FKM

FKM (by ASTM D1418 standard) — equivalent to FPM by ISO/DIN 1629 standard — is the designation for about 80% of fluoroelastomers defined in ASTM D1418. Other fluorinated elastomers include perfluoro-elastomers (FFKM) and Tetrafluoroethylene propylene (FEPM) rubbers. All FKMs contain vinylidene fluoride as a monomer. Originally developed by DuPont under the brand name Viton, FKMs are now manufactured by Chemours and other global companies such as Daikin Chemical (Dai-El), 3M Dyneon, Solvay Specialty Polymers (Tecnoflon), HaloPolymer (Elaftor), and numerous Chinese manufacturers.

FKM materials, including viton o rings, are known for their superior resistance to high temperatures, aggressive chemicals, and oxidation. Although more expensive than neoprene or nitrile rubber elastomers, they are widely used where high temperature rubber gasket material is required.

FKMs can be categorized based on their Viton polymer types, chemical composition, fluorine content, or crosslinking mechanisms.

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 (HFP). Copolymers are the standard type of FKMs showing a good overall performance. Their fluorine content typically ranges around 66 weight percent.
• Type 2 FKMs are composed of VDF, HFP, and tetrafluoroethylene (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 perfluoromethylvinylether (PMVE). The addition of PMVE provides better low temperature flexibility compared to copolymers and terpolymers. Typically the fluorine content of type 3 FKMs ranges from 62 to 68 weight percent.
• Type 4 FKMs are composed of propylene, TFE, and VDF. While base resistance is increased in type 4 FKMs, their swelling properties especially in hydrocarbons 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 for enhanced base and hydrogen sulfide resistance. This makes them ideal for viton o rings in demanding applications where high temperature rubber gasket material is essential.

Crosslinking mechanisms

There are three established crosslinking mechanisms used in the curing process of FKMs.

• Diamine crosslinking using a blocked diamine. In the presence of basic media VDF is vulnerable to dehydrofluorination which enables the addition of the diamine to the polymer chain. Typically magnesium oxide is used to neutralize the resulting hydrofluoric acid and rearrange into magnesium fluoride and water. Although rarely used today, diamine curing provides superior rubber-to-metal bonding properties as compared with other crosslinking mechanisms. The diamine’s capability to be hydrated makes the diamine crosslink vulnerable in aqueous media.
• Ionic crosslinking (dihydroxy crosslinking) was the next step in curing FKMs. This is today the most common crosslinking 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. Dihydroxy aromatic compounds are used as the crosslinking agent and quaternary phosphonium salts are typically used to accelerate the curing process.
• Peroxide crosslinking was originally developed for type 3 FKMs containing PMVE as diamine and bisphenolic crosslinking systems can lead to cleavage in a polymer backbone containing PMVE. While diamine and bisphenolic crosslinking are ionic reactions, peroxide crosslinking is a free radical mechanism. Though peroxide crosslinks are not as thermally stable as bisphenolic crosslinks, they normally are the system of choice in aqueous and nonaqueous electrolytes.

FFKM

FFKM Performance and Application are superior to those of standard FKMs due to their high fluorine content. Classified under ASTM 1418 (ISO/DIN 1629: FFPM), FFKMs can withstand extreme chemical environments and continuous service temperatures up to 327°C (621°F). Some grades, such as Evolast®, operate in the range of -50°C to 340°C.

High temperature rubber gasket material requirements are often best met with FFKM components, especially in settings involving oxygen plasma, aggressive chemicals, or rapid thermal cycling.

For vacuum applications requiring ultra-low outgassing and particle emission, FFKM seals such as Kalrez 9100, SCVBR, or Perlast are custom-manufactured in cleanrooms. These seals are O-plasma cleaned and vacuum baked to achieve Teflon-like outgassing and FKM-level vacuum leak performance. This makes them ideal replacements for metal seals in UHV conditions—though they come at a premium compared to conventional viton o rings.