US3767774A - Surface treatment of previously graphitized carbonaceous fibers - Google Patents
Surface treatment of previously graphitized carbonaceous fibers Download PDFInfo
- Publication number
- US3767774A US3767774A US00171233A US3767774DA US3767774A US 3767774 A US3767774 A US 3767774A US 00171233 A US00171233 A US 00171233A US 3767774D A US3767774D A US 3767774DA US 3767774 A US3767774 A US 3767774A
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- Prior art keywords
- fibrous material
- atmosphere
- fibers
- yarn
- thermal plasma
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/16—Chemical after-treatment of artificial filaments or the like during manufacture of carbon by physicochemical methods
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/26—Plasma torches
- H05H1/30—Plasma torches using applied electromagnetic fields, e.g. high frequency or microwave energy
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Definitions
- Graphite fibers are defined herein fibers'which consist essentially 'of carbon ⁇ and have' afpredominantl Xfr'ay diffraction pattern characteristic' ofv graphite.
- Amorphous carbon fibers are defined as fibers in which the bulk of the fiber-weightfcan be attributedv to carbon and which exhibit ain .essentially amorphous X-ray diffraction pattern.
- Graphite fibers generally have a higher Young's modulus than do amorphous carbon fibers and in addition are more' highlyv electrically and thermally conductive.- v
- a process for-the surface treatment of apredominantly graphitic carbonaceous fibrous material comprises: l (a) electrically inducing heating of a stream of'inert gas i present within a laterally enclosed zone to athernial plasma state 'of at least about one atmosphere pressure wherein from about-5 toabout 50 percent of the ga's is in an --ionized state, and wherein the tip of the thercontinuous lengthfof-a previouslyl graphitized'carbonaw ceou's fibrousfmaterial containing at least about 95 percent carbon by weight and exhibiting a predominantly graphiticiX-ray diffraction'pattern transversely through i' the 'tipofthe resultingithem'tal plasma present in the open atmosphere for aresidence' time of aboutOi-t to bonaceous tibrousmateria-l'- isheated to a maximum ternperature'of about 150G-to 2200 C.
- FIG. 2 is a photograph made with the aid. of a scanning electron microscope ata magnification of 6000 of a portiowcf agraphitic carbon filament vwhich has not undergone surface modification.
- FIG. 3 is a1 photograph made with the aid of a scanning electron microscope at a magnification of 6000 of a portion a similar graphitic carbon filament has I filament tensile properties thereof substantially diminished.
- the starting material y i Y I The carbonaceous fibers which are modified in accordance with the process of the presentinvention contain at least about 95 percent carbon by weightand 'exhibit a predominantly graphitic X-ray diffraction pattern. In a preferred embodimentof the process the vfgraphitized carbonaceous fibers which undergo surface treatment contain at least about 99-percent carbon by weight.
- the graphitized carbonaceous rfibrous materials are provided in a continuous length in any one of-a variety of physical configurations provided substantial access to the fiber surface is possible during the surface modification treatment'described hereafter.
- the fibrous materials may assume'the configuration of a-.continuous length of a multifilament yarn,-tape, tow, strand, cable, or similar fibrous assemblage.
- the fibrous material lis one or more continuous multifilament yarn.
- the previously graphitized carbonaceousfibrous material which is treated in the present processl optionally-may be' provided with a twist-which tends to improve the handling characteristics.
- a twist-which tends to improve the handling characteristics For instance, la twist of about 0.1 to 5 t.p.i.,and preferably about 0.3 to 1.0 t.p.i., may be imparted to a multilament yarn.
- a false twist may be used instead of or in addition to a real twist.
- one may select continuous bundles ofbrous material which possess essentially no twist.
- the graphitized carbonanous fibers which serve as the starting material in the present process may be formed in accordance with a variety of techniques as will be apparent to those skilled in the art.
- organic polymeric fibrous materials which are capable of undergoing thermal stabilization may be initially stabilized by treatment in an appropriate atmosphere at a moderate temperature (e.g. 200 to 400 C.), and subsequently heated in an inert atmosphere at a more highly elevated temperature until a carbonized and graphitized fibrous material is formed.
- the thermally stabilized material may be carbonized by heating in an inert at mosphere at a temperature of about 900 to 1000" C. and subsequently heated to a maximum temperature of 2000 to 3100 C.- (preferably 2400 to 3'100" C.) in an inert atmosphere for a sufficient residence time to produce substantial amounts of graphitic carbon.
- an organic polymeric fibrous material commonly vary with the composition of the precursor as will be apparent to those skilled in the art.
- Suitable organic polymeric fibrous materials from which the graphitized carbonaceous fibrous materials may be derived include an acrylic polymer, a cellulosic polymer, a polyamide, a polybenzimidazole, polyvinyl alcohol, etc. As discussed hereafter, acrylic polymericmaterials areparticularly suited for use as precursors in the formation 'of graphitizcd carbonaceous fibrous materials.
- suitable cellulosic materials include the natural and regenerated forms of cellulose, e.g. rayon.
- suitable polyamide materials include the aromatic polyamides, such as nylon 6T, which is formed by the condensation of hexamethyienediamine and terephthalic acid.
- a n illustrative example of a suitable polybenzimidazole is poly- 2,2' m phcnylene 5,5 bil benzimidazole.
- a fibrous acrylic polymeric material prior-to stabilization may be formed primarily of recurring acrylonitrle units.
- the acrylic polymer should contain not less than about mol percent of recurring acrylonitrile units with not more than l5 mol percent of a lmonovinyl compound which is copolymerizable with acrylonitrle 4such as styrene, methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl pyridine, and the like,.o r a plurality of such monovinyl compounds.
- multifilament bundlesrof an acrylic fibrous material may be initially stabilized in an oxygen-containing atmosphere (i.e. preoxidized) on a continuous basis is accordance with the teachings of U.S. Ser. No. 749,957, filed Aug. 5,v
- the stabilized acrylic fibrous .material which is preoxidized in an oxygen-containing atmosphere is black in appearance, contains a bound oxygen content of at least about 7 percent by weight as determined by the Unter-- zaucher analysis, retains its original fibrous configuration essentially intact, and is non-burning when .subjected to an ordinary match flame.
- a stabilized acrylic fibrous material is carbonized and gmphitized while passing through a temperature gradient present in a heating zone in accordance with the procedures described in commonly assigned U.S. Ser. Nos. 777,275, filed Nov. 20, 1968 of Charles M. Clarke, now abandoned; 17,780. filed Mar. 9, 1970 of Charles M. Clarke, Michael I Ram, and John P. Riggs, now U.S. Pat. No. 3,677,705; and 17,832, filed Mar. 9, 1970 of Charles M. Clarke, Michael I. Ram, and Arnold J. Rosenthal.
- U.S. Ser. Nos. 777,275 filed Nov. 20, 1968 of Charles M. Clarke, now abandoned; 17,780. filed Mar. 9, 1970 of Charles M. Clarke, Michael I Ram, and John P. Riggs, now U.S. Pat. No. 3,677,705; and 17,832, filed Mar. 9, 1970 of Charles M. Clarke, Michael I. Ram, and Arnold J. Rosenthal.
- a continuous length of stabilized acrylic fibrous material whichis non-burning when subjected to an ordinary match Vflamef and derived from an acrylic fibrous material selected from the oroup consisting of an acrylonitrle homopolymer and acrylonitrile copolymers which contain at least about 85 mol percent of acrylonitrle units and up to about 15 mol-percent of onefor more monovinyl units copolymerized therewith is converted to a graphitic fibrous material while preserving the original fibrous configuration 'essentially intact while passing through a carbonization/graphitization heating zone containing an inert gaseous atmosphere and a temperature gradient .in which the fibrous material is raised within a period of about 2t) to about 300 seconds from about 800 C.
- the equipment utilized Ato produce the heating zone used to produce the graphitized carbonaceous starting material. may be varied as will be apparent to those skilled l in the art. It is essential; that the apparatus selected be capable ofproducingthe required temperature while excluding the presence' of an oxidizing atmosphere.
- the continuous length of fibrous,l material undergoing carbonization and graphitization is. heated by use-vofan induction furnace.
- the fibrous vmaterial may be passed in the direction otitevv length through a hollow graphite tube or other susceptor which is situated withinthe windings of an induction coil.
- l field is oorioorltratod, at the tip. of 'tho oorldllotor and the.
- the fibrous material v because of itst small mass yand relatively large surface area instantaneously assumes substantially the same tem- 1 Poratllre as that. ofr the urbanization/graphitizatioll hooi ing z one through which it iis-continuously passed.
- Preferred inert gases for use in the process are monoatomic, e .g. argon,'heliu 'm, neon, z enon and radon. ParticularlyProforredmonoatomio inert eases are arson and helium.' A ⁇ diatomio inert gas such as' nitrogen may alterspiral flow present the ⁇ gas stream accordingly creates a thermal pinch :effect or a vortex stabilization effect wherein thelhermal plasma state is positioned within the lcentral portion of the zone in the substantial absence of contact with the periphery of the laterally enclosed zone. The'periphery of the laterally enclosed zone ⁇ rnay therefore be formed from conventional materials,
- a cooling medium may also cir- .culatewithin the vwall .of the zone.
- the temperature of the gas throughout the thermal plasma commonly ranges from about 4,000 to 20,000 K. Accordingly, the thermal'plasma state is substantially different than conventional plasmas (e.g. glow discharges) which arecncountered in neon lights, etc., due to the ex- I tremely high temperatures in the former because ofthe higher pressure of the gas present and the highervdegree of ionization.
- conventional plasmas e.g. glow discharges
- the tip or tail of the thermal plasma which extends into an open atmosphere commonly measures about 0.5 to 8 inches, ⁇ or more, in length and preferably about 2 to 4 inches in length.
- the tip of, the thermal plasma is comdesired. tho. oolllleilratiorloff tho till.. ofthe. llitrtllellllasma may be modified by the of a de liector.
- the length of the thermal plasma tio also may. b, modiliotl by a'iillnins the liow rato, ottllo.
- the thermal plasma utilized irl the present process is creatori by all tlscirodsle es ttshrliqllo- Ifrl assordance with this, technique the thermalgplasma Vstate is achieved by heatirlsA tbe" setto ioll'iratiolltomlioratllrt by means of oltotrisal. induction created Prsfer'ably by.' 'a sufrrounding coil carrying radio frequenoy (e.g. 0.5 kHz.
- radio frequenoy e.g. 0.5 kHz.
- the thermal plasma slate ' may be effectively controlled.
- the length-of the thermal plasma is alsoirlduenced to a substantial degree by the lonstb of- 'the surrounding coil. If desired. the. massellolielsi may bs .Stro's'tlislltd through the permanent positioning of s' illtta'llio sheet" within the magnetic, ⁇ field created bvftho raslis'frolqllorlsy power'.
- the continuous length of previo graphitized carbo.- naceous fibrous material may be continuously passed'in the direction of its length transversely through the same for a residence time of about 0.4 to 3.5V seconds, and more preferably for a vresidence time of about l to 2 seconds.
- the fibrous material is provided asa relatively more cornpact assemblage of a plurality o f'fibers, then longer residence times within the range indicated advantageously may be employed. Also.
- the fibrous material is heated to a maximum tempfatlll's Qf about 1509 0.2200. C., and more preferably to a maximumtemperature of about 1600 to 2000 C.
- the maximum temperature imparted to the fibrous material may be varied depending upon the exact portion lof the plasma tip which is transversed. The portion ofthe tip closest to the laterally enclosed zone will tend to heat the f i us material to a higher maximum temperature.
- the temperature of bl'Qus material may be determined by optical grignoter ttohoitiuos' which are well known in the art.
- the basic proton of tbs invention may be ,th odllolion of o' millor quantity of an additiye, such as oxygen, into the inert gas Stream which is indllslivoly sonvertoilto a vthermal plasma state.
- an additiye such as oxygen
- inorganic powders such as boron ni-f-v tride or boron carbide, can be'introduced into the inert gas stream, andV ultimately deposited upon the'surface of the fibrous material undergoing treatment.
- the surface treatment of the present process is accomplished in the absence of any-substantial diminution of the single filament tensile properties of the fibrous material. More specifically, the single filament tensile properties (Le. tensile strength and Youngs modulus) are substan tially identical following the surface treatment to those properties exhibited prior to the surface treatment.
- a comparison of fibers of FIGS. 2 (control) and 3 (surface treated in accordance with the present process) indicates that the appearance of the fibrous material following the surface treatment is substantially unchanged, with only a very shallow pitting of the fiber surface being observable.
- FIGS. 2 and 3 show a finely textured surface on the lobes of the fiber; however, the troughs between the lobes of the fiber of FIG. 3 appear to be slightly rougher in texture.
- FIG. 4 indicates the appearance of a fiber which has undergone an excessive and undersirable surface treatment and is excessively pitted.
- the surface modification imparted to the previously carbonaceous' fibrous material through the use of the present process has been found to exhibit an appreciable life which is not diminished to any substantial degree even after the passage of 30, or more days.
- the surface treatment of the present process makes possible improved adhesive bonding between the resulting fibrous material, and a resinous matrix material. Accordingly, graphite fiber reinforced composite materials which incorporate fibers treated as heretofore described exhibit enhanced shear strength, flexural strength, compressive strength, etc.
- the resinous matrix material employed in the formation of such composite materials is commonly a polar thermosetting resin suchas an epoxy,v a polyimide, a polyester, a phenolic, etc.
- the graphitized carbonaccous fibrous material is commonlyprovided ink such resulting composite materials in either an aligned or random fashion in a concentration of about 20 to 70 percent by volume.
- the apparatus wherein the surface modification treat ⁇ ment was conductedvin cludes a vertical quartz tube 1 having a length of'6 inches, an inner diameter of 1% inches, and a ⁇ wall thickness of M6 inch.4
- a larger concentric quartz tube 2 having an internal diameter of 2% inches and a wall thickness of l/ip, inch is provided outside quartz tube 1 and forms a wall cavity 4 wherein a water cooling medium is continuously circulated.
- the cool'- ing medium enters inlet 6 and exits at outlet 8.
- the lower ends of quartz tubes 1 and 2 are mounted in steel base 10.
- a relatively short section of cylindrical Pyrex glass tubing l2 having a length of 2 inches, an inner diameter of 1 inch and a wall thickness of ly inch which is provided with rperforations (not shown) to aid in the mixing of the inert gas.
- An annular space 14 is accordingly provided between the inner wall of quartz tube 1 and the outer wall of Pyrex glass tubing 12.
- Gas inlet tube 16 passes through base 10 and is directed longitudinally along the central region of the zone 20 defined by quartz tube 1.
- Gas inlet tube 22 also is situated within base 10 and communicates tangentially with annular space 14.
- a hollow copper induction coil 24 having an outer diameter of A inch and a wall thickness of M52 inch is wound about and in contact with the outer wall of quartz tube 2.
- the continuous coil has 5 turns which are each separated by 3/s inch. Water is continuously circulated through hollow copper induction coil 24.
- Argon gas is introduced through inlet tube 22 tangentially into annular space 14 at a rate of 20 EL3/hr. This gas accordingly passes spirally along the internal walls of Y zone 20 after passing through Pyrex glass tubing 12.. The' pressure ofthe gas stream passing upwardly through zone 20 is slightly in excess of l atmosphere. Quartz tube ⁇ l. is open to the air atmosphere at 32.
- a thermal plasma 40 is electrically induced within the zone 20 following 'the temporary insertion of a metallic wire (not shown) through opening '32 whereinabout 5 to 15 percent of the argon gasnisin an ionized state.
- Radio frequency power is applied tothe copper induction coil 24 via leads 42 and 44 and highfrequency-l power supply 46.y
- the power supply 46 consists of a Lepel Model No. T-IO-S-MC-E-S high frequency power unit capable of delivering up to a l0 kW signal at a frequency of up to 8 mHz.
- a 10 kv. peak-topeak A.C..signal having a frequency of S mHz. is applied. 1
- the thermal plasma 40 has aV total length of about 6 inches, and a maximum width' of 1%' inches. Approximately 3 inches of the thermal plasma 40 extend beyond the open end 32 of vertical quartz tube 1 into the air atmosphere.
- the temperaturev of the gas within the thermaly plasma ranges from about 4,000 K. at the extreme tip to about 8,000 K. atqthe area surrounded by coil 24.
- the temperature of the gas- ⁇ within the tipportion of the thermal plasma present within the air atmosphere ranges from about 4,000 to 6,000 K.; A
- the previously gr'aphitled carbonaceous yarn 50 is next continuously'- unwound from feed bobbin 52, and is continuously passed in-the direction of .its length-through thetip of the thermal plasma 40 which is presentin the air atmosphere.
- the yarn speed andexact portion of the thermal plasma transversed are varied to producethe surface treatment residence times, and maximum yarn temperatures indicated.
- the position of the yarn withinthe tip of the thermal plasma 40 is governed by the locations of rollers 54 and 56.
- the resulting surface'treated yarn 58 is next passed through liquid resin bath 60 consisting of a liquidepoxy resin-hardener mixture at ambient temperature (i.e. 25 C.) by ⁇ the aid of immersed roller 62, and theresin lmregnated surface treated yarn is Ataken up on bobbin 64 with the aid of roller 66.
- the liquid -resin system was provided as a solventless system which contained parts by weight epoxy resin and about 87 parts by weight of anhydride curing agent. ⁇ 'l
- Composite ⁇ articles were next formed employing the resin impregnated surface modified yarn.
- the composite articles were rectangular bars consisting of about 50 percent by volume of the yarn and having dimensions of l/s inch x ld inch x 5 inches.
- the composite articles were formed by unidirectional layup ⁇ of the required quantity of impregnated yarn in a steell mold and compression molding the layup for2 hours at 95 C., and 3 hours at 200 C. in a heated platen press at about 100 p.s.i. pressure. The mold was cooledslowly and the composite article was removed from the mold cavity and cut to size for testing.
- the horizontal interlaminar shearstrengths reported were determined by short beam testing of the graphite fiber reinforced composite according to the procedure of ASTM D2344-65T as modified' for straight bar testing at a 4:1 span to depth ratio.
- the graphitic carbonaceous yarn undergoing treatment was derived from acrylonitrile homopolymer yarn in laccordance with procedures described in United States Ser. Nos 749,957, filed Aug, 5, i968 and 777,957 filed Nov. 20, 1968.
- the yarn consisted of a 1600 fil. bundle having a total denier of about 1000. had a carbon content in excess of 99 percent by weight, exhibited a predomininantly graphitic X-ray diffraction pattern, a single filament tenacity of about i3 grams per denier and aV single filament Youngs modulus of about 50 million p.s.i.
- the following data summarizes the surface treatment conditions employed and the composite properties achieved.
- the graphitic carbonaceous yarn undergoing treatment was derived from a cellulosic precursor and was commercially available from the Union Carbide Corporation
- a composite article was formed as heretofore described employing anv identical graphitized carbonaceous yarn without subjecting the same under the designation Thornell 5.0 carbon yarn.
- the yam consisted of a 720 fil. bundle having a total denier of about 350, had a carbon content in excess of 99 percent by weight, exhibited a predominantly graphitic X-ray diffraction pattern, a ⁇ single filament tenacity of about 338,000 p.s.i., and a single filament Youngs modulus of about 52 million p.s.i.
- the graphitic carbonaccous yarn undergoing treatment was derived from acrylonitrile homopolymer yarn in accordance with procedures described in United States Ser. Nos. 749,957, filed Aug. 5, 1968, and 777,957, filed Nov. 20, 1968.
- the yarn consisted of a 400 fil. bundle having a total denierof about 400, had a carbon content in ex cess of 99 percent by weight, exhibited a predominantly graphitic X-ray diffraction pattern, a single filament tenacity of about 13 grams per denier and a single filament Youngs modulus of about 70 million p.s.i. v.
- a process for the surface treatment of a predominantly graphitic carbonaceous fibrous material comprising: y
- said'stre'am of inert gas is selected from the gen.' argon, and helium.
- a process for the surface'treatment of a predominantly graphitic carbonaceous fibrous material comprismg:
- said inert gas is selected from the group consisting of nitrogen, argon, and helium.
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Abstract
AN IMPROVED PROCESS IS PROVIDED FOR MODIFYING THE SURFACE CHARACTERISTICS OF A PREDOMINANTLY GRAPHITIC CARBONACEOUS FIBROUS MATERIAL THEREBY TO FACILITATE ENHANCED ADHESION BETWEEN THE FIBROUS MATERIAL AND A MATRIX MATERIAL. THE FIBROUS MATERIAL IS CONTINUOUSLY PASSED FOR AN EXTEREMELY BRIEF RESIDENCE TIME TRANSVERSELY THROUGH THE TIP OF AN INERT GAS THERMAL PLASMA PRESENT IN AN OPEN ATMOSPHERE. COMPOSITED ARTICLES OF ENHANCED INTERLAMINAR SHEAR STRENGTH MAY BE FORMED BY INCORATING THE FIBERS
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US17123371A | 1971-08-12 | 1971-08-12 |
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US3767774A true US3767774A (en) | 1973-10-23 |
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US00171233A Expired - Lifetime US3767774A (en) | 1971-08-12 | 1971-08-12 | Surface treatment of previously graphitized carbonaceous fibers |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4311630A (en) * | 1979-04-17 | 1982-01-19 | California Institute Of Technology | Gasifiable carbon-graphite fibers |
US4503171A (en) * | 1984-01-11 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Graphite reinforced perfluoroelastomer |
US4915925A (en) * | 1985-02-11 | 1990-04-10 | Chung Deborah D L | Exfoliated graphite fibers and associated method |
US6514449B1 (en) | 2000-09-22 | 2003-02-04 | Ut-Battelle, Llc | Microwave and plasma-assisted modification of composite fiber surface topography |
US20140127424A1 (en) * | 2012-11-08 | 2014-05-08 | Ford Global Technologies, Llc | Method and Apparatus for Bonding Functional Groups to the Surface of a Substrate |
EP2904881A4 (en) * | 2012-07-13 | 2016-06-01 | Perkinelmer Health Sci Inc | Torches and methods of using them |
-
1971
- 1971-08-12 US US00171233A patent/US3767774A/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4311630A (en) * | 1979-04-17 | 1982-01-19 | California Institute Of Technology | Gasifiable carbon-graphite fibers |
US4503171A (en) * | 1984-01-11 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Graphite reinforced perfluoroelastomer |
US4915925A (en) * | 1985-02-11 | 1990-04-10 | Chung Deborah D L | Exfoliated graphite fibers and associated method |
US6514449B1 (en) | 2000-09-22 | 2003-02-04 | Ut-Battelle, Llc | Microwave and plasma-assisted modification of composite fiber surface topography |
EP2904881A4 (en) * | 2012-07-13 | 2016-06-01 | Perkinelmer Health Sci Inc | Torches and methods of using them |
US20140127424A1 (en) * | 2012-11-08 | 2014-05-08 | Ford Global Technologies, Llc | Method and Apparatus for Bonding Functional Groups to the Surface of a Substrate |
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Owner name: SUBJECT TO AGREEMENT RECITED SEE DOCUMENT FOR DETA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:BASF STRUCTURAL MATERIALS INC.;REEL/FRAME:004718/0001 Effective date: 19860108 Owner name: BASF AKTIENGESELLSCHAFT, D-6700 LUDWIGSHAFEN, GERM Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:BASF STRUCTURAL MATERIALS INC.;REEL/FRAME:004718/0001 Effective date: 19860108 |