GB2308368A - Perfluoroelastomeric compositions and seals - Google Patents
Perfluoroelastomeric compositions and seals Download PDFInfo
- Publication number
- GB2308368A GB2308368A GB9704231A GB9704231A GB2308368A GB 2308368 A GB2308368 A GB 2308368A GB 9704231 A GB9704231 A GB 9704231A GB 9704231 A GB9704231 A GB 9704231A GB 2308368 A GB2308368 A GB 2308368A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polymer
- seal
- elastomeric composition
- fluorocarbon
- particulate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
An elastomeric composition having improved resistance to chemical attack includes a perfluoroelastomer and a particulate fluorinated graphite polymer having a composition of (CF x ) n where x ranges from about 0.25 to about 1.20 and n is at least about 10 3 . Seals for preventing leakage of a fluid between a first member and a second member are made from the composition, which may also include a non-fibrillating fluorocarbon particulate polymer.
Description
PERFLUOROELASTOMERIC COMPOSITIONS AND SEALS
Field of the Invention
This invention relates to improving the chemical resistance of perfluoroelastomeric compositions and seals.
Background of the Invention ~elastomers nay one used in a variety of processing and manufacturing operations which demand resilience and resistance to high temperatures and chemical attack. For example, elastomeric seals may be used in chemical processing and petroleum refining ec-ipment, such as pump housings, reactors, nixers, compressor casings, valves and other equipment. -lastomeric seals are also used in the semiconauctor manufacturing industry, often in the presence of aggressive chemicals and specialty gases. In the nuclear power industry, such seals may be used in check valves and pressure relief valves where superior- reliability is required.
In analytic and process instrument applications, such as liquid chromatography, microcontamination is often unacceptable and seals or gaskets must possess superior resistance to degradation when subjected to chemical attack.
Chemical and temperature resistant elastomeric seals are also required in the aircraft and aerospace industries, chemical transport industries, and paint and coating operations,- to name a few.
Such seals may be located within complex machinery and process systems, making replacement of failed seals a costly and arduous task. Most elastomeric seal failures are caused by thermal aging and fluid attack. The polymers may degrade by oxidation, chemical attack, breaking of the polymer chain, etc. Swelling may cause the seal to expand out of its retaining grooves and cause leaks in a system. Generally, higher temperatures increase the deteriorative effect of chemicals on polymers. Thermal aging, including temperatures caused by peak loading conditions of equipment, may cause elastomers to become hard and brittle, decreasing the ability of seals to conform to irregular surfaces. In addition, there is evidence that the presence of oxygen nay deteriorate some elastomers subjected to temperatures greater than 200 F.
The prior art discloses a variety of modified fluoroelastomeric materials having various improved physical properties. For example, U.S. Patent No. 4,387,168 discloses an adhesive composition comprising a low molecular weight fluorine-containing elastomer and fibrillated polytetrafluoroethylene (PTFr) which has improved chemical and weather resistance. Examples of suitable elastomers include copolymers of vinylidene fluorice and at least one fluor ne- containing ethylenically unsaturated monomer, such as tetrafluoroethylene (T ), trifluorochloroethylene, trifluoroethylene, hexafluoropropylene (HFP), pentafluoropropylene, perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether) and perfluoro(propyl vinyl ether) . A conventional iller such as silica may be included as an additive in the composition.
The use of a fibrillated filler such as fibrillated PTF is not desirable, however, because the fibrillated iller is deleterious to processibility, hindering milling, r:iixing, extrusion, and mold flow. Articles formed from elastomeric compositions including fibrillated fillers may be stif and have high modulus and die swell values. Articles produced by extruding compositions containing a fibrillating filler typically have poor surface characteristics, such as gaps, cracks, etc. The preform cross-sectlon is usually non--inirorm causing uneven surfaces in the final article. Smooth surface characteristics are particularly important for articles to be used as seals to prevent leakage around the seal area.
U.S. Patent No. 5,057,345 discloses a polymer blend comprising (A) a fluorinated ethylene-propylene copolymer and (B) a fluoroelastomer. The fluoroelastomer comprises a block copolymer having at least one elastomeric segment comprising TFE, vinylidene fluoride and HFP repeating units and at least one nonelastomeric segment comprising TFE and ethylene repeating units. The advantages of these blends include high tensile strength or elongation, low modulus, increased flexibility, improved stress-crack resistance, stress-induced crystallization anå/or optical clarity.
U.S. Patent No. 4,952,630 discloses a dispersion- process-produced, non-melt-processible, particulate, coreshell, TFE copolymer which may be compositioned with an elastomer or plastic. The PTFE resins comprise recurring units of TFS and modifying recurring units of at least one ethylenically unsaturated comonomer that is copolymerizable with the T."- in a dispersion process. Preferred comonomers include 6'.FP and perfluoro(alkyl vinyl ethers). The comonomer may be present throughout the copolymer article, if desired, for example in the core as well as in the shell. The copolymer may be incorporated in an elastomeric or a plastic organic resin. The resulting elastomeric blends have improved tear strength and abrasion resistance. The resulting plastic blends have improved extrusion properties, rate, abrasion resistance, flame resistance and less melt-swell. The elastomer matrix may be any elastomer including, but not iimited to, vinylicene fluoride copolymers. The elastomeric or plastic matrix can contain fillers, such as reinforcing agents or fire retarding agents.
R. Morgan et al., "Reinrorcement of Elastomers With Fluoroplastic Additives", E. I. du Pont de nours & Co.
presentation to the Energy Rubber Group in Arlington, Texas (January 16, 1991) (originally presented at a meeting of the
Rubber Division of the American Chemical Society in Washington, D.C. (October 12, 1990)) discloses that elastomers compositioned with a high molecular weight TFE/HFP fluoroplastic micropowder (Teflon (RTM) MP1500, available from E.
I. du Pont de Nemours of Wilmington. Delaware) improves the tear strength and abrasion resistance and reduces the coefficients of friction of elastomers. The micropowder forms short fibers, ribbons or platelets when compositioned with sufficient shear into elastomers.
U. S. Patent No. 4,713,418 discloses blending a thermoplastic TFE copolymer with a fluoroelastomer at a temperature which is sufficiently high to melt the thermoplastic TFE copolymer. Suitable fluoroelastomers include copolymers of 52 to 79.9 mole percent TFE, 20 to 45 mole percent perfluoro(alkyl vinyl ethers) and a third comonomer which can act as a crosslink site. Carbon black may be added to the blend to improve the strength of articles formed from the blend.
Such prior art fluoroelastomeric materials may ceteriorate when exposed to heat and harsh chemical environments, such as hot aromatics, oils, heat transfer fluids, amines, corrosive acids and steam, typically found in the chemical processing and other high technology industries.
For example, fluoroelastomeric seals are vulnerable to attack from methyl ethyl ketone ("MEK"), diethylamine, aqueous ammonia, glacial acetic acid and other agents.
There is a long-felt need in the art for a process or method for making fluoroelastomeric compositions and seals reinforced with a non-fibrillating filler other than carbon black which may be used to form articles, such as seals, which resist deterioration when exposed to harsh chemical environments and function over a broad spectrum of temperatures from well below freezing to in excess of 450 F without deteriorating, creeping or flowing. Preferably, such compositions and seals would combine the sealing ability of elastomers wit superior chemical resistance over a wide ran o temperatures.
Su@mary of the Invention Bri@fly stated, one aspect of the present invention is an elastomeric composition having improved resistance to
chemical attack, the elastomeric composition comprising a
From one aspect, the present invention resides in an elastomeric composition having improved resistance to chemical attack, comprising a mixture of:
a perfluoroelastomer and
a particulate fluorinated graphite polymer having a composition of (CFx)n where x ranges from about 0.25 to about 1.20 and n is at least about 103.
From a further aspect, the present invention resides in a seal for preventing the leakage of a fluid between a first member and a second member and having improved chemical resistance to the fluid and reduced coefficients of friction at a surface of the seal, the seal comprising a mixture of:
a perfluoroelastomer and
a particulate fluorinated graphite polymer having a composition of (CFx)n where x ranges from about 0.25 to about 1.20 and n is at least about 103.
From a yet further aspect, the present invention resides in a process for improving the resistance to chemical attack and increasing the strength of a perfluoroelastomer, comprising:
mixing the perfluoroelastomer with a non-fibrillating fluorocarbon particulate polymer and a particulate fluorinated graphite polymer having a composition of (CFx)n where x ranges from about 0.25 to about 1.20 and n is at least about 103 to form an elastomeric composition; and
processing the elastomeric composition at a processing temperature less than the melting temperature of the nonfibrillating fluorocarbon particulate polymer to disperse the fluorocarbon polymer and the fluorinated graphite polymer throughout the perfluoroelastomer while maintaining the fluorocarbon polymer and fluorinated graphite polymer in particulate form.
The present invention also resides in a method for increasing the resistance to chemical attack of an elastomeric seal and decreasing the coefficients of friction at a surface of the seal, the seal being for preventing the leakage of a fluid between a first member and a second member, comprising:
mixing a perfluoroelastomer with a non-fibrillating fluorocarbon particulate polymer and a particulate fluorinated graphite polymer having a composition of (CFx)n where x ranges from about 0.25 to about 1.20 and n is at least about 103 to form an elastomeric composition; and
processing the elastomeric composition at a temperature less than the melting temperature of the non-fibrillating fluorocarbon particulate polymer to disperse the fluorocarbon polymer and the fluorinated graphite polymer throughout the elastomeric composition while maintaining the fluorocarbon polymer and the fluorinated graphite polymer in particulate form to form an elastomeric seal, such that the seal has increased resistance to chemical attack and reduced coefficients of friction at the seal surface.
Preferred aspects of the invention are set out in the accompanying claims. Moreover, an alternative method for increasing the resistance to chemical attack of an elastomeric seal and decreasing the coefficients of friction at a surface of the seal is descibed and claimed in co-pending United
Kingdom Patent Application No. 9525977.6 of even date.
BRIEF DESCRIPTION OF TE DL-^INGS The foregoing summary, as well as the detailed
description of the preferred embodiments, will be better
understood when read in conjunction with the appended åravings. For the purpose of illustrating the present
invention, there are shown in the drawings several embodiments
which are presently preferred, it being understood, however,
that the invention is not limited to the specific arrangements
and instrutmentalities disclosed. In the drawings:
Fig. 1 is a schematic diagram of a breakaway and
dynamic friction testing apparatus used to determine the breakaway and dynamic friction values of O-ring seals produced according to the method of the present invention;
Fig. 2 is an enlarged detailed cross-sectional view of a portion of the testing apparatus of Fig. 1;
Fig. 3 is a graph of dynamic friction values of Oring seals produced according co the method of the present invention; and
Fig. 4 is a graph of breakaway friction values of Oring seals produced according to the method of the present invention.
Detailed Descrintion of referred Fnsodinents The compositions of the present invention will now be discussed generally in the context of their use as elastomeric seals. However, the compositions of the present invention are not limited only to use as elastomeric seals, but are also useful for other articles or applications in which improved resistance to chemical attack is desired, such as coatings, laminates, gaskets, tubing, molding articles, etc.
Seals to which the present invention are particularly directed include those for preventing the leakage of a fluid between a first member and a second member, such as a valve bonnet and valve body, a gasket between two flanges, and a rotating shaft and stationary housing, for example.
Further discussion of the first and second member is net believed to be necessary to an understanding of the present invention and will therefore be omitted.
The seal is preferably formed in the shape of an Oring, although the seal may also be formed in the shape of a
V-ring, U-cup, gasket, valve seat, tubing, down hole" packing element, or other sealing parts, including those of custom cesign. One of ordinary skill in the art would understand that the seal may be formed in any desired shape.
Seals are typically designed to prevent the leakage of a fluid, such as a gas, liquid or combination thereof, between a first member and a second member. Such fluids may include, for example, gases such as air, nitrogen, argon, acetylene gas, ammonia cas, blast furnace gas, chlorine gas, coke oven gas, cyanogen gas, hydrogen chloride gas, hydrogen gas, mercury vapors, nitric acid vapors, oxygen, ozone, and other gases too numerous to mention. Examples of liquids include nearly all chemical reagents such as inorganic and organic acids, alkalis, ketones, esters, aldehydes, alcohols, fuels, stean and hot water.
With few exceptions, suc as perfluorinated fluids and alkali metals, perfluoroelastomers are generally resistant to virtually all chemicals. Perfluoroelastomeric seals may be used in harsh chemical environments, such as those encountered in the pu:ring of strong acids and other processing equipment in chemical plants and oil fields, for example. One of ordinary skill in the art would understand that the chemical resistance of perfluoroelastomeric compositions and articles to many other fluids, both in liquid and gaseous form, present at a wide range of temperatures may be improved by the process and method of the present invention.
A perfluoroelastomer is defined herein as an amorphous polyrer of one or more perfluorinated monomers being substantially free of hydrogen substituents. A preferred perfluoroelasto.er for use in the compositions, seals and methods of the present invention is a terpolymer of tetrafluoroethylene, perfluoroalkyl vinyl ether and one of several perfluorinated cure site monomers. The cure site monomer incorporates a functional group which permits crosslinking of the terpolymer. Preferred perfluoroelastomers are capable of maintaining their struc(turaS integrity at0 temperatures ranging fro about -20F/to about 450 F@(RTM) A preferred perfluoroelastomer is CHEMRAZ @@@@@@@ which is commercially available from Greene, Tweed & Co., Inc. o Kulpsville, Pennsylvania. Other preferred perfluoroelastomers which are similar in chemical composition to CHEMRAZ (RTM) include RALREZ/, which is commercially available from E. I. du Pont de (7r!) Nemours of Wilmington, Delaware; SIMRIZ @ which is available from Freudenberg of Germany and DAIEL-PERFLUOR (RTM) which is available from Daikin Industries, Ltd of Osaka, Japan.
Prior art seals mace from elastomeric materials, even fluoroelastomeric materials, are vulnerable to attack from agents such as methyl ethyl ketone (MEK), diethylamine, aqueous ammonia, glacial acetic acid, methyl acrylate, tetrahydrofuran, toluene, and methyl alcohol. In contrast, perfluoroelastomers are impervious to attack by these and many other reagents under standard chemical processing conditions.
Thus, the use of a perfluoroelastomeric composition allows seals to be used in hostile environments over prolonged periods of time and under conditions not previously allowable with seals of the prior art.
It is desirable to have a perfluoroelastomeric seal wherein the chemical resistance, compression set, sealing force retention, resilience and coefficients of friction are irproved over a seal formed only from a perfluoroelastomer.
In order to improve upon these and other properties, according co the present invention a perfluoroelastomer is mixed with a non-fibrillating fluorocarbon particulate polymer to form an elastomeric composition which is processed at a temperature less than the melting temperature of the non-fibrillating fluorocarbon particulate polymer to maintain the fluorocarbon polymer in particulate form, but substantially uniformly blended in the elastomeric composition. The elastomeric compositions and seals formed according to the present invention exhibit less die swell and resist fibrillation and provide improved chemical resistance over typical prior art perfluoroelastorneric compositions using conventional fillers.
The non-fibrillating fluorocarbon particulate polymer may be any fluorocarbon polymer which remains in particulate form and does not fibrillate under typical processing conditions and may, for example, be any of the following: (1) a low molecular weight (i.e., about 50,000 to about 500,000 molecular weight) polytetrafluoroethylene (PTFE) (RTM) homopolymer, such as TEFLON@MP 1100, which is commercially available from du Pont, (2) a copolyme of TFE and (RTM) at least one of (a) hexafluoropropylene, such as TEFLON /PA or TEFLONS P, each of which is commercially available from du (RTM) Pont and (b) a perfluoroalkyl vinyl ether, such as TEFLON (RTM) PFA, which is also commercially available from du Pont, or perfluoromethyl vinyl ether, which is commercially available from Peninsular Chemical Research of Florida; and (3) fluorinated graphite.
Fluorinated graphite@may be prepared by heating graphite in the presence of fluorine gas. The fluorine gas chemically combines with the graphite to produce a material with a composition of (CFx)n' where x ranges from about 0.25 to about 1.20 and n is at least about 103.
As presently preferred, the fluorocarbon polymer is a mixture of (1) a copolymer of TFE and at least one o, .-.:P or
perfluoroalkyl vinyl ether and/or (2) fluorinated graphite@in which x is about 0.9 to about 1.0.
The fluorocarbon polymer comprises up to about 30 wtA of the elastomeric composition and, more preferably, between about 5 and about 15 wt-. of the elastomeric composition. The fluorocarbon polymer generally has an average particle diameter of about 1 to about 50 microns. One of ordinary skill in the art would understand that the selection of a fluorocarbon polymer having a suitable average particle diameter will depend upon such variables as the particular fluorocarbon polymer selected and processing conditions, such as temperature and pressure.
The elastomeric composition may also include one or more additives, such as carbon black, clay, silicon dioxide, barium sulfate,
polymeric fibers, curatives and/or plasticizers. An example of a plasticizer useful in the present elastomer (RTM) composition is a perfluorinated alkyl ether, such as KRYTOX (RTM) which is commercially available from du Pont, or DEMNUM (RTM) which is commercially available from Daikin.
The elastomeric composition is produced by mixing or blending the perfluoroelastomer with one or more nonfibrillating fluorocarbon particulate polymer(s) and any desired additives. For example, the perfluoroelastomer, fluorocarbon polymers and any additives desired may be blended using an internal mixer such as those commercially available from C. W. Brabender Instruments, Inc. of S.
Hackensack, New Jersey or other internal mixers such as are commercially available from Morijama of Farmingdale, New York.
The fluorocarbon particulate polymer, however, must be mixed with the perfluoroelastomer ac a temperature less than the melting temperature of the fluorocarbon particulate polymer to maintain its particulate form, prevent premature cross-linking of the perfluoroelastomer and maintain adequate flow properties.
Once all other ingredients desired are blended, curing agents are add to the blend. An example of a suitable curing agent is a combination of an organic peroxide, such as 2,5-dimethyl-2,5-di(t-butylperoxy) -hexane, and a coupling agent, such as triallyl isocyanurate.
The elastomeric composition is processed at a temperature less than tne melting temperature of the nonfibrillating fluorocarbon particulate polymer to disperse the fluorocarbon polymer throughout the elastomeric composition while maintaining the fluorocarbon polymer in particulat form. For example, the melting temperature of TEFLON SPA is about 1S00C - 2500C, there ore the temperature at which an elastomeric composition containing this fluorocarbon polymer is processed should be less than about 1800C to prevent melting of the fluorocarbon polymer.
Seals may then be formed from the elastomeric composition by a variety of processing methods, such as compression molding, injection molding, extrusion, etc. The processing methods before curing should also be conducted at temperatures less than the melting temperature of the fluorocarbon polymer, preferably less than about 1800C. The seals formed according to the present method have improved resistance to chemical attack when compared to seals mad from a perfluoroelastomer alone. Also, the surface of a seal made according to the present method has lower coefficients of friction than conventional seals which include typical prior art fillers, such as carbon black.
Non-limiting examples of elastomer compositions and seals prepared according to the methods of the present invention are set forth in Examples 1 - 3 below.
EXAMPLE 1 Elastomeric compositions were prepared according to the process of the present invention by blending, at a temperature of about 140 - 1600 , 100 parts of the (emi) perfluoroelastomer CHEMRAZ (RTM) with varying amounts of TEFLON @@@ PA, TEFLON (RTM) FEP, MP 1100, and fluorographite which is commercially available from Ozark Mahoning of Oklahoma having a value of x ranging from about 0.9 to about 1.0. Sample 6 is a control sample filled with 14 parts of carbon black. The curing agent used for each sample was 2.5-dimethyl-2,5-di(t- butylperoxy) -hexane and the coupling agent was triallyl isocyanurate. The amounts o fluorocarbon polymers added to each of samples 1 - 5 are set forth in Table I.
The compositions were mixed in an internal mixer, extruded to form a preform, and compression molded according to standard industry practice at temperatures less than the melting temperature of the fluorocarbon particulate polymer component to form # 214 O-rings. Each O-ring was press cured for 6 minutes at about 320 F (1600C) and subsequently postcured for four hours at about 356 F (800C) in a nitrogen atmosphere. Various physical tests, such as tensile strength.
percent elongation, 100% and 50% modulus (each of the arorementioned tests being conducted according to ASTM D 1414), Durometer "M", specific gravity and compression set (ASTM method D-1414, 214 O-ring), were conducted on each sample, the results of which are set forth in Table I.
The compression set, or permanent deformation in compression, refers to the propensity of an elastomeric material to remain distorted and not return to its original shape after a deforming compressive load has been removed.
The compression set value is expressed as a percentage of the original deflection that the material fails to recover. For example, a compression set value of Oi indicates that the material completely returns to its original shape.
Conversely, a compression set value of 100% indicates that the material does not recover at all from the applied deformation.
A compression set value of 30% signifies that 70% of the original deflection has been recovered. Higher compression set values generally correspond to higher seal leakage rates.
The amount of seal leakage depends upon a variety of factors, such as the degree of seal deformation, system pressure, fluid viscosity and temperature extremes.
A solid O-ring formed from the perfluoroelastomer
CHEMRAZ (RTM) and 14 parts of carbon black has (204 C) a compression set of about over about 70 hours at about 400 F/(ASTM method D-1414, 214 O-ring). The compression set of (RTM) the O-ring of Sample 1, which contains 12 parts of TEFLON/PA blended with 100 parts of the perfluoroelastomer CHEMz/ is only 26%. Seals formed according to the method of the present invention typically have compression set values comparable to or less than those of the perfluoroelastomer CH~M.RAZi with a typical prior art inert filler.
As shown in Table I, the 100% and 50% modulus values and Durometer "M" (Duro "M") values for Sample Nos. 1 - 5, which contain various fluorocarbon fillers of the present invention, are comparable to those of Sample No. 6, which contains carbon black.
The O-rings of Samples 1-6 were subjected to immersion tests according to ASTM-D 471 for 70 hours at room temperature using harsh chemical agents. Table II presents the results of immersion testing of sample O-rings in an TABLE I
SAHPLE PARTS PER 100 PARTS T@@@ILE PERC@@TAC@ 100% 50% DURO SP@CI@IC PERC@@TAC@ NO. PERFLUOROELASTOHER STRENGTH ELO@CATION HODU- MODU- "M" ORAVITY COMPRESSION (p.S.l.) LUS LUS SET (MPa) CAR@ON TEFLON TEFLON FLUORO- MP DLACK PA FEP CRAPHITE 1100 1 - 12 - - - 1100(7.59) 135 700 350 70 1.987 26 2 - - 12 - - 1000(6.90) 125 700 300 69 1.975 36 3 - 6 - 6 - 1100(7.59) 115 900 350 71 1.981 34 4 - - 6 6 - 1100(7.59) 110 1000 400 71 1.989 32 5 - - - 6 6 1050(7.24) 120 @50 350 71 1.991 34 6 14 - - - - 1400(9.65) 120 1050 400 71 1.950 30 CONTROL TABLE II
SAMPLES IMMERSED IN 93% SULFURIC ACID SAMPLE @ensile Strength PERCENT CHANGE PERCENTAGE PERCENT CHANGE CHANGE IN PERCENT NO. (p.s.i.) (MPa) IN TENSILE ELONGATION IN ELONGATION DURO "M" CHANGE IN STRENGTH VOLUME 1 1250(8.62) +14 150 +11 -1 +0.09 2 1400(9.63) +40 155 +24 -1 +0.12 3 1500(10.34) +27 155 +35 0 +0.07 4 1500(10.34) +27 145 +32 0 -0.04 5 1250(8.62) +19 125 +4 0 +0.04 6 1200(8.27) -14 105 -13 -2 +0.91 CONTROL TABLE III
SAMPLES IMMERSED IN FUMING NITRIC ACID PERCENT PERCENT PERCENT SAMPLE Tensile Strength CHANGE IN PERCENTAGE CHANGE IN CHANGE IN CHANGE IN NO. (p.s.i.) (MPa) TENSILE ELONGATION ELONGATION DURO "M" VOLUME STRENGTH 1 1300(8.96) +18 155 +15 -1 +1.49 2 1400(9.65) +40 160 +28 -1 +1.49 3 1350(9.31) +23 145 +26 0 +1.32 4 1250(8.62) +14 135 +23 0 +1.32 5 1100(7.58) 5 120 0 -2 +1.41 1050(7.24) 6 @@ -25 95 -21 0 +5.33 CONTROL TABLE IV
SAMPLES IMMERSED IN PERPLUOROTRIBUTYLAMINE PERCENT PERCENT PERCENT SAMPLE Tensile Strength CHANGE IN PERCENTAGE CHANGE IN CHANGE IN CHANGE IN NO. (p.s.i.)(MPa) TENSILE ELONGATION ELONGATION DURO "M" VOLUME STRENGTH 1 450(3.10) -59 105 -22 -10 +54.20 2 400(2.76) -60 100 -20 -9 +54.83 3 500(3.45) -55 90 -22 -13 +49.99 4 650(4.48) -41 110 0 -10 +48.20 5 500(3.45) -52 100 -17 -11 +50.96 6 400(2.76) -71 60 -50 -6 +43.80 CONTROL aqueous solution of 93% sulfuric acid. Table III presents the results of immersion testing of sample O-rings in fuming nitric acid. Table IV presents the results of immersion testing of sample O-rings in perfluorotributylamine. Samples 1-5 are filled with various combinations of fluorocarbon particulate polymers, while Sample 6 is a control sample filled with carbon black.
As shown in Tables IT, III and IV, the control (Sample 6) containing carbon black filler is more seriously affected by these harsh chemicals in relation to tensile according to the present invention have improved chemical resistance over perfluoroelastomers containing conventional fillers, such as carbon black.
EXAMPLE 2
Elastomer compositions were prepared according to the process of the present invention by blending, at a temperature of about 140 - 1600C, 100 parts of the perfluoroelastomer CHEMRAZ(RTM) with varying amounts of TO ONE PA, silica (R-972, which is commercially available from
Degussa Corporation of Chester, Pennsylvania), fluorographite having a value of x ranging from about 0.9 to about 1.0 (which is commercially available from Ozark Mahoning) and titanium dioxide (which is commercially available from du Pont) (Samples A - C).. Sample D is-a control sample filled with 14 parts of carbon black. The curing agent used for each sample was 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane and the c-oupling agent was triallyl isocyanurate. The amounts of fluorocarbon polymers and other fillers add to each of samples A - C are set forth in Table V.
The compositions were mixed and compression molded according co standard industry praccice in the same marker as that set forth in Example 1 above to form 214 O-rings. Each
O-ring was press cured and subsequently post-cured for four hours in the same manner as that set forth in Example 1 above.
Various physical tests were conducted on each sample, the results of which are set forth in Table V.
TABLE V
PARTS PER 100 PARTS Tensile Strength PERCENTAGE 100% 50% DURO SPECITIC PERFLUOROELASTOMER @LONGATION MODU- MODU- "M" CRAVITY (p.s.i) (MPa) LUS LUS SAMPLE CAR@ON TEFLON SILICA TLUORO- TITANIUM BLACK PA GRAPHITE DIOXID@ A - 6 3 6 1 1360(9.38) 390 560 150 70 1.957 B - 5 2 5 - 1350(9.31) 170 6@0 @@0 70 1.930 C - 10 5 - - 1230(8.48) 180 450 140 70 1.946 D 14 - - - - 1500(10.34) 140 790 210 75 1.904 TABLE VI
SAMPLES IMMERSED IN STEAH (30 DAYS) SAMPLE Tensile Strength PERCENT CHANGE PERCENTAGE PERCENT DURO CHANGE PERCENT NO. (p.s.i.)(MPa) IN TENSILE ELONGATION CHANGE IN "M" IN DURO CHANGE IN STRENGTH ELONGATION "M" VOLUME A 1400(9.65) +3 165 -13 69 -1 +0.4 B 1430(9.86) +6 145 -15 71 +2 +0.6 C 1230(8.48) 0 165 - 9 72 +3 +0.7 D 1640(11.31) +9 120 -15 78 +4 +0.6 TABLE VII
SAMPLES IMMERSED IN HYDRAZINE (30 DAYS) PERCENT PERCENT CHANGE DURO CHANGE PERCENT Tensile Strength SAMPLE CHANGE IN PERCENTAGE IN ELONGATION "M" IN DURO CHANGE IN NO. (p.s.i.)(MPa) TENSILE SLONGATION "M" VOLUME STRENGTH A 1350(9.31) - 1 160 -16 69 -1 +0.2 B 1400(9.65) + 4 155 - 9 71 +2 +0.4 C 1270(8.76) + 3 165 - 8 72 +3 +0.8 D 1700(11.72) +13 125 -11 79 +5 0 TABLE VIII
SAMPLES IMMERSED IN N-METHYLPYRROLIDONE (30 DAYS) PERCENT PERCENT DURO CHANGE PERCENT SAMPLE Tensile Strength CHANGE IN PERCENTAGE CHANGE IN "M" IN DURO CHANGE IN NO. (p.s.i.)(MPa) TENSILE ELONGATION ELONGATION "M" VOLUME STRENGTH A 1240(8.55) -9 150 -21 69 -1 0 B 1240(8.55) -8 135 -21 71 +2 +0.7 C 1290(8.90) +5 175 - 3 72 +3 +0.3 D 1640(11.31) +9 125 -11 78 +4 +0.5 The O-rings of Samples A - D were subjected to immersion tests according to ASTM-D 471 for 30 days using harsh chemical agents. The immersion tests using hydrazine and n-metnylpyrrolidone were conducted at room temperature.
Table VI presents the results of immersion testing of sample
O-rings in steam. Table VII presents the results of immersion testing of sample O-rings in hydrazine. Table VIII presents the results of immersion testing of sample O-rings in nmethylpyrrolidone.
As shown in Tables VI, VII and VIII, the control (Sample D) is generally more seriously affected by these harsh chemicals in relation to tensile strength, elongation, volume swell, and hardness tan any of the samples filled wit the fluorocarbon particulate polymers.
Therefore,perfluoroelastomeric compositions and articles formed according to the present invention have improved chemical resistance over perfluoroelastomers containing conventional fillers, such as carbon black.
EXAMPLE 3
Elastomeric compositions were prepared according to the process of the present invention by blending, at a temperature of about 140 - 160 C, 100 parts of the perfluoroelastomer CHEMRAZ (RTM) with varying amounts of TEFLON (RTM) PA and fluorographite having a value of x ranging from about 0.9 to about 1.0 (which is commercially available from Ozark Mahonina) . The amounts of fluorocarbon polymers added to each of these samples BB and CC are set forth in Table IX.
The compositions of the present invention were mixed and compression molded according to standard industry practice in the same manner as that set forth in Example 1 above to form # 214 O-rings. Each O-ring was press cured and subseouently post-cured for fou)= hours in te same manner as that set forth in Example 1 above. These O-rings were compared with a commercially available O-ring (Sample AA) formed from Kalrez (RTM) (No. 4079) which was obtained from du
Pont.
TABL- IX
PARTS PER 100 FRICTION FORCE L3S AT PARTS PERFLUORO- 0 p.5.1.
ELSTOMER ('1. atO Pa) SAMPLE PERFLUORO- TEFLON FLUORO- r IJUORO- DYNAMIC NO. ELASTOMER PA | GRAPHITE AWAY l WET DRY WET ( DRY AA | .CALREZ I | - - .3(19.1) 6.2(27.6) 17.8(79.2) 38A(170.3 B3 Cr:~MRAZ 3 5 5 ;.7 (16.5) 5.S (24.j) (72.1) 34.6(153.9j CC C:-:EDt?AZ0 1 6 | 6 6 1 (19.1) 4.3(19.1) 14.6(65.0) 28.9(i28.6) Each O-ring was tested to determine its breakaway and dynamic friction values, i.e., frictional drag, under wet and dry conditions. Seals having lower breakaway and dynamic friction values are desirable because they generally wear more slowly ana last longer in service than seals having higher breakaway and dynamic friction values.
Each O-ring was tested using the friction apparatus, indicated generally at 10, shown in Fig. 1. For dry friction testing, each seal was installed in a clean standard gland, indicated generally at 12, without any type of lubrication during either installation or testing. Fig. 2 is an enlarged detailed cross-sectional view of a portion of Fig. 1 showing the seal 14 positioned between the rod 16 and gland 12 for testing of the seal. The @@@ @@ of the aDDaratus 10 was hard
chrome having a 0.998 inch @ diameter and 8 - 12 R, finish. The
gland h inches ad a ciameter of 1.242 inches/and a length of 0.170
The test pressure was 0 c.s.i. The rod was cvcled
for 30 cycles per test at a velocity of 6 in/sec @@@@ and a stroke
length of 6 inches/. To determine the dynamic frictional force value for each O-ring, the rod was maintained under stacic conditions for G hours. For wet testing, both the rod and the gland were lubricated with Mil-H-5606 oil prior to testing.
The wet testing was then conducted in the same manner as the dry testing set forth above.
The dynamic and breakaway frictional force values for each O-ring were recorded using a conventional force transducer and computerized data acquisition system, designated as CRT" in Fig. 1. The dynamic and breakaway frictional force values for each O-ring are set forth in Table
IX. Further details of the data recording system will be omitted because the details are not necessary for one of ordinary skill in the art to understand the present invention.
As shown in Table IX and in Fig. 3, the dynamic frictional values under both wet and dry conditions for the 0rings of Samples 33 and CC, each of whicn were prepared according to the method of the present invencion, aft tower than the dynamic frictional values for the Kalrez @@@@@ O-ring (Sample AA). Likewise, as shown in Table IX and in Fig. , the breakaway frictional values under both wet and dry conditions for the O-rings of Samples BB and CC, each of which were prepared according to the method of the present invention, are lower than the breakaway frictional values for the Kalrez (RTM) O-ring (Sample AA). Therefore, both the dynamic and breakaway frictional values for O-rings formed according to the present method are less than the dynamic and breakaway frictional values for an O-ring formed from Kalrez (RTM) without a non-fibrillating fluorocarbon particulate polymer and are therefore less subject to wear.
In many dynamic sealing applications, low torquf starts, low running friction and reduced wear are important considerations when rating seal performance. The perfluoroelastomer products produced according to this invention provide these improvements as shown in Table V, detailing the coefficient of friction of compositions with and without these fillers.
It will be appreciated by those skilled in the art that changes could be made to the embodimer.ts described above without departing from the broad inventive concept thereof.
It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope o the present invention as defined by the appended claims.
Claims (31)
1. An elastomeric composition having improved resistance to chemical attack, comprising a mixture of:
a perfluoroelastomer and
a particulate fluorinated graphite polymer having a composition of (CFx)n where x ranges from about 0.25 to about 1.20 and n is at least about 103.
2. The elastomeric composition according to claim 1, wherein the perfluoroelastomer is a terpolymer of tetrafluoroethylene, a perfluoroalkyl vinyl ether and a perfluorinated cure site monomer which includes a functional group which permits crosslinking of the terpolymer.
3. The elastomeric composition according to claim 1, wherein the fluorinated graphite polymer has an average particle diameter of about 1 to about 50 microns.
4. The elastomeric composition according to claim 1, wherein the fluorinated graphite polymer comprises up to about 30 wtt of the elastomeric composition.
5. The elastomeric composition according to claim 4, wherein the fluorinated graphite polymer comprises about 5 to about 15 wt of the elastomeric composition.
6. The elastomeric composition of claim 1, wherein the mixture further comprises a non-fibrillating particulate fluorocarbon polymer.
7. The elastomeric composition according to claim 1, further comprising an additive selected from the group consisting of carbon black, clay, silicon dioxide, barium sulfate, polymeric fibers, curatives and plasticizers.
8. The elastomeric composition according to claim 7, wherein the plasticizer is a perfluorinated alkyl polyether.
9. A seal for preventing the leakage of a fluid between a first member and a second member and having improved chemical resistance to the fluid and reduced coefficients of friction at a surface of the seal, the seal comprising a mixture of:
a perfluoroelastomer and
a particulate fluorinated graphite polymer having a composition of (CFz)n where x ranges from about 0.25 to about 1.20 and n is at least about 103.
10. The seal according to claim 9, wherein the seal is formed in the shape of an O-ring.
11. A process for improving the resistance to chemical attack and increasing the strength of a perfluoroelastomer, comprising:
mixing the perfluoroelastomer with a non-fibrillating fluorocarbon particulate polymer and a particulate fluorinated graphite polymer having a composition of (CFx)n where x ranges from about 0.25 to about 1.20 and n is at least about 103 to form an elastomeric composition; and
processing the elastomeric composition at a processing temperature less than the melting temperature of the nonfibrillating fluorocarbon particulate polymer to disperse the fluorocarbon polymer and the fluorinated graphite polymer throughout the perfluoroelastomer while maintaining the fluorocarbon polymer and fluorinated graphite polymer in particulate form.
12. The process according to claim 11, wherein the perfluoroelastomer is a terpolymer of tetrafluoroethylene, a perfluoroalkyl vinyl ether and a perfluorinated cure site monomer which includes a functional group which permits crosslinking of the terpolymer.
13. The process according to claim 11, wherein the fluorocarbon polymer is selected from the group consisting of a low molecular weight (as hereinbefore defined) polytetrafluoroethylene homopolymer and a copolymer of tetrafluoroethylene and at least one of hexafluoropropylene and perfluoroalkyl vinyl ether.
14. The process according to claim 11, wherein the fluorinated graphite polymer has an average particle diameter of about 1 to about 50 microns.
15. The process according to claim 11, wherein the fluorinated graphite polymer comprises up to about 30 wt of the elastomeric composition.
16. The process according to claim 11, wherein the fluorinated graphite polymer comprises about 5 to about 15 wtW of the elastomeric composition.
17. The process according to claim 11, further comprising the step of mixing the elastomeric composition with an additive selected from the group consisting of carbon black, clay, silicon dioxide, barium sulfate, polymeric fibers, curatives and plasticizers.
18. The process according to claim 17, wherein the plasticizer is a perfluorinated alkyl polyether.
19. The process according to claim 11, wherein the processing temperature is less than about 1800C.
20. A method for increasing the resistance to chemical attack of an elastomeric seal and decreasing the coefficients of friction at a surface of the seal, the seal being for preventing the leakage of a fluid between a first member and a second member, comprising:
mixing a perfluoroelastomer with a non-fibrillating fluorocarbon particulate polymer and a particulate fluorinated graphite polymer having a composition of (CFx)n where x ranges from about 0.25 to about 1.20 and n is at least about 103 to form an elastomeric composition; and
processing the elastomeric composition at a temperature less than the melting temperature of the non-fibrillating fluorocarbon particulate polymer to disperse the fluorocarbon polymer and the fluorinated graphite polymer throughout the elastomeric composition while maintaining the fluorocarbon polymer and the fluorinated graphite polymer in particulate form to form an elastomeric seal, such that the seal has increased resistance to chemical attack and reduced coefficients of friction at the seal surface.
21. A seal according to claim 9, wherein the mixture further comprises a non-fibrillating particulate fluorocarbon polymer.
22. A method according to claim 20, wherein the fluorocarbon polymer is selected from the group consisting of (1) a low molecular weight (as hereinbefore defined) polytetrafluoroethylene homopolymer and (2) a copolymer of tetrafluoroethylene and at least one of hexafluoropropylene and a perfluoroalkyl vinyl ether.
23. A method for increasing the resistance to chemical attack of an elastomeric seal and decreasing the coefficients of friction at a surface of the seal, the seal being for preventing the leakage of a fluid between a first member and a second member, comprising:
mixing a perfluoroelastomer with a non-fibrillating fluorocarbon particulate polymer to form an elastomeric composition, wherein the perfluoroelastomer comprises a terpolymer of tetrafluoroethylene, a perfluoroalkyl vinyl ether and a perfluorinated cure site monomer which includes a functional group which permits cross linking of the terpolymer; and
processing the elastomeric composition at a temperature less than the melting temperature of the non-fibrillating fluorocarbon particulate polymer to disperse the fluorocarbon polymer throughout the elastomeric composition while maintaining the fluorocarbon polymer in particulate form to form an elastomeric seal, such that the seal has increased resistance to chemical attack and reduced coefficients of friction at the seal surface.
24. The method according to claim 23, further comprising the step of mixing the elastomeric composition with an additive selected from the group consisting of carbon black, clay, silicon dioxide, barium sulfate, a polymeric fiber, a curative and a plasticizer.
25. The method according to claim 23, wherein the seal is formed in the shape of an O-ring.
26. The method according to claim 23, wherein the processing temperature is less than about 1800C.
27. The method according to claim 23, further comprising the step of mixing the perfluoroelastomer and fluorocarbon particulate polymer with a particulate fluorinated graphite polymer.
28. The method according to claim 23, wherein the fluorocarbon polymer is selected from the group consisting of (1) a low molecular weight (as hereinbefore defined) polytetrafluoroethylene homopolymer and (2) a copolymer of tetrafluoroethylene and at least one of hexafluoropropylene and a perfluoroalkyl vinyl ether.
29. The method according to claim 23, further comprising the step of mixing the elastomeric composition with an additive selected from the group consisting of carbon black, clay, silicon dioxide, barium sulfate, polymeric fiber, a curative and a plasticizer.
30. The method according to claim 23, wherein the seal is formed in the shape of an O-ring.
31. The method according to claim 30, wherein the processing temperature is less than about 180 C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/092,144 US5444116A (en) | 1993-07-14 | 1993-07-14 | Perfluoroelastomeric compositions and seals having improved chemical resistance and methods of making the same |
GB9525977A GB2294465A (en) | 1993-07-14 | 1994-07-06 | Perfluoroelastomeric compositions and methods |
Publications (2)
Publication Number | Publication Date |
---|---|
GB9704231D0 GB9704231D0 (en) | 1997-04-16 |
GB2308368A true GB2308368A (en) | 1997-06-25 |
Family
ID=26308337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9704231A Withdrawn GB2308368A (en) | 1993-07-14 | 1994-07-06 | Perfluoroelastomeric compositions and seals |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2308368A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002028981A1 (en) * | 2000-10-02 | 2002-04-11 | HYDRO-QUéBEC | Hydrophobic composition and use on a substrate for preventing ice formation and corrosion |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4503171A (en) * | 1984-01-11 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Graphite reinforced perfluoroelastomer |
US4713418A (en) * | 1985-12-06 | 1987-12-15 | E. I. Du Pont De Nemours And Company | Blends of fluoroplastics and fluoroelastomers |
-
1994
- 1994-07-06 GB GB9704231A patent/GB2308368A/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4503171A (en) * | 1984-01-11 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Graphite reinforced perfluoroelastomer |
US4713418A (en) * | 1985-12-06 | 1987-12-15 | E. I. Du Pont De Nemours And Company | Blends of fluoroplastics and fluoroelastomers |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002028981A1 (en) * | 2000-10-02 | 2002-04-11 | HYDRO-QUéBEC | Hydrophobic composition and use on a substrate for preventing ice formation and corrosion |
US6974551B2 (en) | 2000-10-02 | 2005-12-13 | Hydro Quebec | Hydrophobic composition and use on a substrate for preventing ice formation and corrosion |
Also Published As
Publication number | Publication date |
---|---|
GB9704231D0 (en) | 1997-04-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5444116A (en) | Perfluoroelastomeric compositions and seals having improved chemical resistance and methods of making the same | |
US20070044906A1 (en) | Multilayer polymeric composites having a layer of dispersed fluoroelastomer in thermoplastic | |
US20070045967A1 (en) | Assemblies sealed with multilayer composite torsion seals having a layer of dispersed fluoroelastomer in thermoplastic | |
US20070048476A1 (en) | Assemblies sealed with multilayer composite compression seals having a layer of dispersed fluoroelastomer in thermoplastic | |
US4362069A (en) | High efficiency, abrasion resistant product and process | |
US20080207819A1 (en) | Compositions based on polyvinylidene fluoride | |
US5218026A (en) | Fluorine-containing elastomer composition | |
US6328316B1 (en) | Rubber seal for semi-dynamic applications | |
JP2002515525A (en) | Thermally stable perfluoroelastomer composition | |
JP4017671B2 (en) | Low permeability fluid seal for flow control device | |
US4830920A (en) | Fluorine-containing elastomer and a shaped article thereof | |
CN105111542A (en) | LNBR (liquid nitrile butadiene rubber) modified NBR (nitrile butadiene rubber) for wear-resistant and oil-resistant screw pump stator and preparation method of NBR | |
US5604285A (en) | Resin composition for sliding part | |
GB2308368A (en) | Perfluoroelastomeric compositions and seals | |
CA2863408C (en) | Rapid gas decompression-resistant fluoroelastomer compositions and molded articles | |
JP2579312B2 (en) | Fluorine-containing elastomer and molded article thereof | |
Maclachlan | Fluorocarbon elastomers: A technical review | |
US9371943B2 (en) | Process for lining metal pipelines | |
Schroeder | Fluorocarbon elastomers | |
JPH07228744A (en) | Fluororesin composition for sliding member | |
Drobny | Fluoro-Inorganic Elastomers | |
Thomas | Fluoroelastomer and perfluoroelastomer compatibility with advanced gas turbine lubricants | |
SCHROEDER | ELASTOMERS | |
Drobny | Fluorocarbon Elastomers | |
West et al. | Fluoroelastomer Polymers—Compounding and Testing for Downhole Environments |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |