FKM is a family of
fluorocarbon
Fluorocarbons are chemical compounds with carbon-fluorine bonds. Compounds that contain many C-F bonds often have distinctive properties, e.g., enhanced stability, volatility, and hydrophobicity. Several fluorocarbons and their derivatives are ...
-based
fluoroelastomer
A fluoroelastomer is a fluorocarbon-based synthetic rubber. Fluoroelastomers generally have wide chemical resistance.
Composition
Several compositions of fluoroelastomers exist including FKM (by ASTM D1418 standard, equivalent to FPM by ISO/DIN ...
materials defined by
ASTM International
ASTM International, formerly known as American Society for Testing and Materials, is a standards organization that develops and publishes voluntary consensus technical international standards for a wide range of materials, products, systems and s ...
standard D1418 and
ISO standard 1629. It is commonly called fluorine rubber or fluoro-rubber. FKM is an abbreviation of Fluorine Kautschuk Material. All FKMs contain
vinylidene fluoride as the common
monomer
A monomer ( ; ''mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or two- or three-dimensional network in a process called polymerization.
Classification
Chemis ...
, to which different other monomers are added for specific types and functionalities, fitting the desired application.
Originally developed by
DuPont
Dupont, DuPont, Du Pont, duPont, or du Pont may refer to:
People
* Dupont (surname) Dupont, also spelled as DuPont, duPont, Du Pont, or du Pont is a French surname meaning "of the bridge", historically indicating that the holder of the surname re ...
(under the brand name Viton, now owned by
Chemours
The Chemours Company (, ) is an American chemical industry, chemical company that was founded in July 2015 as a Corporate spin-off, spin-off from DuPont. It has its corporate headquarters in Wilmington, Delaware, United States. Chemours is the m ...
), FKMs are today also produced by many other companies, including:
Daikin
is a Japanese multinational conglomerate company headquartered in Osaka. Daikin is the world's largest air conditioner manufacturer.
History
Daikin Industries Ltd was founded in 1924 as by Akira Yamada. In 1953, Daiflon or polychloro ...
(Dai-El),
3M (Dyneon),
Solvay S.A. (Tecnoflon),
HaloPolymer (Elaftor),
Gujarat Fluorochemicals
Gujarat Fluorochemicals Limited (GFL) is an industrial refrigerant manufacturer in India. It is one of the largest producers (by volume) of chloromethane, refrigerants and polytetrafluoroethylene (PTFE).
History
The company was incorporated ...
(Fluonox), and several Chinese manufacturers. Fluoroelastomers are more expensive than
neoprene
Neoprene (also polychloroprene) is a family of synthetic rubbers that are produced by polymerization of chloroprene.Werner Obrecht, Jean-Pierre Lambert, Michael Happ, Christiane Oppenheimer-Stix, John Dunn and Ralf Krüger "Rubber, 4. Emulsion Rub ...
or
nitrile rubber
Nitrile rubber, also known as nitrile butadiene rubber, NBR, Buna-N, and acrylonitrile butadiene rubber, is a synthetic rubber derived from acrylonitrile (ACN) and butadiene. Trade names include Perbunan, Nipol, Krynac and Europrene. This rubber is ...
elastomer
An elastomer is a polymer with viscoelasticity (i.e. both viscosity and elasticity) and with weak intermolecular forces, generally low Young's modulus (E) and high failure strain compared with other materials. The term, a portmanteau of ''ela ...
s. They provide additional heat and chemical resistance. FKMs can be divided into different classes on the basis of either their chemical composition, their
fluorine
Fluorine is a chemical element; it has Chemical symbol, symbol F and atomic number 9. It is the lightest halogen and exists at Standard temperature and pressure, standard conditions as pale yellow Diatomic molecule, diatomic gas. Fluorine is extre ...
content, or their
cross-link
In chemistry and biology, a cross-link is a bond or a short sequence of bonds that links one polymer chain to another. These links may take the form of covalent bonds or ionic bonds and the polymers can be either synthetic polymers or natural ...
ing mechanism.
Types
On the basis of their chemical composition FKMs can be divided into the following types:
* Type-1 FKMs are composed of
vinylidene fluoride (VDF) and
hexafluoropropylene
Hexafluoropropylene is the fluoroalkene with the formula CF3CF=CF2. It is the perfluorocarbon counterpart to the hydrocarbon propylene. It is mainly used to produce copolymers with tetrafluoroethylene. Hexafluoropropylene is used as a chemical i ...
(HFP).
Copolymer
In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are som ...
s are the standard type of FKMs showing a good overall performance. Their fluorine content is approximately 66 weight percent.
* Type-2 FKMs are composed of VDF, HFP, and
tetrafluoroethylene
Tetrafluoroethylene (TFE) is a fluorocarbon with the chemical formula . It is a colorless gas. Its structure is . It is used primarily in the industrial preparation of fluoropolymers. It is the simplest perfluorinated alkene.
It was first repor ...
(TFE). Terpolymers have a higher fluorine content compared to copolymers (typically between 68 and 69 weight percent fluorine), which results in better chemical and heat resistance. Compression set and low temperature flexibility may be affected negatively.
* Type-3 FKMs are composed of VDF, TFE, and
perfluoro(methyl vinyl ether)
Perfluoro(methyl vinyl ether) is a perfluorinated compound used as a precursor to fluoropolymers. It is the simplest unsaturated perfluoroether.
Preparation
Preparation begins with hexafluoropropylene oxide (HFPO) and carbonyl fluoride over ...
(PMVE). The addition of PMVE provides better low temperature flexibility compared to copolymers and
terpolymer
In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are som ...
s. Typically, the fluorine content of type-3 FKMs ranges from 62 to 68 weight percent.
* Type-4 FKMs are composed of
propylene
Propylene, also known as propene, is an unsaturated organic compound with the chemical formula . It has one double bond, and is the second simplest member of the alkene class of hydrocarbons. It is a colorless gas with a faint petroleum-like o ...
, TFE, and VDF. While base resistance is increased in type-4 FKMs, their swelling properties, especially in
hydrocarbon
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and Hydrophobe, hydrophobic; their odor is usually fain ...
s, are worsened. Typically, they have a fluorine content of about 67 weight percent.
* Type-5 FKMs are composed of VDF, HFP, TFE, PMVE, and
ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon–carbon bond, carbon–carbon doub ...
. Known for
base resistance and high-temperature resistance to
hydrogen sulfide
Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is toxic, corrosive, and flammable. Trace amounts in ambient atmosphere have a characteristic foul odor of rotten eggs. Swedish chemist ...
.
Cross-linking mechanisms
There are three established
cross-link
In chemistry and biology, a cross-link is a bond or a short sequence of bonds that links one polymer chain to another. These links may take the form of covalent bonds or ionic bonds and the polymers can be either synthetic polymers or natural ...
ing mechanisms used in the curing process of FKMs.
*
Diamine
A diamine is an amine with two amino groups. Diamines are used as monomers to prepare polyamides, polyimides, and polyureas. The term ''diamine'' refers mostly to Primary (chemistry), primary diamines, as those are the most reactive.
In terms of ...
cross-linking using a blocked diamine. In the presence of basic (alkaline) media, VDF is vulnerable to
dehydrofluorination
In chemistry, dehydrohalogenation is an elimination reaction which removes a hydrogen halide from a substrate. The reaction is usually associated with the synthesis of alkenes, but it has wider applications.
Dehydrohalogenation from alkyl hali ...
, which enables the addition of the diamine to the polymer chain. Typically,
magnesium oxide
Magnesium oxide (MgO), or magnesia, is a white hygroscopic solid mineral that occurs naturally as periclase and is a source of magnesium (see also oxide). It has an empirical formula of MgO and consists of a lattice of Mg2+ ions and O2− ions ...
is used to neutralize the resulting
hydrofluoric acid
Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48–52%) but there are also stronger solutions (e.g. 70%) and pure HF has a boiling p ...
and rearrange into
magnesium fluoride
Magnesium fluoride is an ionically bonded inorganic compound with the formula . The compound is a colorless to white crystalline salt and is transparent over a wide range of wavelengths, with commercial uses in optics that are also used in space ...
and water. Although rarely used today, diamine curing provides superior rubber-to-metal
bonding properties as compared with other cross-linking mechanisms. The diamine's capability to be hydrated makes the diamine cross-link vulnerable in aqueous media.
* Ionic cross-linking (
dihydroxy cross-linking) was the next step in curing FKMs. This is today the most common cross-linking chemistry used for FKMs. It provides superior heat resistance, improved hydrolytic stability and better compression set than diamine curing. In contrast to diamine curing, the ionic mechanism is not an addition mechanism but an aromatic
nucleophilic substitution
In chemistry, a nucleophilic substitution (SN) is a class of chemical reactions in which an electron-rich chemical species (known as a nucleophile) replaces a functional group within another electron-deficient molecule (known as the electrophile) ...
. Dihydroxy
aromatic compound
Aromatic compounds or arenes are organic compounds "with a chemistry typified by benzene" and "cyclically conjugated."
The word "aromatic" originates from the past grouping of molecules based on odor, before their general chemical properties were ...
s are used as the cross-linking agent, and
quaternary
The Quaternary ( ) is the current and most recent of the three periods of the Cenozoic Era in the geologic time scale of the International Commission on Stratigraphy (ICS), as well as the current and most recent of the twelve periods of the ...
phosphonium salt
In chemistry, the term phosphonium (more obscurely: phosphinium) describes polyatomic cations with the chemical formula (where R is a hydrogen or an alkyl, aryl, organyl or halogen group). These cations have tetrahedral structures. The salt ...
s are typically used to accelerate the curing process.
*
Peroxide
In chemistry, peroxides are a group of Chemical compound, compounds with the structure , where the R's represent a radical (a portion of a complete molecule; not necessarily a free radical) and O's are single oxygen atoms. Oxygen atoms are joined ...
cross-linking was originally developed for type 3 FKMs containing PMVE as diamine and
bisphenol
The bisphenols () are a group of industrial chemical compounds related to diphenylmethane; commonly used in the creation of plastics and epoxy resins. Most are based on two phenols, hydroxyphenyl functional groups linked by a methylene bridge. Ex ...
ic cross-linking systems can lead to
cleavage
Cleavage may refer to:
Science
* Cleavage (crystal), the way in which a crystal or mineral tends to split
* Cleavage (embryo), the division of cells in an early embryo
* Cleavage (geology), foliation of rock perpendicular to stress, a result of ...
in a polymer
backbone chain
In polymer science, the polymer chain or simply backbone of a polymer is the main chain of a polymer. Polymers are often classified according to the elements in the main chains. The character of the backbone, i.e. its flexibility, determines the ...
containing PMVE. While diamine and bisphenolic cross-linking are
ionic reaction
Ionic bonding is a type of chemical bonding that involves the electrostatic attraction between oppositely charged ions, or between two atoms with sharply different electronegativities, and is the primary interaction occurring in ionic compounds. ...
s, peroxide cross-linking is a
free-radical
In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired valence electron.
With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spont ...
mechanism. Though peroxide cross-links are not as thermally stable as bisphenolic cross-links, they normally are the system of choice in aqueous media and nonaqueous
electrolyte
An electrolyte is a substance that conducts electricity through the movement of ions, but not through the movement of electrons. This includes most soluble Salt (chemistry), salts, acids, and Base (chemistry), bases, dissolved in a polar solven ...
media.
Properties
Fluoroelastomers provide excellent high temperature (up to 500°F or 260°C) and aggressive fluids resistance when compared with other
elastomers
An elastomer is a polymer with viscoelasticity (i.e. both viscosity and Elasticity (physics), elasticity) and with weak intermolecular forces, generally low Young's modulus (E) and high failure strain compared with other materials. The term, a ...
, while combining the most effective stability to many sorts of chemicals and fluids such as oil,
diesel,
ethanol
Ethanol (also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound with the chemical formula . It is an Alcohol (chemistry), alcohol, with its formula also written as , or EtOH, where Et is the ps ...
mix or body fluid.
The performance of fluoroelastomers in aggressive chemicals depends on the nature of the base polymer and the compounding ingredients used for molding the final products (e.g.
o-rings
An O-ring, also known as a packing or a toric joint, is a mechanical gasket in the shape of a torus; it is a loop of elastomer with a round cross-section, designed to be seated in a groove and compressed during assembly between two or more part ...
). Some formulations are generally compatible with
hydrocarbons
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic; their odor is usually faint, and may b ...
, but incompatible with
ketones
In organic chemistry, a ketone is an organic compound with the structure , where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group (a carbon-oxygen double bond C=O). The simplest ketone is acetone ( ...
such as
acetone
Acetone (2-propanone or dimethyl ketone) is an organic compound with the chemical formula, formula . It is the simplest and smallest ketone (). It is a colorless, highly Volatile organic compound, volatile, and flammable liquid with a charact ...
and
methyl ethyl ketone
Butanone, also known as methyl ethyl ketone (MEK) or ethyl methyl ketone, is an organic compound with the formula CH3C(O)CH2CH3. This colorless liquid ketone has a sharp, sweet odor reminiscent of acetone. It is produced industrially on a large s ...
,
ester
In chemistry, an ester is a compound derived from an acid (either organic or inorganic) in which the hydrogen atom (H) of at least one acidic hydroxyl group () of that acid is replaced by an organyl group (R). These compounds contain a distin ...
solvents such as
ethyl acetate
Ethyl acetate commonly abbreviated EtOAc, ETAC or EA) is the organic compound with the formula , simplified to . This flammable, colorless liquid has a characteristic sweet smell (similar to pear drops) and is used in glues, nail polish removers, ...
,
amines
In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...
, and
organic acids
An organic acid is an organic compound with acidic properties. The most common organic acids are the carboxylic acids, whose acidity is associated with their carboxyl group –COOH. Sulfonic acids, containing the group –SO2OH, are r ...
such as
acetic acid
Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main compone ...
.
They can be easily distinguished from many other elastomers because of their high
density
Density (volumetric mass density or specific mass) is the ratio of a substance's mass to its volume. The symbol most often used for density is ''ρ'' (the lower case Greek letter rho), although the Latin letter ''D'' (or ''d'') can also be u ...
of over 1800 kg/m
3, significantly higher than most types of rubber.
Applications
Because of their outstanding performance they find use in a number of sectors, including the following:
* Chemical process and
petroleum refining
An oil refinery or petroleum refinery is an industrial process plant where petroleum (crude oil) is transformed and refined into products such as gasoline (petrol), diesel fuel, asphalt base, fuel oils, heating oil, kerosene, liquefied petr ...
, where they are used for seals, pumps, gaskets and so on, due to their resistance to chemicals;
* Analysis and process instruments: separators, diaphragms, cylindrical fittings, hoops, gaskets, etc.
*
Semiconductor
A semiconductor is a material with electrical conductivity between that of a conductor and an insulator. Its conductivity can be modified by adding impurities (" doping") to its crystal structure. When two regions with different doping level ...
manufacturing;
* Food and pharmaceutical, because of their low degradation, also in contact with fluids;
*
Aviation
Aviation includes the activities surrounding mechanical flight and the aircraft industry. ''Aircraft'' include fixed-wing and rotary-wing types, morphable wings, wing-less lifting bodies, as well as lighter-than-air aircraft such as h ...
and
aerospace
Aerospace is a term used to collectively refer to the atmosphere and outer space. Aerospace activity is very diverse, with a multitude of commercial, industrial, and military applications. Aerospace engineering consists of aeronautics and astron ...
: high operating temperatures and high altitudes require superior heat and low-temperature resistance.
They are suitable for the production of wearables, due to low wear and discoloration even during prolonged lifetimes in contact with skin oils and frequent exposure to light, while guaranteeing high comfort and stain resistance;
The
automotive industry
The automotive industry comprises a wide range of company, companies and organizations involved in the design, Business development, development, manufacturing, marketing, selling, Maintenance, repairing, and Custom car, modification of motor ve ...
represents their main application sector, where constant reach for higher efficiencies push manufacturers towards high-performing materials. An example are FKM o-rings used as an upgrade to the original neoprene seals on Corvair pushrod tubes that deteriorated under the high heat produced by the engine, allowing oil leakage. FKM tubing or lined hoses are commonly recommended in automotive and other transportation fuel applications when high concentrations of biodiesel are required. Studies indicate that types B and F (FKM- GBL-S and FKM-GF-S) are more resistant to acidic biodiesel. (This is because biodiesel fuel is unstable and oxidizing.)
FKM O-rings have been used safely for some time in
scuba diving
Scuba diving is a Diving mode, mode of underwater diving whereby divers use Scuba set, breathing equipment that is completely independent of a surface breathing gas supply, and therefore has a limited but variable endurance. The word ''scub ...
by divers using gas blends referred to as
nitrox
Nitrox refers to any gas mixture composed (excepting trace gases) of nitrogen and oxygen. It is usually used for mixtures that contain less than 78% nitrogen by volume. In the usual application, underwater diving, nitrox is normally distinguished ...
. FKMs are used because they have a lower probability of catching fire, even with the increased percentages of oxygen found in nitrox. They are also less susceptible to decay under increased oxygen conditions.
While these materials have a wide range of applications, their cost is prohibitive when compared to other types of elastomers, meaning that their adoption must be justified by the need for outstanding performance (as in the aerospace sector) and is inadvisable for low-cost products.
FKM rubber is widely used in the watch strap industry due to its superior resistance to chemicals, extreme temperatures, and wear. It is commonly found in premium aftermarket watch straps, offering durability and a comfortable fit.
FKM/butyl gloves are highly impermeable to many strong organic solvents that would destroy or permeate commonly used gloves (such as those made with
nitrile
In organic chemistry, a nitrile is any organic compound that has a functional group. The name of the compound is composed of a base, which includes the carbon of the , suffixed with "nitrile", so for example is called " propionitrile" (or pr ...
s).
Precautions
At high temperatures or in a fire, fluoroelastomers decompose and may release
hydrogen fluoride
Hydrogen fluoride (fluorane) is an Inorganic chemistry, inorganic compound with chemical formula . It is a very poisonous, colorless gas or liquid that dissolves in water to yield hydrofluoric acid. It is the principal industrial source of fluori ...
. Any residue must be handled using protective equipment.
See also
*
Magnesium/Teflon/Viton
*
FFKM
FFKMs (by ASTM 1418 standard) (equivalent to FFPMs by ISO/DIN 1629 standard) are perfluoroelastomeric compounds containing an even higher amount of fluorine than FKM fluoroelastomers.
They have improved resistance to high temperatures and chemic ...
, perfluoro-elastomers
*
FEPM, tetrafluoro ethylene/propylene elastomers
*
PVDF
Polyvinylidene fluoride or polyvinylidene difluoride (PVDF) is a highly non-reactive thermoplastic fluoropolymer produced by the polymerization of vinylidene difluoride. Its chemical formula is (C2H2F2)''n''.
PVDF is a specialty plastic used ...
, polyvinylidene fluoride
References
*
* Overview of different types and their applications.
External links
Properties of Elastomers - Chemical Resitancelist(PDF; 0,6 MB)
Designing with Fluoroelastomers(PDF; 0,8 MB)
{{DEFAULTSORT:FKM
Organofluorides
Elastomers
Materials science
Fluoropolymers