soluble high molecular weight polyaminonitrile

1.2.4 Other Routes

A.

Carbon-Carbon Coupling Routes

Nickel-catalyzed coupling of chlorophenyl groups in a dipolar aprotic solvent such as

DMAc was reported to produce poly(ether ketone)s.

36

Dichlorides containing ether and

ketone linkages polymerized in the presence of Zn/NiCl2 complexes with triphenylphosphine

and bipyridine in DMAc at 90

C (Scheme 1.13).

For soluble meta isomers, poly(ether

ketone)s with inherent viscosity up to 0.87 dL/g (in NMP) could be obtained. The reaction must
be performed under an inert atmosphere and in the absence of water. The zinc dust used must
have a low level of oxide and a high surface area. The optimum reaction temperature in DMAc
was about 80 C.

Higher reaction temperatures gave lower molecular weight. Because of

their crystallinity and the resulting insolubility in DMAc, poly(ether ketone)s with all paralinkages could not be obtained in high molecular weight.
B. Ring Opening Polymerization
Recently nucleophilic ring opening polymerization of macrocyclic arylene ether ketone
oligomers has been reported as a means of direct conversion of low viscosity cyclic species to
form high performance poly(ether ketone)s. Colquhoun at ICI reported the first synthesis of
macrocyclic monomers containing ether and ketone linkages through nickel catalyzed
coupling of aryl dihalides under pseudo high dilution conditions. Gibson and Chen synthesized
poly(ether ether ketone) single size macrocycles and macrocyclic oligomer mixtures by both
nucleophilic aromatic substitution and Friedel-Crafts acylation. The ring opening polymerization
is initiated by a catalytic amount of nucleophiles, such as CsF or potassium salts of phenoxides.
Control of ring opening polymerization is difficult. Complete conversion of the monomers is
very difficult to achieve. In some cases, melting points of the cyclics or cyclic mixtures are too
high for practical ring opening polymerization.

VII. Fabrication
With the development of Additive Manufacture (AM) process, the manufacturing of PEEK parts
with complex shape has been studied based on the Selective Laser Sintering (SLS) process [8, 9]. The
method is at the early stage with more work to be done on the melting and crystallization as well as the
kinetics and time-temperature behavior of the process. Motivated by the importance of PEEK components
in future engineering applications, we investigated the use of another AM process in the fabrication of
PEEK components.
The mask-image-projection based Stereolithography (MIP-SL) is an AM process, in which
projection images are projected on photosensitive resin. An illustration of the MIP-SL process is shown
in Figure 1a. The mask images can be dynamically defined by a Digital Micromirror Device (DMD) [10,
11] with micro mirrors that can turn on or off a pixel. In the MIP-SL process, a 3-Dimensional (3D)
model of a designed part is first sliced into layers of 2-Dimensional (2D) mask images. The mask images
are then sent to a DMD and projected on a liquid resin surface. The photocurable resin is selectively cured
and forms one layer. The fabrication of next layer goes on after raising the Z-stage. The building job of
the designed part is finished until all the layers have been built.

Figure 30: An illustration of the MIP-SL process and a

bottom-up projection setup

Figure 30b shows a bottom-up projection setup that can be used in the MIP-SL process. In the
setup, the layer thickness of the part can be well controlled due to the constraint curing. However, the
separation force between the tank and the cured layer could be large. Zhou, et al. [12] studied the
separation force and presented a two channel tank for the bottom-up MIP-SL system. The developed two
channel design is shown in Figure 31, in which half of the tank is coated with a PDMS film while the
other half has no coating. The separation force between the cured layer and the tank becomes much
smaller by moving the platform from the left channel (i.e. the channel with PDMS film coating) to the
right channel (i.e. the channel without PDMS film coating) before lifting the platform up.

Figure 31: A two-channel tank design for the bottom-up

projection setup.

In this paper, we investigated the two channel design for the fabrication of green parts of PEEK
composite. We also studied the sintering process and material properties of sintered PEEK composite
parts. The paper is organized as follows. An overview of the PEEK fabrication process is described in
section 2. The green part fabrication based on the MIP-SL process is discussed in Section 3. The
sintering process is presented in Section 4. Section 5 presets the testing results on various material
properties of the fabricated parts. Finally we draw conclusions in Section 6.

2. Process Overview
Similar to the fabrication process of PZT components, our PEEK fabrication process includes two major
steps, green part fabrication and sintering of the fabricated green parts. An illustration of the
process is shown in Figure 32. In order to use the MIP-SL process, composite slurry is first produced by
mixing PEEK powder and photosensitive resin. The PEEK slurry should be mixed well in order to
fabricate good quality parts. After the slurry has been prepared, the green parts with desired shapes can
be fabricated using the MIP-SL process. A main challenge in this step is the recoating of the PEEK slurry
which can have a much higher viscosity due to the addition of PEEK powder. Finally, green parts are
sintered for achieving improved material properties. The challenge in this step is to understand the proper
settings of the sintering process such that the fabricated PEEK parts can have desired material properties.

The preparing of PEEK slurry is important. It is desired to have homogenous slurry such that the
fabricated parts could have isotropic property. The PEEK powder used in our study is PEEK 150PF from
VICTREX Co. The powder is in spherical shape with particle size of 40 m. The photocurable liquid
resin used in our study is SI500 from EnvisionTec Inc. A precision weight scale was used in determining
the weight ratios of the PEEK slurry and a stirring machine was used in preparing the slurry. An example
of the PEEK slurry is shown in Figure 4.

The viscosity of the mixed slurry increases with a higher weight ratio of PEEK powder in the
mixture. When more powder is added, the mixed slurry will have a higher viscosity. Accordingly we can
classify the PEEK slurry into three groups.

(1) Slurry that can flow: When the ratio of the PEEK powder in the slurry is less than 27.5%, it is
observed that the slurry can flow to refill voids during the recoating process;
(2) Slurry that cannot flow but can attach to dipped surfaces when taking out: When the ratio
of the PEEK powder in the slurry is between 27.5% and 33.8%, it is observed that the slurry
cannot flow by itself but can attached to surfaces that are dipped into the slurry;
(3) Slurry that cannot flow or attach to dipped surfaces: When the ratio of the PEEK powder in
the slurry is over 33.8%, the mixture is similar to paste. It cannot flow or be spread out easily.
Further, it will not attach to dipped surfaces.
In our study, we also found that the stirring of the mixture becomes rather difficult when the weight
ratio of the PEEK powder is above 37%. It is possible to reduce the slurrys viscosity by adding chemical
solutions such as isopropanol; however, the material properties of the fabricated PEEK parts may also be
affected by the additional solutions. We only tested the PEEK slurry by directly mixing PEEK powder
with liquid resin in our study. A better slurry preparation approach is desired for achieving a higher
percentage of PEEK powder in the mixed slurry in the future research.

3. Green Part Fabrication

For each group of the slurry with different viscosities, we developed corresponding material refilling
strategies in the bottom-up MIP-SL process.
3.1 Fabricating green parts with slurry that can flow
For the slurry in the first group, we used the two channel system that was developed for liquid resin.
Since the slurry can flow by itself, the fabrication procedure in building green parts is similar to the one as
presented in [12], which is shown in Figure 34.

3.2 Fabricating green parts with slurry that can attach to dipped surfaces
For the slurry in the second group, the slurry cannot flow freely on the PDMS surface; however, it can
attach to dipped surfaces. We used a modified fabrication procedure as shown in Figure 6. After the build
part and the platform are moved rightward to the channel without the PDMS film (Step b). We move
them down by a certain distance d and dip into the slurry (step c). The attached slurry on both bottom and
side surfaces can bring certain amount of material that is adequate for building a new layer. Although the
amount of the material attached to the dipped surfaces requires more effort to model, it is observed that
more materials will be brought up if the distance d is larger. In addition, it was found that the dipped
material cannot be evenly spread out on the PDMS film when the platform was lowered to form one layer
thickness (step f). In order to fill the whole gap related to the next layer with slurry, an addition
rubbing mechanism is used in our fabrication procedure. As shown in step g and h, the part is moved
left and right to better spread the dipped material on the PDMS film.

Figure 37 shows a part that was built with and without extra rubbing motion. For a layer with a big area, the
lack of material will cause defects in the cured layer. Note that a previous layer that was incompletely built
will adversely affect all the following layers. The advantage of using rubbing mechanism is that the
material can be spread out evenly; however, a drawback is that small features on the part could be broken
during the rubbing movement.

3.3 Fabricating green parts with slurry that cannot flow or attach to dipped surfaces
For the slurry in the third group, it cannot flow freely nor attach to dipped surfaces. Instead, additional
spreading forces are required that can push the slurry into the formed gap related to a new layer. In our
experiments, we used a simple design as shown in Figure 38a for pushing the paste-like slurry. In the
design, we fill slurry in a closed tank that contains the platform inside. As shown in Figure 38b, the
slurry will be pushed to fill the region related to the next layer when the platform is moved back and
force.

Accordingly, a modified fabrication procedure is shown in Figure 39. As shown in the

illustration, the slurry in the enclosed tank is pushed between the left and right channels when the
platform is moved. Consequently, the slurry can be ensured to refill the left channel when the platform
is moved down to form a new layer. Note that there will be certain void generated in the tank during the
building process. This is because the platform is moved upward by a layer distance while the total
volume of the tank is fixed. To refill the void, additional slurry can be estimated and added into the tank
during the building process.

Figure 40 shows the building results of some test parts based on the developed pushing mechanism. As
shown in the testing results, the simple approach can ensure the uniform spreading of the slurry on the
PDMS film for forming thin layers (50 m used in the tests).

3.4 Cleaning procedures of green parts

Comparing to the MIP-SL process for liquid resin, the cleaning procedure for PEEK slurry is relatively
more difficult due to the higher viscosity value of the slurry. The procedures we used in our tests include
following steps with an example as shown in Figure 41.
(1) Remove the part from the platform and gently clean it with a soft paper napkin;
(2) Clean the part using an ultrasound cleaner filled with isopropyl alcohol for 10 minutes;
(3) Use an electric fan to dry the part and remove alcohol;
(4) Use a brush to clean any residue attached to part surfaces.
Steps (2)-(4) may be repeated if the part has some hard-to-clean features such as deep holes.

4. Sintering Process of Green Parts

The slurry-based MIP-SL process can build parts with the desired shapes defined by computer-aided
design (CAD) models. In this paper, we call such parts without heat treatment green parts. Since the
fabricated green parts may not have the desired material properties, we studied the sintering of green parts
and related material property changes.
o

PEEK is a semicrystalline thermoplastic with the glass transition temperature of ~143 C and the
o
melting point of ~343 C. In comparison, the photopolymer used in our study (SI500) has a glass
o
transition temperature of 61 C. Accordingly, the heat treatment procedure we designed is shown in
o
o
Figure 12. Various sintering temperatures ranging from 200 C to 320 C were set on the temperature
curve. During the sintering process, a furnace filled with nitrogen was used to avoid oxidation.

Figure 43a shows an example of the built green part and the related sintered part (sintering
o
temperature at 275 C). Figure 13b shows a set of gears that were sintered at different temperatures
o
o
ranging from 200 C to 320 C. Compared to the fabricated green part that is also shown in Figure 13b, the
o
dimensions of the sintered gears do not change much until ~300 C. When the sintering temperature is set
o
at 320 C, the green part shrinks significantly (~20%).

As discussed in [14], sintering is a physically complex phenomenon, which results in numerous

structural changes mass and significant improvement of its mechanical properties. The sintering
mechanism includes both surface and bulk transports. The initial stage of sintering mainly depends on
surface diffusion. During the stage, there is little shrinkage. In contrast, the intermediate and final stages
of sintering primarily depend on mass transport. A series of processes including interparticle bonding,
neck growth, pore channel closure, pore rounding, and pore shrinkage will happen during the stages.

The test results as shown in Figure 13b illustrate that:

o

(1) When the sintering temperature is 290 C, surface diffusion dominates the sintering of PEEK
composite. The sintered parts are dimensionally accurate;
o

(2) When the sintering temperature is >300 C, mass transport exists in the sintering process of
PEEK composite. Accordingly, the sintered part will shrink significantly.
Since large shrinkages are undesirable, the sintering temperatures in our material property study are
o
o
set from 200 C to 290 C.

VIII. Testing
5.
Material
Property
Sintered Parts

of

5.1 Tensile
test
We conducted tensile tests on the sintered parts. The tensile testing system we
used is a 5KN Deben Micro Tensile module that is shown in Figure 44. Tensile bars
with standard shapes and dimensions that are required by the testing machine were
built. A sample test bar is shown in Figure 15a. A microscope combined with high
resolution CCD was used to capture the shape changes of the tensile bar during the
test. Figure 45 shows some example images of a tensile bar before and after the
tensile test.

The strain-stress curves generated from the tensile tests are shown in Figure
46. The Youngs Modulus values of the related parts are shown in Table 1. It can be
observed that the PEEK composite after sintering becomes stronger yet more brittle
than the green part.

5.2 Hardness test

Hardness tests on the sintered parts were conducted using a ROCKWELL hardness
tester as shown in Figure 17. The scale of the hardness testing results is HRF. The
testing results are shown in Table 2. Based on the results, we can see that the
hardness of the built PEEK composite is affected by the sintering temperature. In
addition, the sintered parts are harder than the green part. They are also harder
than the part that is built in photocurable resin. In addition, the hardness of the
sintered parts generally increases for a higher sintering temperature within our
study range.

5.3
Scanning
microscope images

electron

A Hitachi field emission scanning electron microscope (SEM) was used in capturing
the micro-scale images of both the green and sintered parts. Figure 48 shows a
comparison of the captured SEM images. It can be observed that the boundary of
PEEK particles is obvious in the green part; however, it is difficult to distinguish the
o
PEEK particles in the sintered sample (sintering temperature at 260 C for 1 hour).
This verifies that the initial stage of sintering based on surface diffusion happens
during the heat treatment process. The surface diffusion can be between
neighboring PEEK particles and between PEEK particles and photocurable polymers.

The developed additive manufacturing process includes slurry preparation, green

part fabrication, and sintering. It is found that it is hard to generate mixed slurry
with more than
37% of PEEK powders in the mixture without using additional chemical solutions.
Hence the developed fabrication process will only be suitable for fabricating
components of PEEK composite instead of pure PEEK. Three different recoating
strategies have been developed for PEEK slurry with high viscosity values. The
developed approaches can also be used in fabricating other types of powder-resin
mixed slurry. We demonstrated that the sintering process can improve the
strength and hardness of the built green parts. In addition, the sintered PEEK
composite parts can have better material properties than those made in
photocurable polymers without any PEEK particles.
The MIP-SL process can fabricate components with complex shapes.