CA2285592A1 - Flexible graphite composite - Google Patents
Flexible graphite composite Download PDFInfo
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- CA2285592A1 CA2285592A1 CA002285592A CA2285592A CA2285592A1 CA 2285592 A1 CA2285592 A1 CA 2285592A1 CA 002285592 A CA002285592 A CA 002285592A CA 2285592 A CA2285592 A CA 2285592A CA 2285592 A1 CA2285592 A1 CA 2285592A1
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- sheet
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/02—Sealings between relatively-stationary surfaces
- F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
- F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
- F16J15/104—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing characterised by structure
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/536—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite based on expanded graphite or complexed graphite
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/82—Asbestos; Glass; Fused silica
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
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- C04B2235/5224—Alumina or aluminates
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- C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
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- C04B2235/5264—Fibers characterised by the diameter of the fibers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- 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
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
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- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
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Abstract
Flexible graphite sheet having embedded ceramic fibers extending from its surfaces into the sheet to increase the permeability of the sheet to resin.
Description
FLEXIBLE GRAPHITE COMPOSITE
FIELD OF THE INVENTION
The present invention relates to a composite of flexible graphite and needle-shaped ceramic particles which can be used in the making of gaskets.
BACKGROUND OF THE INVENTION
The term "flexible graphite" as used herein represents the exfoliated reaction product of rapidly heated natural graphite particles which have been treated with an agent that intercalates into the crystal-structure of the graphite to expand the intercalated particles at least 80 or more times in the direction perpendicular to the carbon layers in the crystal structure. Flexible graphite and the making thereof is described in U.S. Pat. No. 3,404,061 Shane et al.
Expanded, i.e. exfoliated graphite may be compressed into thin sheets (hereinafter referred as flexible graphite "foil") with a density approaching theoretical density, although a density of about 50 to 85 lbs./ft.' is suitable for most applications, including compression into shapes suitable as seal rings in engine exhaust and other applications.
A common method for making expandable graphite particles, described by Shane et al in U.S. Patent No. 3,404,061 the disclosure of which is incorporated herein by reference. In the typical practice of this method, natural graphite flakes are intercalated by dispersing the flakes in a solution containing an oxidizing agent e.g., a mixture of nitric and sulfuric acid. The intercalation solution contains oxidizing and other intercalating agents known in the art. Examples include those containing oxidizing agents and oxidizing mixtures, such as solutions containing nitric acid, potassium chlorate, chromic acid, potassium permanganate, potassium chromate, potassium dichromate, perchloric acid, and the like, or mixtures, such as for example, concentrated nitric acid and chlorate, chromic acid and phosphoric acid, sulfuric acid and nitric acid, or mixtures of a strong organic acid, e.g. trifluoroacetic acid, and a strong oxidizing agent soluble in the organic acid. A preferred intercalating agent is a solution of a mixture of sulfuric acid, or sulfuric acid and phosphoric acid, and an oxidizing agent, i.e. nitric acid, perchloric acid, chromic acid, potassium permanganate, hydrogen peroxide, iodic or periodic acids, or the like. Although less preferred, the intercalation solutions may contain metal halides such as ferric chloride, and ferric chloride mixed with sulfuric acid, or a halide, such as bromine as a solution of bromine and sulfuric acid or bromine in an organic solvent. After the flakes are intercalated excess solution is drained from the flakes and after washing with water, the intercalated graphite flakes are dried and are expandable upon exposure to a flame for only a few seconds. The thus treated particles of graphite are hereafter referred to as "particles of intercalated graphite" .
Upon exposure to high temperature, the particles of intercalated graphite expand in dimension as much as 80 to 1000 or more times its original volume in an accordion-like fashion in the c-direction, _i.e. in the direction perpendicular to the crystalline planes of the constituent graphite particles. The exfoliated graphite particles are vermiform in appearance, and are therefore commonly referred to as worms. The worms may be compressed together into flexible sheets which, unlike the original graphite flakes, can be formed and cut into various shapes.
Flexible graphite foil is coherent, with good handling strength, and flexible graphite foil can be wound into rolls and can also be wrapped around metal fixtures such as mandrels, possesses desirable heat transfer properties and is, accordingly, particularly useful for high temperature applications such as engine exhaust seal ring applications. It has been proposed to increase the sealability of flexible graphite sheet or foil by impregnating the same with resin. However, the surface layers of flexible graphite sheet or foil, due to the alignment of exfoliated graphite particles and the constituent layers of atoms parallel to the surface of the flexible sheet or foil, resist resin impregnation when the sheet or foil is immersed in liquid resin. However, due to the well known anisotropy of flexible graphite, resin will flow readily within the flexible graphite sheet in directions parallel to the opposed parallel planar surfaces of the sheet or foil and the planes of the constituent graphite particles of the sheet, i.e. transverse to the "c axis" direction of the graphite particles if penetration into the flexible graphite sheet can first be achieved.
Accordingly, it is an object of the present invention to provide a flexible graphite sheet, or foil, of increased permeability to enable increased resin impregnation.
FIELD OF THE INVENTION
The present invention relates to a composite of flexible graphite and needle-shaped ceramic particles which can be used in the making of gaskets.
BACKGROUND OF THE INVENTION
The term "flexible graphite" as used herein represents the exfoliated reaction product of rapidly heated natural graphite particles which have been treated with an agent that intercalates into the crystal-structure of the graphite to expand the intercalated particles at least 80 or more times in the direction perpendicular to the carbon layers in the crystal structure. Flexible graphite and the making thereof is described in U.S. Pat. No. 3,404,061 Shane et al.
Expanded, i.e. exfoliated graphite may be compressed into thin sheets (hereinafter referred as flexible graphite "foil") with a density approaching theoretical density, although a density of about 50 to 85 lbs./ft.' is suitable for most applications, including compression into shapes suitable as seal rings in engine exhaust and other applications.
A common method for making expandable graphite particles, described by Shane et al in U.S. Patent No. 3,404,061 the disclosure of which is incorporated herein by reference. In the typical practice of this method, natural graphite flakes are intercalated by dispersing the flakes in a solution containing an oxidizing agent e.g., a mixture of nitric and sulfuric acid. The intercalation solution contains oxidizing and other intercalating agents known in the art. Examples include those containing oxidizing agents and oxidizing mixtures, such as solutions containing nitric acid, potassium chlorate, chromic acid, potassium permanganate, potassium chromate, potassium dichromate, perchloric acid, and the like, or mixtures, such as for example, concentrated nitric acid and chlorate, chromic acid and phosphoric acid, sulfuric acid and nitric acid, or mixtures of a strong organic acid, e.g. trifluoroacetic acid, and a strong oxidizing agent soluble in the organic acid. A preferred intercalating agent is a solution of a mixture of sulfuric acid, or sulfuric acid and phosphoric acid, and an oxidizing agent, i.e. nitric acid, perchloric acid, chromic acid, potassium permanganate, hydrogen peroxide, iodic or periodic acids, or the like. Although less preferred, the intercalation solutions may contain metal halides such as ferric chloride, and ferric chloride mixed with sulfuric acid, or a halide, such as bromine as a solution of bromine and sulfuric acid or bromine in an organic solvent. After the flakes are intercalated excess solution is drained from the flakes and after washing with water, the intercalated graphite flakes are dried and are expandable upon exposure to a flame for only a few seconds. The thus treated particles of graphite are hereafter referred to as "particles of intercalated graphite" .
Upon exposure to high temperature, the particles of intercalated graphite expand in dimension as much as 80 to 1000 or more times its original volume in an accordion-like fashion in the c-direction, _i.e. in the direction perpendicular to the crystalline planes of the constituent graphite particles. The exfoliated graphite particles are vermiform in appearance, and are therefore commonly referred to as worms. The worms may be compressed together into flexible sheets which, unlike the original graphite flakes, can be formed and cut into various shapes.
Flexible graphite foil is coherent, with good handling strength, and flexible graphite foil can be wound into rolls and can also be wrapped around metal fixtures such as mandrels, possesses desirable heat transfer properties and is, accordingly, particularly useful for high temperature applications such as engine exhaust seal ring applications. It has been proposed to increase the sealability of flexible graphite sheet or foil by impregnating the same with resin. However, the surface layers of flexible graphite sheet or foil, due to the alignment of exfoliated graphite particles and the constituent layers of atoms parallel to the surface of the flexible sheet or foil, resist resin impregnation when the sheet or foil is immersed in liquid resin. However, due to the well known anisotropy of flexible graphite, resin will flow readily within the flexible graphite sheet in directions parallel to the opposed parallel planar surfaces of the sheet or foil and the planes of the constituent graphite particles of the sheet, i.e. transverse to the "c axis" direction of the graphite particles if penetration into the flexible graphite sheet can first be achieved.
Accordingly, it is an object of the present invention to provide a flexible graphite sheet, or foil, of increased permeability to enable increased resin impregnation.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 shows, in an enlarged cross-section sketch of a sheet of flexible graphite (original thickness of 0.01 inch) containing ceramic fibers in accordance with the present invention;
Figures 2 through 6 are electron microscope views (original magnification 100X) at increasing electron beam intensity voltages (2.5 KV to 40 KV) of a portion of a planar surface of a flexible graphite sheet containing ceramic fibers in accordance with the present invention.
SUMMARY OF THE INVENTION
The present invention relates to a composite of a sheet of flexible graphite having opposed parallel, planar outer surfaces and needle-shaped ceramic fiber panicles which are embedded in the flexible sheet and which extend from interior the flexible sheet to at least one of the planar outer surfaces of the flexible graphite sheet.
DETAILED DESCRIPTION
In the practice of a particular embodiment of the present invention, intercalated natural graphite flakes are mixed and blended with from about 1.5 to 30 % by weight of needle-shaped ceramic fiber particles having a length of 0.15 to 1.5 millimeters. The width of the particles should be from 0.04 to 0.004 mm. The ceramic fiber particles are non-reactive and non-adhering to graphite and are stable at temperatures up to 2000°F, preferably 2500°F.
_ T__ _ _ _ _ Suitable ceramic fiber particles are formed of macerated quartz glass fibers, carbon and graphite fibers, zirconia, boron nitride, silicon carbide and magnesia fibers, naturally occurring mineral fibers such as calcium metasilicate fibers, calcium aluminum silicate fibers, aluminum oxide fibers and the like.
The mixture of intercalated natural graphite flake and needle-shaped ceramic fiber particles, in which the graphite flake and ceramic fiber particles are in general alignment, is exposed to a flame at a temperature up to 2500°F
to exfoliate, i.e. expand the intercalated graphite flake into expanded graphite particles from 80 to 1000 times the volume of the unexpended intercalated natural graphite flake which surround and entrap the needle-shaped ceramic fiber particles. Due to the expansion, the ceramic fiber particles are no longer in substantial alignment with the graphite particles but are randomly positioned in the mixture of exfoliated graphite and ceramic fiber. The mixture of exfoliated graphite particles and randomly oriented needle-shaped ceramic fiber particles is roll-pressed into sheet or foil typically 0.1 to 3.5 mm thick.
The resultant sheet, or foil, is characterized by having needle-shaped particles extending from interior of the flexible graphite sheet to and through at least one of the opposed planar surfaces of the flexible graphite sheet. Since the needle-shaped ceramic fiber particles are non-reactive and non-adhering to the graphite in the flexible sheet, a plurality of annular channels surrounding the respective needle-shaped particles is provided in the flexible graphite sheet extending from the opposed surfaces of the sheet into the body of the sheet.
These channels, with the flexible graphite sheet immersed in liquid resin, receive the resin which then infiltrates the flexible graphite sheet in the more permeable direction parallel to the planar surfaces of the flexible graphite sheet and the pressed, exfoliated graphite particles forming the sheet, assisted by channels formed by needle shaped ceramic fiber particles embedded between, but not penetrating the planar parallel surfaces of the flexible graphite sheet.
The ceramic fiber particles remain stable during all steps of the processing treatment so that the channels are not blocked by melted fiber or fiber decomposition products. After curing of the resin, within the graphite sheet the sealability of the flexible graphite sheet is enhanced for gaskets formed from said sheet. In a preferred embodiment the resin-containing sheet is calendered by roll pressing between pressure rolls.
Figure 1 is a drawing sketch based on microscope observations of 0.01 inch thick sheets of flexible graphite which shows a flexible graphite sheet 10, in cross-section, with parallel opposed planar surfaces 22, 24. Embedded ceramic fiber particles are shown at 30. Penetration of sheet 10 by ceramic fibers 30 is illustrated at 40.
EXAMPLE I
Natural graphite flake, sized 80 % by weight held on 50 mesh was treated in a mixture of 90 wt. % sulfuric acid and 10 wt. % nitric acid. The thus treated intercalated graphite flake was water washed and dried to about 1 % by weight water. One ( 1 ) pound of this intercalated flake was mixed with 0.15 pounds of needle-shaped ceramic fiber of commercially available calcium metasilicate sized mostly with a 15 to 25 % aspect ratio. The mixture of intercalated graphite and calcium metasilicate fiber was introduced into a furnace of 2500°F to obtain rapid expansion of the intercalated graphite flake into vermicular worm-shaped particles having a volume of about 325 times that of the unexpanded intercalated flake. The expanded worm-shaped particles .
surrounded the admixed calcium metasilicate fibers and the mixture was rolled into a flexible graphite sheet 0.01 inch thick and 24 inches wide in which admixed calcium metasilicate fibers extended from a surface of the sheet into the body of the sheet which contained about 12 % by weight of the calcium metasilicate fiber.
The electron microscope view of Figure 2 (100X- see 100 micron scale) shows the upper portion of a ceramic fiber 100 which penetrates a planar surface 22 of a flexible graphite sheet. Figures 3 to 6, at increasing voltages, look "deeper" into the flexible graphite sheet and show the penetration of ceramic fiber 100 into the flexible graphite sheet. Ceramic fibers embedded in the flexible graphite sheet below surface 72 are shown at 140, 160.
EXAMPLE II
A sample of the sheet of Example I, 8 inches wide was immersed in and pulled through a solution of resin 10 % phenolic resin with acetone diluent at a rate of 10 feet per minute. After immersion and drying, the sample showed an increase in weight of 18. 7 % .
The sample was further treated by heating to 235°C to stabilize the _g_ resin and the sheet was calendered between pressure rolls to a density of 1.5 gms/cc. The calendered sheet was soaked in oil and water and was unaffected.
A control sheet without any added ceramic fiber or resin additives exposed to the same test conditions increased about 35 % in weight and 8 % in thickness.
Sample sheets with 5 % , 15 % and 25 % by weight of calcium metasilicate fibers as additive were pulled through resin at a rate of IO feet per minute and were saturated with resin at about I7-19 % by weight of resin. A
control sample without any added ceramic fiber retained only 5 % by weight of resin at the same pull rate of 10 feet per minute.
Figure 1 shows, in an enlarged cross-section sketch of a sheet of flexible graphite (original thickness of 0.01 inch) containing ceramic fibers in accordance with the present invention;
Figures 2 through 6 are electron microscope views (original magnification 100X) at increasing electron beam intensity voltages (2.5 KV to 40 KV) of a portion of a planar surface of a flexible graphite sheet containing ceramic fibers in accordance with the present invention.
SUMMARY OF THE INVENTION
The present invention relates to a composite of a sheet of flexible graphite having opposed parallel, planar outer surfaces and needle-shaped ceramic fiber panicles which are embedded in the flexible sheet and which extend from interior the flexible sheet to at least one of the planar outer surfaces of the flexible graphite sheet.
DETAILED DESCRIPTION
In the practice of a particular embodiment of the present invention, intercalated natural graphite flakes are mixed and blended with from about 1.5 to 30 % by weight of needle-shaped ceramic fiber particles having a length of 0.15 to 1.5 millimeters. The width of the particles should be from 0.04 to 0.004 mm. The ceramic fiber particles are non-reactive and non-adhering to graphite and are stable at temperatures up to 2000°F, preferably 2500°F.
_ T__ _ _ _ _ Suitable ceramic fiber particles are formed of macerated quartz glass fibers, carbon and graphite fibers, zirconia, boron nitride, silicon carbide and magnesia fibers, naturally occurring mineral fibers such as calcium metasilicate fibers, calcium aluminum silicate fibers, aluminum oxide fibers and the like.
The mixture of intercalated natural graphite flake and needle-shaped ceramic fiber particles, in which the graphite flake and ceramic fiber particles are in general alignment, is exposed to a flame at a temperature up to 2500°F
to exfoliate, i.e. expand the intercalated graphite flake into expanded graphite particles from 80 to 1000 times the volume of the unexpended intercalated natural graphite flake which surround and entrap the needle-shaped ceramic fiber particles. Due to the expansion, the ceramic fiber particles are no longer in substantial alignment with the graphite particles but are randomly positioned in the mixture of exfoliated graphite and ceramic fiber. The mixture of exfoliated graphite particles and randomly oriented needle-shaped ceramic fiber particles is roll-pressed into sheet or foil typically 0.1 to 3.5 mm thick.
The resultant sheet, or foil, is characterized by having needle-shaped particles extending from interior of the flexible graphite sheet to and through at least one of the opposed planar surfaces of the flexible graphite sheet. Since the needle-shaped ceramic fiber particles are non-reactive and non-adhering to the graphite in the flexible sheet, a plurality of annular channels surrounding the respective needle-shaped particles is provided in the flexible graphite sheet extending from the opposed surfaces of the sheet into the body of the sheet.
These channels, with the flexible graphite sheet immersed in liquid resin, receive the resin which then infiltrates the flexible graphite sheet in the more permeable direction parallel to the planar surfaces of the flexible graphite sheet and the pressed, exfoliated graphite particles forming the sheet, assisted by channels formed by needle shaped ceramic fiber particles embedded between, but not penetrating the planar parallel surfaces of the flexible graphite sheet.
The ceramic fiber particles remain stable during all steps of the processing treatment so that the channels are not blocked by melted fiber or fiber decomposition products. After curing of the resin, within the graphite sheet the sealability of the flexible graphite sheet is enhanced for gaskets formed from said sheet. In a preferred embodiment the resin-containing sheet is calendered by roll pressing between pressure rolls.
Figure 1 is a drawing sketch based on microscope observations of 0.01 inch thick sheets of flexible graphite which shows a flexible graphite sheet 10, in cross-section, with parallel opposed planar surfaces 22, 24. Embedded ceramic fiber particles are shown at 30. Penetration of sheet 10 by ceramic fibers 30 is illustrated at 40.
EXAMPLE I
Natural graphite flake, sized 80 % by weight held on 50 mesh was treated in a mixture of 90 wt. % sulfuric acid and 10 wt. % nitric acid. The thus treated intercalated graphite flake was water washed and dried to about 1 % by weight water. One ( 1 ) pound of this intercalated flake was mixed with 0.15 pounds of needle-shaped ceramic fiber of commercially available calcium metasilicate sized mostly with a 15 to 25 % aspect ratio. The mixture of intercalated graphite and calcium metasilicate fiber was introduced into a furnace of 2500°F to obtain rapid expansion of the intercalated graphite flake into vermicular worm-shaped particles having a volume of about 325 times that of the unexpanded intercalated flake. The expanded worm-shaped particles .
surrounded the admixed calcium metasilicate fibers and the mixture was rolled into a flexible graphite sheet 0.01 inch thick and 24 inches wide in which admixed calcium metasilicate fibers extended from a surface of the sheet into the body of the sheet which contained about 12 % by weight of the calcium metasilicate fiber.
The electron microscope view of Figure 2 (100X- see 100 micron scale) shows the upper portion of a ceramic fiber 100 which penetrates a planar surface 22 of a flexible graphite sheet. Figures 3 to 6, at increasing voltages, look "deeper" into the flexible graphite sheet and show the penetration of ceramic fiber 100 into the flexible graphite sheet. Ceramic fibers embedded in the flexible graphite sheet below surface 72 are shown at 140, 160.
EXAMPLE II
A sample of the sheet of Example I, 8 inches wide was immersed in and pulled through a solution of resin 10 % phenolic resin with acetone diluent at a rate of 10 feet per minute. After immersion and drying, the sample showed an increase in weight of 18. 7 % .
The sample was further treated by heating to 235°C to stabilize the _g_ resin and the sheet was calendered between pressure rolls to a density of 1.5 gms/cc. The calendered sheet was soaked in oil and water and was unaffected.
A control sheet without any added ceramic fiber or resin additives exposed to the same test conditions increased about 35 % in weight and 8 % in thickness.
Sample sheets with 5 % , 15 % and 25 % by weight of calcium metasilicate fibers as additive were pulled through resin at a rate of IO feet per minute and were saturated with resin at about I7-19 % by weight of resin. A
control sample without any added ceramic fiber retained only 5 % by weight of resin at the same pull rate of 10 feet per minute.
Claims (8)
1. A flexible graphite sheet having opposite planar outer surfaces, said flexible graphite sheet having embedded therein a dispersion of a plurality of needle-shaped ceramic fiber particles which are non-reactive with flexible graphite and stable at temperatures up to 1371.1°C (2500°F) in an amount of about 1.5 to 30%
by weight, said needle-shaped ceramic fiber particles extending into said graphite sheet from at least one of said planar outer surfaces to increase the permeability of the graphite sheet to a liquid resin solution.
by weight, said needle-shaped ceramic fiber particles extending into said graphite sheet from at least one of said planar outer surfaces to increase the permeability of the graphite sheet to a liquid resin solution.
2. A flexible graphite sheet as claimed in claim 1, wherein the sheet is a roll-pressed sheet having a thickness of from 0.1 to 3.5 mm.
3. A flexible graphite sheet as claimed in claim 1, wherein the needle shaped ceramic fibers are selected from macerated quartz glass fibers, carbon fibers, graphite fibers, zirconia fibers, boron nitride fibers, silicon carbide fibers, magnesia fibers, calcium metasilicate fibers, calcium aluminium silicate fibers and aluminium oxide fibers.
4. A flexible graphite sheet as claimed in claim 1, wherein the needle shaped ceramic fiber particles are calcium metasilicate particles.
5. A flexible graphite sheet as claimed in claim 1, wherein said needle shaped ceramic fiber particles have a length of from 0.15 to 1.5 millimetres.
6. A flexible graphite sheet as claimed in claim 1, wherein a plurality of annular channels surround respective needle shaped ceramic fiber particles extending from at least one of said planar outer surfaces of the graphite sheet.
7. A method for making a flexible graphite sheet having opposite planar outer surfaces which is permeable to liquid resin solution, which comprises:
(i) treating natural graphite flake with an intercalating solution to obtain heat expandable, intercalated graphite flake particles;
(ii) mixing from about 1.5 to 30% by weight of needle-shaped ceramic fiber particles with said intercalated graphite flake particles to provide a blended mixture, said needle-shaped ceramic fiber particles being non-reactive with flexible graphite and stable at temperatures up to 1371.1°C (2500°F);
(iii) passing said blended mixture of intercalated natural graphite flake particles and needle-shaped ceramic fiber particles through a flame to cause rapid exfoliation of said intercalated natural graphite particles and provide a mixture of said needle-shaped ceramic fiber particles with exfoliated graphite particles; and (iv) passing said mixture of needle-shaped particles and exfoliated graphite particles between pressure rolls to form a compressed sheet of flexible graphite having embedded therein a dispersion of a plurality of needle-shaped particles which extend from at least one of said planar outer surfaces into the sheet.
(i) treating natural graphite flake with an intercalating solution to obtain heat expandable, intercalated graphite flake particles;
(ii) mixing from about 1.5 to 30% by weight of needle-shaped ceramic fiber particles with said intercalated graphite flake particles to provide a blended mixture, said needle-shaped ceramic fiber particles being non-reactive with flexible graphite and stable at temperatures up to 1371.1°C (2500°F);
(iii) passing said blended mixture of intercalated natural graphite flake particles and needle-shaped ceramic fiber particles through a flame to cause rapid exfoliation of said intercalated natural graphite particles and provide a mixture of said needle-shaped ceramic fiber particles with exfoliated graphite particles; and (iv) passing said mixture of needle-shaped particles and exfoliated graphite particles between pressure rolls to form a compressed sheet of flexible graphite having embedded therein a dispersion of a plurality of needle-shaped particles which extend from at least one of said planar outer surfaces into the sheet.
8. A method as claimed in claim 2, wherein (i) the sheet of step (iv) is immersed in resin which penetrates the sheet; (ii) the resin is stabilized by heating;
and (iii) the resin containing sheet is calendered by passing the resin containing sheet between pressure rolls.
and (iii) the resin containing sheet is calendered by passing the resin containing sheet between pressure rolls.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US08/833,136 US5902762A (en) | 1997-04-04 | 1997-04-04 | Flexible graphite composite |
US08/833,136 | 1997-04-04 | ||
PCT/US1998/006476 WO1998045224A1 (en) | 1997-04-04 | 1998-04-03 | Flexible graphite composite |
Publications (1)
Publication Number | Publication Date |
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CA2285592A1 true CA2285592A1 (en) | 1998-10-15 |
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ID=25263537
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002285592A Abandoned CA2285592A1 (en) | 1997-04-04 | 1998-04-03 | Flexible graphite composite |
Country Status (8)
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US (2) | US5902762A (en) |
CN (1) | CN1259111A (en) |
AT (1) | ATE226184T1 (en) |
CA (1) | CA2285592A1 (en) |
DE (1) | DE69808739T2 (en) |
ES (1) | ES2186151T3 (en) |
RU (1) | RU2185352C2 (en) |
TW (1) | TW397776B (en) |
Families Citing this family (144)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5902762A (en) * | 1997-04-04 | 1999-05-11 | Ucar Carbon Technology Corporation | Flexible graphite composite |
WO1999019908A1 (en) * | 1997-10-14 | 1999-04-22 | Matsushita Electric Industrial Co., Ltd. | Thermal conductive unit and thermal connection structure using same |
CA2338460A1 (en) * | 1998-06-02 | 1999-12-29 | Thomas William Weber | Formable flexible graphite sealing composites |
CA2344509C (en) * | 1999-04-07 | 2008-03-25 | Graftech Inc. | Flexible graphite article and method of manufacture |
US20020054995A1 (en) * | 1999-10-06 | 2002-05-09 | Marian Mazurkiewicz | Graphite platelet nanostructures |
AU2261101A (en) | 1999-12-17 | 2001-06-25 | Loctite Corporation | Impregnation of a graphite sheet with a sealant |
AU2096201A (en) | 1999-12-17 | 2001-06-25 | Loctite Corporation | Textured graphite sheet infused with a sealant |
US6479182B1 (en) | 2000-09-28 | 2002-11-12 | Graftech Inc. | Fuel cell electrode assembly with selective catalyst loading |
US20030108731A1 (en) * | 2000-01-24 | 2003-06-12 | Mercuri Robert Angelo | Molding of fluid permeable flexible graphite components for fuel cells |
BR0107793A (en) * | 2000-01-24 | 2002-10-29 | Graftech Inc | Fluid-permeable graphite article with increased electrical and thermal conductivity |
US6468686B1 (en) * | 2000-01-24 | 2002-10-22 | Graftech Inc. | Fluid permeable flexible graphite fuel cell electrode with enhanced electrical and thermal conductivity |
US6413671B1 (en) * | 2000-04-10 | 2002-07-02 | Gaftech Inc. | Flexible graphite article and fuel cell electrode with enhanced electrical and thermal conductivity |
US6528199B1 (en) | 2000-04-14 | 2003-03-04 | Graftech Inc. | Graphite article useful as an electrode for an electrochemical fuel cell |
US6506484B1 (en) * | 2000-01-24 | 2003-01-14 | Graftech Inc. | Fluid permeable flexible graphite article with enhanced electrical and thermal conductivity |
US6399204B1 (en) | 2000-01-26 | 2002-06-04 | Garlock, Inc. | Flexible multi-layer gasketing product |
US6482520B1 (en) | 2000-02-25 | 2002-11-19 | Jing Wen Tzeng | Thermal management system |
US6841250B2 (en) | 2000-02-25 | 2005-01-11 | Advanced Energy Technology Inc. | Thermal management system |
US6503626B1 (en) | 2000-02-25 | 2003-01-07 | Graftech Inc. | Graphite-based heat sink |
US20040072055A1 (en) * | 2000-04-14 | 2004-04-15 | Getz Matthew George | Graphite article useful as a fuel cell component substrate |
US6555271B1 (en) * | 2000-06-20 | 2003-04-29 | Graftech Inc. | Anode for lithium-ion battery |
US6503652B2 (en) | 2000-06-29 | 2003-01-07 | Graftech Inc. | Fuel cell assembly method with selective catalyst loading |
US6413663B1 (en) | 2000-06-29 | 2002-07-02 | Graftech Inc. | Fluid permeable flexible graphite fuel cell electrode |
WO2002066245A1 (en) * | 2000-11-02 | 2002-08-29 | Graftech Inc. | Flexible graphite sheet having increased isotropy |
US6605379B1 (en) | 2000-11-03 | 2003-08-12 | Grafttech Inc. | Hydrophobic fuel cell electrode |
US6521369B1 (en) | 2000-11-16 | 2003-02-18 | Graftech Inc. | Flooding-reducing fuel cell electrode |
US6517964B2 (en) * | 2000-11-30 | 2003-02-11 | Graftech Inc. | Catalyst support material for fuel cell |
DE10060838A1 (en) * | 2000-12-07 | 2002-06-13 | Sgl Carbon Ag | Resin-impregnated expanded graphite products, useful as sealing elements, fuel cell components or heat-conducting elements, comprises a solvent-free low-viscosity acrylic resin |
US8382004B2 (en) * | 2001-04-04 | 2013-02-26 | Graftech International Holdings Inc. | Flexible graphite flooring heat spreader |
US20020157818A1 (en) * | 2001-04-04 | 2002-10-31 | Julian Norley | Anisotropic thermal solution |
US20020157819A1 (en) * | 2001-04-04 | 2002-10-31 | Julian Norley | Graphite-based thermal dissipation component |
US20020164483A1 (en) * | 2001-04-04 | 2002-11-07 | Mercuri Robert Angelo | Graphite article having predetermined anisotropic characteristics and process therefor |
US7166912B2 (en) * | 2001-04-05 | 2007-01-23 | Advanced Energy Technology Inc. | Isolated thermal interface |
US6538892B2 (en) | 2001-05-02 | 2003-03-25 | Graftech Inc. | Radial finned heat sink |
US20020166654A1 (en) | 2001-05-02 | 2002-11-14 | Smalc Martin D. | Finned Heat Sink Assemblies |
US6702970B2 (en) | 2001-05-03 | 2004-03-09 | Advanced Energy Technology Inc. | Process to reduce sticking during surface treatment of graphite articles |
US6604457B2 (en) | 2001-05-11 | 2003-08-12 | Graftech Inc. | Process and apparatus for embossing graphite articles |
US6663807B2 (en) | 2001-05-14 | 2003-12-16 | Advanced Energy Technology Inc. | Process for complex shape formation using flexible graphite sheets |
US6673289B2 (en) | 2001-05-30 | 2004-01-06 | Advanced Energy Technology Inc. | Manufacture of materials from graphite particles |
US6582846B2 (en) | 2001-05-31 | 2003-06-24 | Graftech, Inc. | Method for preparing fuel cell component substrate of flexible graphite material having improved catalytic properties |
US7232601B2 (en) * | 2001-05-31 | 2007-06-19 | Advanced Energy Technology Inc. | Method for preparing composite flexible graphite material |
US20020182476A1 (en) * | 2001-05-31 | 2002-12-05 | Reynolds Robert Anderson | Method for preparing fuel cell component substrate of flexible graphite material having improved thermal and electrical properties |
US6613252B2 (en) | 2001-06-01 | 2003-09-02 | Advanced Energy Technology Inc. | Molding of materials from graphite particles |
US20020180094A1 (en) * | 2001-06-01 | 2002-12-05 | Gough Jeffrey John | Hydrophobic fuel cell component |
US7094311B2 (en) * | 2001-06-01 | 2006-08-22 | Advanced Energy Technology Inc. | Assembling bipolar plates |
US20030000640A1 (en) * | 2001-06-01 | 2003-01-02 | Graftech Inc. | Assembling bipolar plates |
US20050003200A1 (en) * | 2001-08-31 | 2005-01-06 | Julian Norley | Resin-impregnated flexible graphite articles |
US6758263B2 (en) * | 2001-12-13 | 2004-07-06 | Advanced Energy Technology Inc. | Heat dissipating component using high conducting inserts |
US6757154B2 (en) | 2001-12-13 | 2004-06-29 | Advanced Energy Technology Inc. | Double-layer capacitor components and method for preparing them |
US6746768B2 (en) | 2001-12-26 | 2004-06-08 | Advanced Energy Technology Inc. | Thermal interface material |
US20050175838A1 (en) * | 2001-12-26 | 2005-08-11 | Greinke Ronald A. | Thermal interface material |
US7108055B2 (en) * | 2002-03-29 | 2006-09-19 | Advanced Energy Technology Inc. | Optimized heat sink using high thermal conducting base and low thermal conducting fins |
US6841248B2 (en) | 2002-03-29 | 2005-01-11 | Advanced Energy Technology Inc. | Graphite article comprising a compressed mass of impregnated graphite particles and a reactive lubricant |
US7182898B2 (en) * | 2002-05-13 | 2007-02-27 | Advanced Energy Technology Inc. | Process for complex shape formation using flexible graphite sheets |
US6884745B2 (en) * | 2002-06-28 | 2005-04-26 | Advanced Energy Technology Inc. | Perforated cylindrical fuel cells |
US20050155743A1 (en) * | 2002-06-28 | 2005-07-21 | Getz George Jr. | Composite heat sink with metal base and graphite fins |
US6960402B2 (en) * | 2002-06-28 | 2005-11-01 | Advanced Energy Technology Inc. | Perforated cylindrical fuel cells |
US20040000735A1 (en) * | 2002-06-28 | 2004-01-01 | Graftech Inc. | Partially expanded, free flowing, acid treated graphite flake |
US20040062977A1 (en) * | 2002-10-01 | 2004-04-01 | Graftech, Inc. | Fuel cell power packs and methods of making such packs |
US20040062978A1 (en) * | 2002-10-01 | 2004-04-01 | Graftech, Inc. | Fuel cell power packs and methods of making such packs |
US7206189B2 (en) * | 2002-12-20 | 2007-04-17 | Advanced Energy Technology Inc. | Composite electrode and current collectors and processes for making the same |
US6830595B2 (en) * | 2002-12-20 | 2004-12-14 | Advanced Energy Technology Inc. | Method of making composite electrode and current collectors |
US20040121122A1 (en) * | 2002-12-20 | 2004-06-24 | Graftech, Inc. | Carbonaceous coatings on flexible graphite materials |
US20040118553A1 (en) * | 2002-12-23 | 2004-06-24 | Graftech, Inc. | Flexible graphite thermal management devices |
US20050064959A1 (en) * | 2003-09-23 | 2005-03-24 | Ortiz Luis M. | Promotional golf tee including a flat, flexible upper portion, alignement means and anchoring mechanism |
US7276273B2 (en) * | 2003-10-14 | 2007-10-02 | Advanced Energy Technology Inc. | Heat spreader for display device |
US7160619B2 (en) * | 2003-10-14 | 2007-01-09 | Advanced Energy Technology Inc. | Heat spreader for emissive display device |
US8211260B2 (en) | 2003-10-14 | 2012-07-03 | Graftech International Holdings Inc. | Heat spreader for plasma display panel |
US7666270B1 (en) | 2003-10-14 | 2010-02-23 | Graftech International Holdings Inc. | Heat spreader for display panel |
US7138029B2 (en) * | 2003-10-14 | 2006-11-21 | Advanced Energy Technology Inc. | Heat spreader for plasma display panel |
US7303820B2 (en) * | 2003-10-14 | 2007-12-04 | Graftech International Holdings Inc. | Heat spreader for display device |
US7150914B2 (en) * | 2003-10-14 | 2006-12-19 | Advanced Energy Technology Inc. | Heat spreader for emissive display device |
US7292441B2 (en) * | 2003-11-25 | 2007-11-06 | Advanced Energy Technology Inc. | Thermal solution for portable electronic devices |
US6982874B2 (en) | 2003-11-25 | 2006-01-03 | Advanced Energy Technology Inc. | Thermal solution for electronic devices |
US20050136187A1 (en) * | 2003-12-23 | 2005-06-23 | Weber Thomas W. | Method of improving adhesion of a coating to a flexible graphite material |
US7324576B2 (en) * | 2004-01-20 | 2008-01-29 | Graftech International Holdings Inc. | Joint strengthening ring for graphite electrodes |
US20050175062A1 (en) * | 2004-01-20 | 2005-08-11 | Brian Bowman | End-face seal for graphite electrodes |
US7324577B2 (en) * | 2004-01-20 | 2008-01-29 | Graftech International Holdings Inc. | End-face seal for male-female electrode joints |
US7466739B2 (en) * | 2004-01-20 | 2008-12-16 | Graftech International Holdings Inc. | Locking ring for graphite electrodes |
US20070047613A1 (en) * | 2004-01-20 | 2007-03-01 | Brian Bowman | Locking ring for graphite electrodes having friction layer |
US20070280327A1 (en) * | 2004-01-20 | 2007-12-06 | Smith Robert E | Electrode joint |
US7206330B2 (en) * | 2004-01-20 | 2007-04-17 | Ucar Carbon Company Inc. | End-face seal for graphite electrodes |
US7108917B2 (en) * | 2004-01-28 | 2006-09-19 | Advanced Energy Technology Inc. | Variably impregnated flexible graphite material and method |
US20050189673A1 (en) * | 2004-02-26 | 2005-09-01 | Jeremy Klug | Treatment of flexible graphite material and method thereof |
US7393587B2 (en) * | 2004-09-17 | 2008-07-01 | Graftech International Holdings Inc. | Sandwiched finstock |
US20060070720A1 (en) * | 2004-09-17 | 2006-04-06 | Capp Joseph P | Heat riser |
US7799428B2 (en) * | 2004-10-06 | 2010-09-21 | Graftech International Holdings Inc. | Sandwiched thermal solution |
US7306847B2 (en) * | 2005-01-28 | 2007-12-11 | Graftech International Holdings Inc. | Heat spreader for display device |
US20060225874A1 (en) * | 2005-04-11 | 2006-10-12 | Shives Gary D | Sandwiched thermal article |
US9081220B2 (en) | 2005-06-27 | 2015-07-14 | Graftech International Holdings Inc. | Optimized frame system for a display device |
US9104058B2 (en) | 2005-06-27 | 2015-08-11 | Graftech International Holdings Inc. | Optimized frame system for a liquid crystal display device |
US9087669B2 (en) | 2005-06-27 | 2015-07-21 | Graftech International Holdings Inc. | Display device having improved properties |
US7385819B1 (en) | 2005-06-27 | 2008-06-10 | Graftech International Holdings Inc. | Display device |
US7505275B2 (en) * | 2005-11-04 | 2009-03-17 | Graftech International Holdings Inc. | LED with integral via |
US7365988B2 (en) | 2005-11-04 | 2008-04-29 | Graftech International Holdings Inc. | Cycling LED heat spreader |
US7889502B1 (en) | 2005-11-04 | 2011-02-15 | Graftech International Holdings Inc. | Heat spreading circuit assembly |
US7303005B2 (en) * | 2005-11-04 | 2007-12-04 | Graftech International Holdings Inc. | Heat spreaders with vias |
US20070257359A1 (en) * | 2006-05-03 | 2007-11-08 | Reis Bradley E | Thermal Management Device For A Memory Module |
KR20080006304A (en) * | 2006-07-12 | 2008-01-16 | 삼성전자주식회사 | Organic light emitting diode display and method for manufacturing thereof |
US7420810B2 (en) * | 2006-09-12 | 2008-09-02 | Graftech International Holdings, Inc. | Base heat spreader with fins |
US7592695B2 (en) * | 2006-12-11 | 2009-09-22 | Graftech International Holdings Inc. | Compound heat sink |
US7824651B2 (en) * | 2007-05-08 | 2010-11-02 | Nanotek Instruments, Inc. | Method of producing exfoliated graphite, flexible graphite, and nano-scaled graphene platelets |
US20090101306A1 (en) * | 2007-10-22 | 2009-04-23 | Reis Bradley E | Heat Exchanger System |
US20100009174A1 (en) * | 2008-07-10 | 2010-01-14 | Reis Bradley E | Heat Dissipation For Low Profile Devices |
US20100314081A1 (en) * | 2009-06-12 | 2010-12-16 | Reis Bradley E | High Temperature Graphite Heat Exchanger |
US8081468B2 (en) | 2009-06-17 | 2011-12-20 | Laird Technologies, Inc. | Memory modules including compliant multilayered thermally-conductive interface assemblies |
US8405600B2 (en) * | 2009-12-04 | 2013-03-26 | Graftech International Holdings Inc. | Method for reducing temperature-caused degradation in the performance of a digital reader |
DE102010002989A1 (en) * | 2010-03-17 | 2011-09-22 | Sgl Carbon Se | Material composition, its production and use |
US9267184B2 (en) | 2010-02-05 | 2016-02-23 | Ati Properties, Inc. | Systems and methods for processing alloy ingots |
US8230899B2 (en) | 2010-02-05 | 2012-07-31 | Ati Properties, Inc. | Systems and methods for forming and processing alloy ingots |
US10207312B2 (en) | 2010-06-14 | 2019-02-19 | Ati Properties Llc | Lubrication processes for enhanced forgeability |
US20120033384A1 (en) * | 2010-08-06 | 2012-02-09 | Pillai Unnikrishnan G | Graphite wrapped heat spreading pillow |
US9475709B2 (en) | 2010-08-25 | 2016-10-25 | Lockheed Martin Corporation | Perforated graphene deionization or desalination |
US8361321B2 (en) * | 2010-08-25 | 2013-01-29 | Lockheed Martin Corporation | Perforated graphene deionization or desalination |
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US9539636B2 (en) | 2013-03-15 | 2017-01-10 | Ati Properties Llc | Articles, systems, and methods for forging alloys |
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WO2015069382A2 (en) * | 2013-09-18 | 2015-05-14 | Narendra Jeffri J | Flexible composites containing graphite and fillers |
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WO2016088682A1 (en) * | 2014-12-02 | 2016-06-09 | 積水化学工業株式会社 | Thermally-conductive sheet and method for producing same |
AU2016303048A1 (en) | 2015-08-05 | 2018-03-01 | Lockheed Martin Corporation | Perforatable sheets of graphene-based material |
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IT201600114685A1 (en) * | 2016-11-14 | 2018-05-14 | Silcart Spa | DEVICE FOR THE SUPPORT AND FIXING OF HEATING PIPELINES OF A HEATING SYSTEM PLACED IN UNDERWOODS, WALLS OR CEILINGS OF BUILDINGS |
WO2019060503A2 (en) | 2017-09-20 | 2019-03-28 | eChemion, Inc. | Manufacturing enhanced graphite metallic bipolar plate materials |
RU2706103C1 (en) * | 2018-06-29 | 2019-11-13 | Акционерное общество Научно-производственное объединение "УНИХИМТЕК" (АО НПО "УНИХИМТЕК") | Graphite foil, sheet material based thereon, seal and method of producing |
US11382261B2 (en) | 2018-08-28 | 2022-07-12 | Amvac Chemical Corporation | System and method for stacking containers |
DE102019209766A1 (en) * | 2019-07-03 | 2021-01-07 | Audi Ag | Fuel cell plate, bipolar plate and fuel cell device |
DE102021206824A1 (en) * | 2021-06-30 | 2023-01-05 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Thermal interface material, energy storage with a thermal interface material and method for their production |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB991581A (en) * | 1962-03-21 | 1965-05-12 | High Temperature Materials Inc | Expanded pyrolytic graphite and process for producing the same |
JPS5488911A (en) * | 1977-12-26 | 1979-07-14 | Matsushita Electric Ind Co Ltd | Production of thin ceramic sheet |
JPS6016385B2 (en) * | 1977-12-28 | 1985-04-25 | 日本カ−ボン株式会社 | Manufacturing method of flexible graphite products |
US4190257A (en) * | 1978-02-01 | 1980-02-26 | Union Carbide Corporation | Packing ring containing flexible graphite |
US4642201A (en) * | 1985-08-27 | 1987-02-10 | Intercal Company | Compositions for improving the stability of intercalated graphite structural members |
JP2503497B2 (en) * | 1987-03-30 | 1996-06-05 | 日立化成工業株式会社 | Graphite / fiber composite material |
DE3871660T2 (en) * | 1987-08-26 | 1993-01-21 | Matsushita Electric Ind Co Ltd | METHOD FOR PRODUCING A GRAPHITE FILM OR SHEET AND RADIATION-OPTICAL DEVICE USING THE GRAPHITE SHEET. |
JPH01123991A (en) * | 1987-11-09 | 1989-05-16 | Nikkiso Co Ltd | Heat-insulating structure of internal heat type high-temperature high-pressure device |
US5225379A (en) * | 1988-02-09 | 1993-07-06 | Ucar Carbon Technology Corporation | Composites of flexible graphite particles and amorphous carbon |
US4826181A (en) * | 1988-02-09 | 1989-05-02 | Union Carbide Corporation | Seal utilizing composites of flexible graphite particles and amorphous carbon |
US5228701A (en) * | 1988-03-22 | 1993-07-20 | Ucar Carbon Technology Corporation | Flexible graphite articles with an amorphous carbon phase at the surface |
US4911972A (en) * | 1988-08-12 | 1990-03-27 | Union Carbide Corporation | Insulating composite gasket |
US5225262A (en) * | 1991-04-29 | 1993-07-06 | A. W. Chesterton Co. | Braided high-temperature packing comprising a core of folded flexible graphite sheet |
US5176863A (en) * | 1991-08-06 | 1993-01-05 | Ucar Carbon Technology Corporation | Flexible graphite composite fire retardant wallpaper and method |
US5683778A (en) * | 1992-12-09 | 1997-11-04 | Crosier; Robert A. | Braided graphite-foil and method of production |
JP2619818B2 (en) * | 1994-11-21 | 1997-06-11 | 日本ピラー工業株式会社 | Thermal expansion inorganic fiber sealing material |
JPH08169478A (en) * | 1994-12-20 | 1996-07-02 | Taiyo Chem Kk | Heat generating sheet for microwave heating cooking and production thereof |
US5531454A (en) * | 1994-12-29 | 1996-07-02 | Indian Head Industries, Inc. | Expandable gasket, sealed joint and method of forming same |
US5902762A (en) * | 1997-04-04 | 1999-05-11 | Ucar Carbon Technology Corporation | Flexible graphite composite |
US5846459A (en) * | 1997-06-26 | 1998-12-08 | Ucar Carbon Technology Corporation | Method of forming a flexible graphite sheet with decreased anisotropy |
-
1997
- 1997-04-04 US US08/833,136 patent/US5902762A/en not_active Expired - Lifetime
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1998
- 1998-03-30 TW TW87104727A patent/TW397776B/en active
- 1998-04-03 CA CA002285592A patent/CA2285592A1/en not_active Abandoned
- 1998-04-03 RU RU99123046A patent/RU2185352C2/en not_active IP Right Cessation
- 1998-04-03 CN CN98805838A patent/CN1259111A/en active Pending
- 1998-04-03 ES ES98917979T patent/ES2186151T3/en not_active Expired - Lifetime
- 1998-04-03 DE DE69808739T patent/DE69808739T2/en not_active Expired - Lifetime
- 1998-04-03 AT AT98917979T patent/ATE226184T1/en not_active IP Right Cessation
- 1998-08-19 US US09/136,323 patent/US6074585A/en not_active Expired - Fee Related
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TW397776B (en) | 2000-07-11 |
RU2185352C2 (en) | 2002-07-20 |
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