PEEK
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Polyether ether ketone (PEEK) is a colourless organic
thermoplastic A thermoplastic, or thermosoft 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 associate ...
polymer A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
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 bet ...
(PAEK) family, used in engineering applications. The polymer was first developed in November 1978, later being introduced to the market by Victrex PLC, then Imperial Chemical Industries (ICI) in the early 1980s.


Synthesis

PEEK polymers are obtained by step-growth polymerization by the di
alkylation Alkylation is the transfer of an alkyl group from one molecule to another. 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 effecti ...
of bis
phenolate Phenolates (also called phenoxides) are anions, salts, and esters of phenols. They may be formed by reaction of phenols with strong base. Properties Alkali metal phenolates, such as sodium phenolate hydrolyze in aqueous solution to form basic s ...
salts. Typical is the reaction of 4,4'-difluorobenzophenone 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. ...
with sodium carbonate. 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 hydro ...
solvents - such as diphenyl sulfone.


Properties

PEEK is a semicrystalline
thermoplastic A thermoplastic, or thermosoft 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 associate ...
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 E, the Young modulus, or the modulus of elasticity in tension or compression (i.e., negative tension), is a mechanical property that measures the tensile or compressive stiffness of a solid material when the force is applied le ...
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), a Roman coin of nearly solid gold * Solidus (punctuation), or slash, a punctuation mark * Solidus (chemistry), the line on a phase diagram below which a substance is completely solid * ...
temperature. It is highly resistant to
thermal degradation Thermal decomposition, or thermolysis, is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic as heat is req ...
, as well as to attack by both organic and aqueous environments. It is attacked by halogens and strong Brønsted 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 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 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 energy. Pumps can be classified into three major groups according to the method they ...
,
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 each component in a mixture. It relies on pumps to pa ...
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 fitting ...
, and
electrical cable An electrical cable is an assembly of one or more wires running side by side or bundled, which is used to carry electric current. One or more electrical cables and their corresponding connectors may be formed into a ''cable assembly'', whic ...
insulation. It is one of the few plastics compatible with
ultra-high vacuum Ultra-high vacuum (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 a gas molecule is greater than approximately ...
applications, which makes it suitable for aerospace, automotive, and chemical industries. PEEK is used in medical implants, 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 neurosurgical or orthopedic surgical technique that joins two or more vertebrae. This procedure can be performed at any level in the spine (cervical, thoracic, or lumbar) and pre ...
devices and reinforcing rods. It is radiolucent, 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 500 °F/260 °C). 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 called ''filament freeform fabrication'', is a 3D printing process that uses a continuous filament of a thermoplastic material. Filam ...
(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 or
extrusion Extrusion is a process used to create objects of a fixed cross-sectional profile by pushing material through a die of the desired cross-section. Its two main advantages over other manufacturing processes are its ability to create very complex ...
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 called ''filament freeform fabrication'', is a 3D printing process that uses a continuous filament of a thermoplastic material. Filam ...
– 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, and are supported by the surrounding soft and hard tissues of the oral cavity. Conventional dentures are removable ( removable partial denture o ...
. In its solid state PEEK is readily machinable, for example, by
CNC Numerical control (also computer numerical control, and commonly called CNC) is the automated control of machining tools (such as drills, lathes, mills, grinders, routers and 3D printers) by means of a computer. A CNC machine processes a p ...
milling machines Milling is the process of machining using rotary cutters to remove material by advancing a cutter into a workpiece. This may be done by varying direction on one or several axes, cutter head speed, and pressure. Milling covers a wide variety of d ...
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. P ...
; 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 ( alternatively spelt orthopaedics), is the branch of surgery concerned with conditions involving the musculoskeletal system. Orthopedic surgeons use both surgical and nonsurgical means to treat musculoskeletal ...
.


References

{{Plastics Polyethers Organic polymers Thermoplastics Fused filament fabrication