Fluorine-containing elastomer compositions including microdiamond

Abstract

This paper discloses a curable fluoropolymer composition comprising at least one curable fluoropolymer, having at least one fluorinated monomer and at least one fluorinated curing monomer containing at least one curing site; at least one curing agent; and microdiamond particles having an average particle size of greater than 0.1 micrometers to about 100 micrometers. This composition can be fluorinated or perfluorinated. Articles formed from the composition described herein can be used at high operating temperatures and exhibit one or more of the following: reduced microparticle formation, reduced high-temperature compression set, reduced adhesion, enhanced resistance to fluorinated plasmas, oxygen plasmas, hydrogen plasmas, and combinations thereof, and improved physical properties.

Description

[Technical Field] This invention relates to fluoroelastomer compositions comprising microdiamond fillers to provide one or more of the following properties: reduced microparticle formation, reduced high-temperature compression set, reduced adhesion, enhanced plasma resistance in fluorinated, oxygen-based, hydrogen-based, and mixtures of such plasmas, ability to operate at high temperatures, and improved physical properties. Cross-reference to related applications. Pursuant to 35 USC §119(e), this U.S. non-provisional patent application claims priority to U.S. Provisional Patent Application No. 62 / 891,865, filed August 26, 2019, entitled "Fluorine-containing composition comprising microdiamonds," the entire disclosure of which is incorporated herein by reference. [Previous Technology] Fluorinated elastomers, including fluoroelastomers (FKM), perfluoroelastomers (FFKM), and blends comprising tetrafluoroethylene (TFE) and other partially or fully fluorinated monomers, are known for their chemical resistance, solvent resistance, and heat resistance, and are therefore widely used in sealing and other materials for harsh environments. The required characteristics of these materials are highly specific to their end applications, and the demand for highly resistant compounds continues to increase, particularly for FFKM compounds used in semiconductors and other "clean" methods that avoid contamination. In the aerospace, semiconductor, and chemical and pharmaceutical manufacturing industries, where sealing properties are required in harsh chemical environments and may withstand extremely high temperatures of at least 350°C, the ability of these materials to withstand such high temperatures and / or harsh chemicals such as oxygen-based plasmas, fluorinated plasmas, and / or hydrogen-based plasmas has become increasingly important. Therefore, this technology requires the development of elastomers that simultaneously attempt to reduce seal atomization, reduce compression set (especially at higher operating temperatures), enhance plasma resistance, reduce adhesion, and improve physical properties. There is a ongoing need in this technology to develop elastomeric sealing compositions that can achieve this capability and operate in such harsh environments. The goal is to use this excellent, high-temperature resistant, and environmentally resistant material to form molded components, such as seals and gaskets, that can withstand deformation and retain their shape under such severe loads. While strength and other physical properties may benefit from the addition of fillers, additives typically negatively impact compression set and other elastomeric sealing properties. Therefore, a careful balance must be struck between the filler used to achieve sufficient strength, the ability to withstand harsh conditions, and the maintenance of adequate sealing properties such as reasonably low compression set. FFKM materials are typically prepared from perfluorinated monomers, including at least one perfluorinated curing site monomer with functional groups containing curing sites. The monomers are polymerized to form a curable perfluorinated polymer with curing sites, which crosslinks upon reaction with a curing agent. During curing (crosslinking), the material forms an elastomer. A typical FFKM composition includes a perfluorinated polymer, a curing agent that reacts with the reactive curing site groups on the curing site monomer, and any desired filler. The resulting cured perfluorinated elastomer exhibits elastomer characteristics. FFKMs typically also include one or more perfluorinated monomers, but non-perfluorinated monomers such as vinylidene fluoride can also be incorporated, serving as both monomers and curing sites. FFKM and / or FKM are commonly known as O-rings and related sealing components for high-end sealing applications. FFKM is particularly sought after due to its high heat resistance, plasma resistance, chemical resistance, and tolerance to other harsh environments. There is a continuous need to develop novel perfluoroelastomer compositions to meet increasing demands and challenges, providing higher levels of heat, chemical, and / or plasma resistance, and developing suitable physical properties for various end applications. Efforts are ongoing to reduce micronization and maintain or reduce compression set (especially at high temperatures and lower adhesion). Industry demands, particularly in the semiconductor sector, continue to require enhanced performance in these seals to meet increasingly demanding environmental requirements and lower contamination and micronization requirements for novel end-use applications, while maintaining the sealing properties and physical strength of the elastomer. Therefore, there is always a need for better properties using low-micronization compounds, i.e., those that introduce little or no harmful contamination into the end-use environment. In the prior art, fillers and filler combinations used to achieve the desired properties and elastomer properties include both inorganic and organic fillers. Typical fillers known in the semiconductor and other industries include carbon black, silicon dioxide, alumina, TFE-based fluoroplastics, barium sulfate, fluorinated graphite, nanodiamonds, treated carbon, and other polymers and plastics. Fillers used in some FFKM compositions for semiconductor applications include various fluoroplastic filler particles formed from polytetrafluoroethylene (PTFE) or perfluorinated copolymers such as copolymers of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) (also known as FEP-type copolymers) or copolymers of TFE and perfluoroalkyl vinyl ethers (PAVE) (known as PFA-type copolymers). Such FFKM and / or FKM compositions may comprise only a single curable polymer, or sometimes a blend of one or more such curable polymers. Fluorinated elastomers are also available, which have a single curing site on a curing site monomer in a curable perfluoropolymer used in the composition, or have more than one curing site monomer having the same or different curing sites. There are many potential combinations of materials that can be used, and the challenge is to achieve higher heat resistance, chemical resistance, and plasma resistance for a variety of end applications, as well as better improvements to these properties, without sacrificing mechanical and sealing properties such as compression set and improving upon them. An attempt to introduce plasma-resistant properties can be found in U.S. Patent Application Publication No. 2009 / 0023852 A1, which describes a fluorinated elastomer composition for preparing molded articles with small weight changes when exposed to NF3, O2, and CF4 plasmas. The composition includes a fluorinated elastomer and a nano-sized carbon allotrope with an average particle size of up to 0.1 micrometers; the allotrope may be diamond. This disclosure teaches that particle sizes larger than 0.1 micrometers can cause problems and affect semiconductor defect rates, showing that if individual particles in the filler have a size larger than 0.1 micrometers, the filler should be further pulverized to produce a smaller size. U.S. Patent No. 6,946,513 B2 provides an elastomeric composition prepared using clean fillers, suitable as a molding material for semiconductor manufacturing apparatuses. The filler may be a carbon filler, such as carbon black, graphitized carbon black, or graphite. The filler may be in particle or fiber form, wherein the particle size is preferably no greater than 5 micrometers. U.S. Patent No. 9,725,582 B2 provides a fluoropolymer composition for use in molded products, exhibiting excellent tensile strength. The fluoropolymer composition comprises a fluoropolymer and fluorinated nanodiamonds present in a mass ratio of 0.001 to 5% based on the fluoropolymer. The fluorinated nanodiamonds are described as powders having an average particle size of 0.001 to 1 micrometer. International Patent Publication WO 2016 / 104604 A1 describes a fluorinated elastomer composition for forming molded articles with improved chemical resistance, solvent resistance, and heat resistance. The sealing material also exhibits improved plasma resistance and can be used in the working chamber of a semiconductor manufacturing apparatus. The composition comprises a fluorinated elastomer having 0.0001-4 parts by mass of fullerene relative to 100 parts by mass of the fluorinated elastomer. U.S. Patent No. 9,512,302 B2 provides a fluoropolymer coating with improved tribological properties. In one embodiment, the invention relates to a slurry composition of a fluoropolymer and nanodiamond particles with specific properties. The nanodiamond particles may be in single or aggregate form, and the particle size is preferably between 0.008 micrometers and 0.030 micrometers. The concentration of nanodiamond particles in the slurry is at most 5% by weight. Despite the above, prior art has attempted to integrate highly plasma-resistant carbon-based fillers into fluoroelastomers and perfluoroelastomers because such materials lack resin strength. The use of high-strength particles such as nanodiamonds has been shown to be disadvantageous when particle size increases due to defect rates, which are typically related to micronization or other factors, and are also considered unsuitable for providing strength without sacrificing the excellent elastomer properties of such materials. Therefore, there remains a need in the art to obtain sufficient physical properties, or to improve them while maintaining the elastomer's sealing properties and enhancing its resistance to harsh plasma environments. [Summary of the Invention] The present invention includes a curable fluoroelastomer composition comprising at least one curable fluoropolymer containing at least one fluorinated monomer, and at least one fluorinated curing monomer containing at least one curing site; and microdiamond particles having an average particle size of greater than 0.10 micrometers to about 100 micrometers. In one specific example, the microdiamond particles may have an average particle size of greater than 0.1 micrometers to about 10 micrometers, or an average particle size of about greater than 0.1 micrometers to about 5 micrometers. The average particle size of the microdiamonds may also be about 0.20 micrometers to about 2 micrometers, or about 0.25 micrometers to about 1 micrometer. In another specific example, the microdiamond particles may have an average particle size of about 0.25 micrometers to about 0.5 micrometers. The microdiamond particles may have a shape selected from spherical particles, fibers, or flasks. The microdiamond particles may be natural and / or synthetic microdiamond particles. The particles may exist in the form of agglomerated aggregates or clusters. In one specific example, the composition comprises about 0.1 to about 100 parts by weight of at least one curable fluoropolymer with microdiamond particles per 100 parts by weight, more preferably about 1 to about 50 parts by weight of at least one curable fluoropolymer with microdiamond particles per 100 parts by weight. More preferably, the composition comprises about 2 to about 20 parts by weight of at least one curable fluoropolymer with microdiamond particles per 100 parts by weight. At least one curable fluoropolymer may be a curable perfluoropolymer, wherein at least one fluorinated monomer is tetrafluoroethylene and the perfluoropolymer may further contain a perfluoroalkyl vinyl ether monomer, and at least one fluorinated curing site monomer may be a perfluorinated curing site monomer. In another specific example, at least one curable fluoropolymer may be a curable perfluoropolymer, at least one fluorinated monomer may be tetrafluoroethylene, the curable perfluoropolymer may further contain a perfluoroalkyl vinyl ether monomer, and the curable perfluoropolymer may contain fluoroplastic particles. In each specific example of the composition described above, the composition may also contain at least one curing agent, which may be added to the fluoroelastomer composition prior to curing the composition. In one specific example, the at least one curing agent may be a peroxide curing system. The curable fluoropolymer may also be a first perfluoropolymer, wherein at least one fluorinated monomer is tetrafluoroethylene and the perfluoropolymer further comprises a perfluoroalkyl vinyl ether monomer, and wherein at least two fluorinated curing site monomers are present, each having at least one curing site, and the composition includes two or more curing agents, one of which may be a peroxide curing system. In such a specific example, the curable fluorinated elastomer composition may comprise a blend of this curable perfluoropolymer and a second curable perfluoropolymer comprising tetrafluoroethylene, a second perfluoroalkyl vinyl ether monomer, and a perfluorinated curing site monomer, wherein the second perfluoropolymer contains fluoroplastic particles and also contains at least two curing agents, one of which may be a peroxide curing system. In specific examples of such blended fluoropolymers, the weight percentage of the first curable perfluoropolymer to the weight percentage of the second curable perfluoropolymer can range from about 5:95 to about 95:5, about 20:80 to about 80:20, about 40:60 to about 60:40, or about 50:50. In this specific example, the amount of each of the at least two curing site monomers of the first curable perfluoropolymer in the first curable perfluoropolymer may be from about 0.1 to about 10 moles, and the amount of at least one curing site monomer of the second curable perfluoropolymer in the second curable perfluoropolymer may be from about 0.1 to about 10 moles. Furthermore, the curing site of the at least two curing site monomers in the first curable perfluoropolymer may be a nitrogen-containing curing site. In this case, the first curable perfluoropolymer may comprise a first curing site monomer containing a primary cyano curing site and a second curing site monomer containing a secondary cyano curing site. In a specific example of blending, at least one of the at least two curing sites of the monomer in the first curable perfluoropolymer may be selected from the group consisting of cyano, carboxyl, carbonyl, alkoxycarbonyl and combinations thereof. In the methods described above, the method may also include adding at least one curing agent to the fluoroelastomer composition prior to curing the composition, and in a preferred embodiment, including at least two curing agents. Furthermore, the at least two curing agents are present in the blended composition in a total amount of about 0.2 to about 10 parts by weight of the curable perfluoropolymer per 100 parts by weight of the composition. In this embodiment, each of the at least two curing agents is present in the composition in an amount of about 0.1 parts by weight to about 6 parts by weight of the curable perfluoropolymer per 100 parts by weight. In another blending embodiment, the at least two curing agents may comprise a first curing agent present in the composition in an amount of about 0.5 parts by weight to about 4 parts by weight of the curable perfluoropolymer per 100 parts by weight, and a second curing agent present in the composition in an amount of about 0.3 parts by weight to about 2 parts by weight of the curable perfluoropolymer per 100 parts by weight. In a specific example, the first curing agent is [Figure] (XII) and the second curing agent is [Figure], wherein each R1 is independently -NH2, -NHR2, -OH, or -SH; R2 is a monovalent organic group; and R6 is -SO2, -O-, -CO-, an alkylene group of 1 to 6 carbon atoms, a perfluoroalkylene group of 1 to 10 carbon atoms, a single bond, or a group as described in formula (IX): [Figure] In another specific example, the second curing agent is a compound according to formula (X): [Figure] wherein R7 is independently selected from hydrogen, alkyl groups of 1 to about 10 carbon atoms; partially fluorinated or perfluorinated alkyl groups of 1 to 10 carbon atoms; phenyl; benzyl; or fluorinated or partially fluorinated phenyl; fluorinated or partially fluorinated benzyl; or phenyl or alkyl groups having a functional group of low carbon alkyl or perfluoroalkyl. In another preferred embodiment, the second curing agent may be diaminophenol or a salt thereof. The second curable perfluoropolymer may also contain curing site monomers having curing sites selected from the group consisting of halogen, nitrogen-containing groups, carboxyl groups, alkoxy carbonyl groups, and combinations thereof. In another preferred embodiment, at least two curing agents are selected from the group consisting of: [Figure] (XII), diaminophenol and combinations thereof. In another preferred embodiment, the first curing agent may be a compound according to formula (XII) and the second curing agent may be diaminophenol. In one specific example of the curable fluorinated elastomer composition of the present invention, the composition may include a second curable fluoropolymer comprising tetrafluoroethylene and at least one second fluorinated monomer, one of which is a curing site monomer comprising at least one second curing site. In this specific example, the first curable fluoropolymer and / or the second curable fluoropolymer may be perfluoropolymers, and the first curable fluoropolymer and the second curable fluoropolymer are preferably different. The present invention further includes a cured fluorinated elastomer, which is formed by curing the curable fluorinated composition described above. The present invention also includes molded articles, which are formed by heating, curing and molding the above-described components. The present invention further includes a method for forming a fluoroelastomer article with reduced microparticle size, comprising: preparing a curable fluoroelastomer composition comprising at least one curable fluoropolymer containing at least one fluorinated monomer, and at least one fluorinated curing site monomer containing at least one curing site; adding microdiamond particles having an average particle size of greater than 0.10 micrometers to about 100 micrometers to the curable fluoroelastomer composition; and curing the curable fluoroelastomer composition to form a fluoroelastomer article, wherein when the fluoroelastomer article and a second fluoroelastomer article are exposed to fluorinated plasma, oxygen plasma, hydrogen plasma, and combinations thereof, the fluoroelastomer article exhibits reduced microparticle size compared to a second fluoroelastomer article having the same fluoroelastomer composition but not including microdiamond particles. In this method, the curable fluoroelastomer composition may further include at least one filler, and the method may further include adding microdiamond particles to the fluoroelastomer composition while adding at least one filler to at least one first curable fluoropolymer. In the methods described above, at least one curable fluoropolymer may be a perfluoropolymer, the fluorinated monomer may be tetrafluoroethylene, at least one fluorinated curing site monomer may be a perfluorinated curing site monomer, and the perfluoropolymer may additionally contain perfluoroalkyl vinyl ethers. In the methods described above, the method may also include adding a curing agent to the fluorinated elastomer composition before curing the composition. In the method, the fluoroelastomer article preferably also has a compression set value of 250°C / 70 hours / 25% reduction in deformation compared to the second fluoroelastomer article. In this specific example, the curable fluoroelastomer composition used to form the second fluoroelastomer article may additionally include carbon black filler. In the method, the fluoroelastomer article preferably also has reduced adhesion compared to the second fluoroelastomer article. In this specific example, the curable fluoroelastomer composition used to form the second fluoroelastomer article may additionally include carbon black filler. In the method, the fluoroelastomer article has, in addition to being superior to the second fluoroelastomer article, improved tolerance to fluorinated plasma, oxygen plasma, hydrogen plasma, and combinations thereof. In the method, the fluoroelastomer article is superior to the second fluoroelastomer article in that it also has improved physical properties. In the method described, the fluoroelastomer article exhibits a better and lower compression set at 350°C / 70 hours / 18% deformation compared to the second fluoroelastomer article. In this specific example, the curable fluoroelastomer composition used to form the second fluoroelastomer article may additionally include carbon black filler. The present invention also includes a method for forming a fluoroelastomer article with reduced compression set, comprising: preparing a curable fluoroelastomer composition comprising at least one first curable fluoropolymer containing at least one fluorinated monomer, and at least one fluorinated curing monomer containing at least one curing site; adding microdiamond particles having an average particle size greater than 0.10 micrometers to 100 micrometers to the curable fluoroelastomer composition; and curing the curable fluoroelastomer composition to form a fluoroelastomer article, wherein the fluoroelastomer article has a compression set reduction value of 250°C / 70 hours / 25% compared to a second fluoroelastomer article formed from the same curable fluoroelastomer composition but excluding the microdiamond particles. In this method, at least one curable fluoropolymer may be a perfluoropolymer, the fluorinated monomer is tetrafluoroethylene, at least one fluorinated curing monomer may be a perfluorinated curing monomer, and the perfluoropolymer may additionally contain perfluoroalkyl vinyl ethers. In the methods described above, the method may also include adding a curing agent to the fluorinated elastomer composition before curing the composition. In the method, when the fluoroelastomer article and the second fluoroelastomer article are exposed to fluorinated plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof, the fluoroelastomer article exhibits better performance and reduced microparticle formation compared to the second fluoroelastomer article. In a specific example of this method, the curable fluoroelastomer composition used to form the second fluoroelastomer article further includes carbon black filler. In the method described, the fluoroelastomer article is superior to the second fluoroelastomer article in that it also exhibits reduced adhesion. In this specific example, the cured fluoroelastomer composition used to form the second fluoroelastomer article may additionally contain carbon black filler. In the method, the fluoroelastomer article is superior to the second fluoroelastomer article in that it also has improved tolerance to fluorinated plasma, oxygen plasma, hydrogen plasma, and combinations thereof. In the method, the fluoroelastomer article is superior to the second fluoroelastomer article and also has improved physical properties. In the method, the fluoroelastomer article preferably also has a compression set value of 18% reduction in deformation at 350°C / 70 hours compared to the second fluoroelastomer article. In a specific example of this method, the curable fluoroelastomer composition used to form the second fluoroelastomer article may additionally include carbon black filler. The present invention also includes a method for forming a fluoroelastomer article with reduced adhesion, comprising: preparing a curable fluoroelastomer composition comprising at least one first curable fluoropolymer containing at least one fluorinated monomer, and at least one fluorinated curing site monomer containing at least one curing site; adding microdiamond particles having an average particle size greater than 0.10 micrometers to 100 micrometers to the curable fluoroelastomer composition; and curing the curable fluoroelastomer composition to form a fluoroelastomer article, wherein the fluoroelastomer article has reduced adhesion compared to a second fluoroelastomer article formed from the same curable fluoroelastomer composition as a curable fluoroelastomer but excluding the microdiamond particles. In the method, at least one curable fluoropolymer may be a perfluoropolymer, the fluorinated monomer may be tetrafluoroethylene, at least one fluorinated curing monomer may be a perfluorinated curing monomer, and the perfluoropolymer may additionally contain perfluoroalkyl vinyl ethers. In the methods described above, the method may also include adding a curing agent to the fluorinated elastomer composition before curing the composition. In the method, the fluoroelastomer article preferably also has a compression set value of 250°C / 70 hours / 25% reduction in deformation compared to the second fluoroelastomer article. In this specific example, the curable fluoroelastomer composition used to form the second fluoroelastomer article may additionally include carbon black filler. In the method, when the fluoroelastomer article and the second fluoroelastomer article are exposed to fluorinated plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof, the fluoroelastomer article exhibits better performance and reduced microparticle formation compared to the second fluoroelastomer article. In a specific example of this method, the curable fluorinated elastomer composition used to form the second fluoroelastomer article may additionally include carbon black filler. In the method, the fluoroelastomer article is superior to the second fluoroelastomer article in that it also has improved tolerance to fluorinated plasma, oxygen plasma, hydrogen plasma, and combinations thereof. In the method, the fluoroelastomer article is superior to the second fluoroelastomer article and also has improved physical properties. In the method described, the fluoroelastomer article exhibits a better reduction in compression set at 350°C / 70 hours / 18% deformation compared to the second fluoroelastomer article. In this specific example, the curable fluoroelastomer composition used to form the second fluoroelastomer article may additionally include carbon black filler. The present invention further includes a method for forming a fluoroelastomer article with reduced microparticle size, comprising: preparing a curable fluoroelastomer composition comprising at least one curable fluoropolymer containing at least one fluorinated monomer, and at least one fluorinated curing site monomer containing at least one curing site; adding microdiamond particles having an average particle size of greater than 0.10 micrometers to about 100 micrometers to the curable fluoroelastomer composition; and curing the curable fluoroelastomer composition to form a fluoroelastomer article, wherein the fluoroelastomer article can be used at an operating temperature of at least about 350°C. In the methods described above, the method may also include adding a curing agent to the fluorinated elastomer composition before curing the composition. In the method, the fluoroelastomer article can be a perfluoroelastomer article. In the method, the fluoroelastomer article preferably has a compression set value of 18% reduction in deformation at 350°C / 70 hours compared to a second fluoroelastomer article formed from the same curable fluoroelastomer composition but excluding microdiamond particles. In this specific example, the curable fluoroelastomer composition used to form the second fluoroelastomer article further includes carbon black filler.

Implementation Method

Claims

1. A curable fluoroelastomer composition comprising at least one curable fluoropolymer selected from (i) a curable fluoropolymer comprising at least two fluorinated monomers, one of which is a fluorinated olefin or a fluorinated alkyl vinyl ether, and the other is vinylidene fluoride or at least one fluorinated curing site monomer comprising at least one curing site, and (ii) a curable perfluoropolymer comprising one or more perfluorinated olefin or perfluorinated alkyl vinyl ether monomers and at least one perfluorinated fluorinated curing site monomer comprising at least one curing site; and microdiamond particles having an average particle size of greater than 0.10 micrometers to about 100 micrometers, wherein when the composition is cured, the resulting fluoroelastomer or perfluoroelastomer has reduced microparticle size and enhanced plasma resistance.

2. The curable fluorinated elastomer composition of claim 1, wherein the microdiamond particles have an average particle size of more than 0.1 micrometers to about 10 micrometers.

3. The curable fluorinated elastomer composition of claim 2, wherein the microdiamond particles have an average particle size of about 0.1 micrometers to about 5 micrometers.

4. The curable fluorinated elastomer composition of claim 2, wherein the microdiamond particles have an average particle size of about 0.20 micrometers to about 2 micrometers.

5. The curable fluorinated elastomer composition of claim 4, wherein the microdiamond particles have an average particle size of about 0.25 micrometers to about 1 micrometer.

6. The curable fluorinated elastomer composition of claim 1, wherein the microdiamond particles have an average particle size of about 0.25 micrometers to about 0.5 micrometers.

7. The curable fluorinated elastomer composition of claim 1, wherein the microdiamond particles have a shape selected from spherical particles, fibers or flasks.

8. A curable fluorinated elastomer composition as claimed in claim 1, wherein the microdiamond particles are natural microdiamond particles or synthetic microdiamond particles.

9. The curable fluorinated elastomer composition of claim 1, wherein the microdiamond particles are a mixture of natural microdiamond particles and synthetic microdiamond particles.

10. A curable fluorinated elastomer composition as claimed in claim 1, wherein the particles are in the form of a polymer or aggregate.

11. The curable fluoroelastomer composition of claim 1, wherein the composition comprises about 0.1 to about 100 parts by weight of the at least one curable fluoropolymer of microdiamond particles per 100 parts by weight.

12. The curable fluoroelastomer composition of claim 11, wherein the composition comprises about 1 to about 50 parts by weight of the at least one curable fluoropolymer of microdiamond particles per 100 parts by weight.

13. The curable fluoroelastomer composition of claim 12, wherein the composition comprises about 2 to about 20 parts by weight of the at least one curable fluoropolymer of microdiamond particles per 100 parts by weight.

14. The curable fluoroelastomer composition of claim 1, wherein the at least one curable fluoropolymer is a curable perfluoropolymer comprising tetrafluoroethylene and perfluoroalkyl vinyl ether and at least one perfluorinated curing site monomer.

15. The curable fluoroelastomer composition of claim 14, further comprising at least one curing agent.

16. The curable fluoroelastomer composition of claim 1, wherein the at least one curable fluoropolymer is a curable perfluoropolymer comprising tetrafluoroethylene and perfluoroalkyl vinyl ether monomers, and wherein the curable perfluoropolymer contains fluoroplastic particles.

17. The curable fluoroelastomer composition of claim 16, further comprising at least one curing agent.

18. The curable fluoropolymer composition of claim 1, wherein the curable fluoropolymer is a perfluoropolymer comprising tetrafluoroethylene and perfluoroalkyl vinyl ether monomers, and at least two perfluorinated fluorinated curing monomers are present, each having at least one curing site.

19. The curable fluoroelastomer composition of claim 18, further comprising at least one curing agent.

20. The curable fluoroelastomer composition of claim 19, wherein the composition comprises a blend of the curable perfluoropolymer and a second curable perfluoropolymer, the second curable perfluoropolymer comprising tetrafluoroethylene, a second perfluoroalkyl vinyl ether monomer and a perfluorinated curing site monomer, and wherein the second curable perfluoropolymer contains fluoroplastic particles, and the composition further comprises at least two curing agents.

21. The curable fluoroelastomer composition of claim 20, wherein the weight percentage of the curable perfluoropolymer to the weight percentage of the second curable perfluoropolymer ranges from about 5:95 to about 95:

5.

22. The curable fluoroelastomer composition of claim 21, wherein the weight percentage of the curable perfluoropolymer to the weight percentage of the second curable perfluoropolymer ranges from about 20:80 to about 80:

20.

23. The curable fluoroelastomer composition of claim 22, wherein the weight percentage of the curable perfluoropolymer to the weight percentage of the second curable perfluoropolymer ranges from about 40:60 to about 60:

40.

24. The curable fluoroelastomer composition of claim 23, wherein the weight percentage of the curable perfluoropolymer to the weight percentage of the second curable perfluoropolymer is in the range of about 50:

50.

25. The curable fluorinated elastomer composition of claim 20, wherein each of the at least two perfluorinated curable monomers of the curable perfluoropolymer is present in the curable perfluoropolymer in an amount of about 0.1 to about 10 moles, and the perfluorinated curable monomer of the second curable perfluoropolymer is present in the second curable perfluoropolymer in an amount of about 0.1 to about 10 moles.

26. The curable fluoroelastomer composition of claim 20, wherein the curable perfluoropolymer comprises at least two curing site monomers having nitrogen-containing curing sites, and the nitrogen-containing curing sites being a primary cyano-curing site on a first curing site monomer of the curable perfluoropolymer and a secondary cyano-curing site on a second curing site monomer of the curable perfluoropolymer.

27. The curable fluorinated elastomer composition of claim 20, wherein at least one curing site in each of the at least two perfluorinated curing site monomers in the curable perfluoropolymer is selected from the group consisting of cyano, carboxyl, carbonyl, alkoxycarbonyl and combinations thereof.

28. The curable fluoroelastomer composition of claim 20, wherein the at least two curing agents are present in the composition in a total amount of about 0.2 to about 10 parts by weight of the curable perfluoropolymer per 100 parts by weight of the composition.

29. The curable fluoroelastomer composition of claim 28, wherein the at least two curing agents are present in the composition in a total amount of about 0.2 parts by weight to about 6 parts by weight of the curable perfluoropolymer per 100 parts by weight of the composition.

30. The curable fluoroelastomer composition of claim 20, wherein the at least two curing agents comprise a first curing agent and a second curing agent, the first curing agent being present in the composition in an amount of about 0.5 parts by weight to about 4 parts by weight per 100 parts by weight of the curable perfluoropolymer, and the second curing agent being present in the composition in an amount of about 0.3 parts by weight to about 2 parts by weight per 100 parts by weight of the curable perfluoropolymer.

31. The curable fluorinated elastomer composition as claimed in claim 20, wherein the first curing agent is 31. And the second curing agent is 31. Each R1 is independently -NH2, -NHR2, -OH, or -SH; R2 is a monovalent organic group; and R6 is -SO2, -O-, -CO-, an alkyl group of 1 to 6 carbon atoms, a perfluoroalkyl group of 1 to 10 carbon atoms, a single bond, or a group as shown in formula (IX):

32. The curable fluoroelastomer composition of claim 31, wherein the second curing agent is a compound according to formula (X):

32. wherein R7 is independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms; a partially fluorinated or perfluorinated alkyl group having 1 to 10 carbon atoms; a phenyl group; a benzyl group; a fluorinated phenyl group; a fluorinated benzyl group; or a phenyl or alkyl group having a functional group of a low carbon alkyl or perfluoroalkyl group, or the second curing agent is a diaminophenol or a salt thereof.

33. The curable fluorinated elastomer composition of claim 32, wherein the fluorinated phenyl group is a partially fluorinated phenyl group.

34. The curable fluorinated elastomer composition of claim 32, wherein the fluorinated benzyl group is a partially fluorinated benzyl group.

35. The curable fluorinated elastomer composition of claim 32, wherein the second curing agent is diaminophenol or a salt thereof.

36. The curable fluoroelastomer composition of claim 20, wherein the second curable perfluoropolymer comprises a curable site monomer having a curable site selected from the group consisting of halogen, nitrogen-containing groups, carboxyl groups, alkoxy carbonyl groups and combinations thereof.

37. The curable fluoroelastomer composition of claim 20, wherein the at least two curing agents are selected from the group consisting of:

37. Diaminophenols and their combinations.

38. A cured fluorinated elastomer formed by curing a curable fluorinated elastomer composition as claimed in claim 1.

39. A molded article formed by thermosetting and molding a curable fluorinated elastomer composition as claimed in claim 1.

40. A method of forming a fluoroelastomer article with reduced microparticle formation, comprising: preparing a curable fluoroelastomer composition comprising at least one curable fluoropolymer selected from (i) a curable fluoropolymer comprising at least two fluorinated monomers, one of which is a fluorinated olefin or a fluorinated alkyl vinyl ether, and the other is vinylidene fluoride or at least one fluorinated curing site monomer comprising at least one curing site, and (ii) a curable fluoropolymer comprising one or more perfluorinated olefins or perfluorinated alkyl vinyl ether monomers and at least one curing site. A curable perfluoropolymer of a perfluorinated curable monomer; adding microdiamond particles having an average particle size of more than 0.10 micrometers to about 100 micrometers to the curable fluorinated elastomer composition; and curing the curable fluorinated elastomer composition to form a fluorinated elastomer article, wherein when the fluorinated elastomer article and a second fluorinated elastomer article are exposed to at least one of a fluorinated plasma, an oxygen plasma, a hydrogen plasma, and combinations thereof, the fluorinated elastomer article has reduced microparticle formation compared to the second fluorinated elastomer article having the same fluorinated elastomer composition but not including the microdiamond particles.

41. The method of claim 40, wherein the curable fluoroelastomer composition includes at least one filler, and the method further includes adding the microdiamond particles to the fluoroelastomer composition while adding the at least one filler to the at least one curable fluoropolymer.

42. The method of claim 40, further comprising adding at least one curing agent to form the fluoroelastomer article prior to curing the curable fluoroelastomer composition.

43. The method of claim 40, wherein the at least one curable fluoropolymer is a perfluoropolymer, the fluorinated monomer is tetrafluoroethylene, the at least one fluorinated curing monomer is a perfluorinated curing monomer, and the perfluoropolymer further comprises a perfluoroalkyl vinyl ether.

44. The method of claim 40, wherein the fluoroelastomer article has a reduced compression set value compared to the second fluoroelastomer article at 250°C / 75 hours / 25% deformation.

45. The method of claim 44, wherein the curable fluoroelastomer composition used to form the second fluoroelastomer article further comprises carbon black filler.

46. ​​The method of claim 45, wherein the fluoroelastomer article has reduced adhesive force compared to the second fluoroelastomer article.

47. The method of claim 40, wherein the fluoroelastomer article has improved tolerance to fluorinated plasma, oxygen plasma, hydrogen plasma and combinations thereof compared to the second fluoroelastomer article.

48. The method of claim 40, wherein the fluoroelastomer article has improved physical properties compared to the second fluoroelastomer article.

49. The method of claim 40, wherein the fluoroelastomer article has a reduced compression set value compared to the second fluoroelastomer article at 350°C / 70 hours / 18% deformation.

50. A method of forming a fluoroelastomer article having reduced compression set, comprising: preparing a curable fluoroelastomer composition comprising at least one first curable fluoropolymer selected from (i) a curable fluoropolymer comprising at least two fluorinated monomers, one of which is a fluorinated olefin or a fluorinated alkyl vinyl ether, and the other is vinylidene fluoride or at least one fluorinated curing site monomer comprising at least one curing site, and (ii) a curable fluoropolymer comprising one or more perfluorinated olefin or perfluorinated alkyl vinyl ether monomers and up to A curable perfluoropolymer comprising at least one perfluorinated fluorinated curing monomer containing at least one curing site; adding microdiamond particles having an average particle size greater than 0.10 micrometers to 100 micrometers to the curable fluorinated elastomer composition; and curing the curable fluorinated elastomer composition to form the fluorinated elastomer article, wherein the fluorinated elastomer article has a compression set value of 250°C / 70 hours / 25% reduction in deformation compared to a second fluorinated elastomer article formed from the same curable fluorinated elastomer composition but excluding the microdiamond particles.

51. The method of claim 50, wherein the at least one first curable fluoropolymer is a perfluoropolymer comprising tetrafluoroethylene, the at least one fluorinated curable monomer is a perfluorinated curable monomer and the perfluoropolymer further comprises a perfluoroalkyl vinyl ether, and the method further comprises adding at least one curing agent to form the fluoroelastomer article prior to curing the curable fluoroelastomer composition.

52. The method of claim 50, wherein the fluoroelastomer article: (i) has reduced microparticle formation compared to the second fluoroelastomer article when the fluoroelastomer article and the second fluoroelastomer article are exposed to fluorinated plasma, oxygen plasma, hydrogen plasma, and combinations thereof; or (ii) has reduced adhesive force compared to the second fluoroelastomer article; or (iii) has improved resistance to fluorinated plasma, oxygen plasma, hydrogen plasma, and combinations thereof compared to the second fluoroelastomer article; or (iv) has improved physical properties compared to the second fluoroelastomer article.

53. The method of claim 50, wherein the fluoroelastomer article has a reduced compression set value compared to the second fluoroelastomer article at 350°C / 70 hours / 18% deformation.

54. The method of claim 50 or 53, wherein the curable fluoroelastomer composition used to form the second fluoroelastomer article further comprises carbon black filler.

55. A method of forming a fluoroelastomer article with reduced adhesion, comprising: preparing a curable fluoroelastomer composition comprising at least one curable fluoropolymer selected from (i) a curable fluoropolymer comprising at least two fluorinated monomers, one of which is a fluorinated olefin or a fluorinated alkyl vinyl ether, and the other is vinylidene fluoride or at least one fluorinated curing site monomer comprising at least one curing site, and (ii) a curable perfluoropolymer comprising one or more perfluorinated olefin or perfluorinated alkyl vinyl ether monomers and at least one perfluorinated fluorinated curing site monomer comprising at least one curing site; adding microdiamond particles having an average particle size greater than 0.10 micrometers to 100 micrometers to the curable fluoroelastomer composition; and curing the curable fluoroelastomer composition to form the fluoroelastomer article, wherein the fluoroelastomer article has reduced adhesion compared to a second fluoroelastomer article formed from the same curable fluoroelastomer composition as the curable fluoroelastomer but excluding the microdiamond particles.

56. A method of forming a fluoroelastomer article with reduced microparticle size, comprising: preparing a curable fluoroelastomer composition comprising at least one curable fluoropolymer selected from (i) a curable fluoropolymer comprising at least two fluorinated monomers, one of which is a fluorinated olefin or a fluorinated alkyl vinyl ether, and the other is vinylidene fluoride or at least one fluorinated curing site monomer comprising at least one curing site, and (ii) a curable perfluoropolymer comprising one or more perfluorinated olefin or perfluorinated alkyl vinyl ether monomers and at least one perfluorinated fluorinated curing site monomer comprising at least one curing site; adding microdiamond particles having an average particle size of about 0.10 micrometers to about 100 micrometers to the curable fluoroelastomer composition; and curing the curable fluoroelastomer composition to form the fluoroelastomer article, wherein the fluoroelastomer article can be used at an operating temperature of at least about 350°C.