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Polyether ether ketone (PEEK) is a beige coloured
organic Organic may refer to: * Organic, of or relating to an organism, a living entity * Organic, of or relating to an anatomical organ Chemistry * Organic matter, matter that has come from a once-living organism, is capable of decay or is the product ...
thermoplastic A thermoplastic, or thermosoftening plastic, is any plastic polymer material that becomes pliable or moldable at a certain elevated temperature and solidifies upon cooling. Most thermoplastics have a high molecular weight. The polymer chains as ...
polymer A polymer () is a chemical substance, substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeat unit, repeating subunits derived from one or more species of monomers. Due to their br ...
in the
polyaryletherketone Polyaryletherketone (PAEK) is a family of semi-crystalline thermoplastics with high-temperature stability and high mechanical strength whose molecular backbone contains alternately ketone (R-CO-R) and ether groups (R-O-R). The linking group R betw ...
(PAEK) family, used in engineering applications. It was invented in November 1978 and brought to market in the early 1980s by part of Imperial Chemical Industries (ICI), the PEEK division was acquired through a management buyout, giving rise to Victrex PLC.


Synthesis

PEEK polymers are obtained by
step-growth polymerization In polymer chemistry, 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. Ma ...
by the di
alkylation Alkylation is a chemical reaction that entails transfer of an alkyl group. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effecting al ...
of bis
phenolate Phenolates (also called phenoxides) are anions, salt (chemistry), salts, and esters of phenols, containing the phenolate ion. They may be formed by reaction of phenols with strong base. Properties Alkali metal phenolates, such as sodium phenoxi ...
salts. Typical is the reaction of
4,4'-difluorobenzophenone 4,4’-Difluorobenzophenone is an organic compound with the formula of (FC6H4)2CO. This colorless solid is commonly used as a precursor to PEEK, or polyetherether ketone, a so-called high performance polymer. Because PEEK is resistant to attack, ...
with the disodium salt of
hydroquinone Hydroquinone, also known as benzene-1,4-diol or quinol, is an aromatic organic compound that is a type of phenol, a derivative of benzene, having the chemical formula C6H4(OH)2. It has two hydroxyl groups bonded to a benzene ring in a ''para' ...
, which is generated in situ by
deprotonation Deprotonation (or dehydronation) is the removal (transfer) of a proton (or hydron, or hydrogen cation), (H+) from a Brønsted–Lowry acid in an acid–base reaction.Henry Jakubowski, Biochemistry Online Chapter 2A3, https://employees.csbsju.ed ...
with
sodium carbonate Sodium carbonate (also known as washing soda, soda ash, sal soda, and soda crystals) is the inorganic compound with the formula and its various hydrates. All forms are white, odourless, water-soluble salts that yield alkaline solutions in water ...
. The reaction is conducted around 300 °C in polar
aprotic A polar aprotic solvent is a solvent that lacks an acidic proton and is polar. Such solvents lack hydroxyl and amine groups. In contrast to protic solvents, these solvents do not serve as proton donors in hydrogen bonding In chemistry, a hydr ...
solvents - such as
diphenyl sulfone Diphenyl sulfone is an organosulfur compound with the formula (C6H5)2SO2. It is a white solid that is soluble in organic solvents. It is used as a high temperature solvent. Such high temperature solvents are useful for processing highly rigid pol ...
.


Properties

PEEK is a semicrystalline
thermoplastic A thermoplastic, or thermosoftening plastic, is any plastic polymer material that becomes pliable or moldable at a certain elevated temperature and solidifies upon cooling. Most thermoplastics have a high molecular weight. The polymer chains as ...
with excellent mechanical and chemical resistance properties that are retained to high temperatures. The processing conditions used to mould PEEK can influence the crystallinity and hence the mechanical properties. Its
Young's modulus Young's modulus (or the Young modulus) is a mechanical property of solid materials that measures the tensile or compressive stiffness when the force is applied lengthwise. It is the modulus of elasticity for tension or axial compression. Youn ...
is 3.6 GPa and its tensile strength is 90 to 100 MPa. PEEK has a
glass transition temperature The glass–liquid transition, or glass transition, is the gradual and reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle "glassy" state into a viscous or rub ...
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 with temperature between room temperature and
solidus Solidus (Latin for "solid") may refer to: * Solidus (coin) The ''solidus'' (Latin 'solid'; : ''solidi'') or ''nomisma'' () was a highly pure gold coin issued in the Later Roman Empire and Byzantine Empire. It was introduced in the early ...
temperature. It is highly resistant to
thermal degradation Thermal decomposition, or thermolysis, is a chemical decomposition of a substance caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic ...
, as well as to attack by both organic and aqueous environments. It is attacked by halogens and strong Brønsted and
Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any ...
s, 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 form with a high surface-area-to-volume ratio, such as a fine powder or thin film. It has high resistance to biodegradation.


Applications

PEEK is used to fabricate items for demanding applications, including bearings,
piston A piston is a component of reciprocating engines, reciprocating pumps, gas compressors, hydraulic cylinders and pneumatic cylinders, among other similar mechanisms. It is the moving component that is contained by a cylinder (engine), cylinder a ...
parts,
pumps A pump is a device that moves fluids (liquids or gases), or sometimes slurries, by mechanical action, typically converted from electrical energy into hydraulic or pneumatic energy. Mechanical pumps serve in a wide range of applications such ...
,
high-performance liquid chromatography High-performance liquid chromatography (HPLC), formerly referred to as high-pressure liquid chromatography, is a technique in analytical chemistry used to separate, identify, and quantify specific components in mixtures. The mixtures can origin ...
columns, compressor plate
valves A valve is a device or natural object that regulates, directs or controls the flow of a fluid (gases, liquids, fluidized solids, or slurries) by opening, closing, or partially obstructing various passageways. Valves are technically fittings, ...
, and
electrical cable Electricity is the set of physical phenomena associated with the presence and motion of matter possessing an electric charge. Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as described by Maxwel ...
insulation Insulation may refer to: Thermal * Thermal insulation, use of materials to reduce rates of heat transfer ** List of insulation materials ** Building insulation, thermal insulation added to buildings for comfort and energy efficiency *** Insulated ...
. It is one of the few plastics compatible with
ultra-high vacuum Ultra-high vacuum (often spelled ultrahigh in American English, UHV) is the vacuum regime characterised by pressures lower than about . UHV conditions are created by pumping the gas out of a UHV chamber. At these low pressures the mean free path of ...
applications, which makes it suitable for aerospace, automotive, and chemical industries. PEEK is used in
medical implant An implant is a medical device manufactured to replace a missing biological structure, support a damaged biological structure, or enhance an existing biological structure. For example, an implant may be a rod, used to strengthen weak bones. Med ...
s, for example in creating a partial replacement skull in neurosurgical applications. PEEK is used in
spinal fusion Spinal fusion, also called spondylodesis or spondylosyndesis, is a surgery performed by Orthopedic surgery#Practice, orthopaedic surgeons or neurosurgeons that joins two or more vertebrae. This procedure can be performed at any level in the spine ...
devices and reinforcing rods. It is
radiolucent Radiodensity (or radiopacity) is opacity to the radio wave and X-ray portion of the electromagnetic spectrum: that is, the relative inability of those kinds of electromagnetic radiation to pass through a particular material. Radiolucency or hypod ...
, but it is hydrophobic causing it to not fully fuse with bone. PEEK seals and manifolds are commonly used in fluid applications. PEEK also performs well in high temperature applications (up to 260 °C/500 °F). Because of this and its low thermal conductivity, it is also used in
fused filament fabrication Fused filament fabrication (FFF), also known as fused deposition modeling (with the trademarked acronym FDM), or ''filament freeform fabrication'', is a 3D printing process that uses a continuous filament of a thermoplastic material. Filament is ...
(FFF) printing to thermally separate the hot end from the cold end.


Processing options

PEEK melts at a relatively high temperature (343 °C / 649.4 °F) compared to most other thermoplastics. In the range of its melting temperature it can be processed using
injection moulding Injection moulding (U.S. spelling: injection molding) is a manufacturing process for producing parts by injecting molten material into a mould, or mold. Injection moulding can be performed with a host of materials mainly including metals (for ...
or
extrusion Extrusion is a process used to create objects of a fixed cross section (geometry), cross-sectional profile by pushing material through a Die (manufacturing), die of the desired cross-section. Its two main advantages over other manufacturing pro ...
methods. It is technically feasible to process granular PEEK into filament form and 3D printing parts from the filament material using
fused deposition modeling Fused filament fabrication (FFF), also known as fused deposition modeling (with the trademarked acronym FDM), or ''filament freeform fabrication'', is a 3D printing process that uses a continuous filament of a thermoplastic material. Filament is ...
– FDM (or fused filament fabrication – FFF) technology. PEEK filaments have been demonstrated for producing medical devices up to class IIa. With this new filament, it is possible to use the FFF method for different medical applications like
dentures Dentures (also known as false teeth) are prosthetic devices constructed to replace missing teeth, supported by the surrounding soft and hard tissues of the oral cavity. Conventional dentures are removable ( removable partial denture or comp ...
. In its solid state PEEK is readily machinable, for example, by
CNC Computer numerical control (CNC) or CNC machining is the automated control of machine tools by a computer. It is an evolution of numerical control (NC), where machine tools are directly managed by data storage media such as punched cards or ...
milling machines Milling is the process of machining using rotary Milling cutter, cutters to remove material by advancing a cutter into a workpiece. This may be done by varying directions on one or several axes, cutter head speed, and pressure. Milling covers a w ...
and is commonly used to produce high-quality plastic parts that are thermostable and both electrically and thermally insulating. Filled grades of PEEK can also be CNC machined, but special care must be taken to properly manage stresses in the material. PEEK is a high-performance polymer, but its high price, due to its complex production process, restricts its use to only the most demanding applications.


Shape-memory PEEK in biomechanical applications

PEEK is not traditionally a
shape-memory polymer Shape-memory polymers (SMPs) are polymeric smart materials that have the ability to return from a deformed state (temporary shape) to their original (permanent) shape when induced by an external stimulus (trigger), such as temperature change. ...
; however, recent advances in processing have allowed shape-memory behaviour in PEEK with mechanical activation. This technology has expanded to applications in
orthopaedic surgery Orthopedic surgery or orthopedics (American and British English spelling differences, alternative spelling orthopaedics) is the branch of surgery concerned with conditions involving the musculoskeletal system. Orthopedic surgeons use both surgic ...
.


References

{{Plastics Polyethers Organic polymers Thermoplastics Fused filament fabrication