# US 5,705,122 A · A method of making a composite ceramic fiber from pre-ceramic polymers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,705,122 A - Document ID: US5705122A - Status: Granted - Kind: A - Application number: 08/211,835 - Filed: 1994-04-29 - Granted: 1998-01-06 - Earliest claimed: 1991-10-30 - Inventors: Dennis John Gerard Curran - Web page: https://patentgrep.com/patent/US5705122A ## CPC - C04B 35/62227: {obtaining fibres} - D01F 9/08: of inorganic material (working or processing of metal wire B21F; from softened glass, minerals or slags C03B37/00) - C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE - D01F: CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS ## Abstract The invention pertains to a composite ceramic fibre which is made from a self-supporting composite polymeric fibre by the conjugate spinning of at least two dissimilar pre-ceramic polymers in shapes varying from cylindrical to ribbon-like, and pyrolysing the spun fibre to form a composite bilateral, core sheath or matrix-fibril ceramic fibre having regions with ceramic compositions derived from each of the polymers, enabling physical and chemical characteristics to be widely varied for use as matrix reinforcements and other applications. A pyrolysis furnace includes countercurrent controlled atmosphere gas flow for chemically stabilizing or modifying the fibres. ## Claims ### Claim 1 A method for making a composite ceramic fibre which comprises: conjugate spinning continuous lengths of a plurality of different fiber forming pre-ceramic polymers to form a self-supporting composite pre-ceramic polymeric fiber having at least two pre-ceramic polymeric components which each extend continuously along the length of said pre-ceramic fiber; pyrolyzing said composite pre-ceramic fiber thereby converting said composite pre-ceramic fiber into a composite ceramic fiber having at least two ceramic components which each extend continuously along the length of said ceramic fiber; said fiber forming pre-ceramic polymers including repeating units containing a ceramic-forming element other than carbon and oxygen. ### Claim 2 (depends on 1) A method according to claim 1 wherein the conjugate spinning is carried out to form a composite bilateral or core-sheath fibre structure. ### Claim 3 (depends on 2) A method according to claim 2 wherein the conjugate spinning is carried out to form a core, an intermediate sheath and an outer sheath. ### Claim 4 (depends on 2) A method according to claim 2 wherein a first polymeric ceramic precursor is co-extruded around a central core of a second polymeric ceramic precursor, and the second polymer is from 5 to 85% of the whole, by weight, at the point of extrusion. ### Claim 5 (depends on 1) A method according to claim 1 wherein the conjugate spinning is carried out by a method selected from the group consisting of wet spinning, dry spinning, melt spinning, dispersion spinning, emulsion spinning, and reaction spinning. ### Claim 6 (depends on 1) A method according to claim 1 wherein the dissimilar pre-ceramic polymers are immiscible. ### Claim 7 (depends on 1) A method according to claim 1 wherein the proportion of each pre-ceramic polymer is at least 5% by weight of the whole fibre before pyrolysis. ### Claim 8 (depends on 1) A method according to claim 1 wherein the pre-ceramic polymer is selected from the group consisting of organometallic and inorganic fibre-forming polymers, being polymeric compounds of ceramic-forming elements. ### Claim 9 (depends on 1) A method according to claim 1 wherein at least one of the pre-ceramic polymers is a pre-ceramic organic polymer. ### Claim 10 (depends on 1) A method according to claim 1 wherein at least one of the pre-ceramic polymers contains metal atoms in its repeating groups. ### Claim 11 (depends on 10) A method according to claim 10 wherein the metal is at least one selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, aluminium, gallium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, lanthanum, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and the lanthanoids. ### Claim 12 (depends on 1) A method according to claim 1 wherein at least one of the pre-ceramic polymers includes non-metals or metalloids selected from the group consisting of carbon, boron, silicon, nitrogen, oxygen, phosphorus, sulfur, germanium, and arsenic. ### Claim 13 (depends on 1) A method according to claim 1 wherein the composite polymeric fibre comprises a pre-ceramic polymer that is without metals and includes silicon or boron. ### Claim 14 (depends on 1) A method according to claim 1 wherein the composite polymeric fibre comprises a pre-ceramic polymer that forms a glass upon pyrolysis. ### Claim 15 (depends on 14) A method according to claim 14 wherein the glass is an aluminosilicate. ### Claim 16 (depends on 1) A method according to claim 1 wherein the composite polymeric fibre comprises a pre-ceramic alkoxide polymer. ### Claim 17 (depends on 1) A method according to claim 1 wherein the composite polymeric fibre comprises a pre-ceramic polyorganosiloxane. ### Claim 18 (depends on 1) A method according to claim 1 wherein the composite polymeric fibre comprises a pre-ceramic co-ordination polymer containing a co-ordination compound or metal complex in its repeating unit. ### Claim 19 (depends on 18) A method according to claim 18 wherein the said co-ordination polymer comprises a substituted metallocene. ### Claim 20 (depends on 19) A method according to claim 19 wherein the metallocene is a transition metal: cyclopentadiene pi-complex. ### Claim 21 (depends on 18) A method according to claim 18 wherein the said co-ordination polymer comprises a polymer of an organo-metallic co-ordination compound copolymerised with other species. ### Claim 22 (depends on 1) A method according to claim 1 wherein the composite polymeric fibre comprises a pre-ceramic organo-metallic vinyl polymer. ### Claim 23 (depends on 22) A method according to claim 22 wherein the vinyl polymer is a fibre-forming copolymer of two or more organo-metallic vinyl monomers. ### Claim 24 (depends on 1) A method according to claim 1 wherein the composite polymers fibre includes a refractory, ceramic, pre-ceramic and/or metal additive to modify the stoichiometry of the ceramic product upon pyrolysis. ### Claim 25 (depends on 24) A method according to claim 24 wherein the ceramic additive is incorporated by mixing with unpyrolysed polymer, or by surface coating it, in an amount up to 80% of the total weight. ### Claim 26 (depends on 24) A method according to claim 24 wherein the additive is selected from the group consisting of silicon nitride, silicon carbide and silicon hexaboride, and carbides, nitrides, carbonitrides, carboborides, diborides, silicides and carbosilicides of transition metals. ### Claim 27 (depends on 24) A method according to claim 24 wherein the additive is the ceramic oxide of a metal in the pre-ceramic polymer. ### Claim 28 (depends on 24) A method according to claim 24 wherein the additive comprises up to 80% by weight of a finely divided metal, silicon or boron. ### Claim 29 (depends on 1) A method according to claim 1 wherein the spun fibre is drawn whereby to orient the polymer chains and develop tensile strength before pyrolysis. ### Claim 30 (depends on 1) A method according to claim 1 wherein the fibre is spun at an initial diameter of 50 to 200 microns. ### Claim 31 (depends on 1) A method according to claim 1 wherein the spun fibre is given a preliminary surface oxidation before pyrolysis. ### Claim 32 (depends on 1) A method according to claim 1 wherein the spun fibre is given a preliminary heat treatment at about 300.degree. to 700.degree. C. in a controlled atmosphere prior to storage before pyrolysis. ### Claim 33 (depends on 1) A method according to claim 1 wherein the pyrolysis temperature is from 600.degree. C. to 2000.degree. C. ### Claim 34 (depends on 1) A method according to claim 1 wherein the pyrolysis step is performed by passing the spun pre-ceramic fibre to and through a controlled atmosphere furnace, and pyrolysing the fibre in the furnace. ### Claim 35 (depends on 34) A method according to claim 34 wherein the controlled atmosphere is provided by a gas which passes counter-current to the fibre or fibres through the furnace, and the furnace is divided into a fibre pre-heater zone, a pyrolysis zone, and a fibre after-cooler zone. ### Claim 36 (depends on 34) A method according to claim 34 wherein the controlled atmosphere is a reducing atmosphere provided by carbon monoxide, carbon dioxide, hydrogen, ammonia, or mixtures thereof. ### Claim 37 (depends on 34) A method according to claim 34 wherein the controlled atmosphere is a carburising atmosphere provided by methane, ethane, acetylene, or mixtures thereof. ### Claim 38 (depends on 34) A method according to claim 34 wherein the controlled atmosphere is a nitriding atmosphere provided by ammonia, nitrogen or hydrogen/ammonia mixtures. ### Claim 39 (depends on 34) A method according to claim 34 wherein chopped short fibres are pyrolysed during tumbling through a rotary cylindrical furnace. ### Claim 40 (depends on 1) A method according to claim 1 wherein the pyrolysed ceramic fibre is modified after pyrolysis by subjecting the fibre at elevated temperatures to a reactive material in vapour form. ### Claim 41 (depends on 40) A method according to claim 40 wherein the reactive material is selected from the group consisting of organometallic compounds, and metal and non-metal halides, in a carrier gas. ### Claim 42 (depends on 1) A method according to claim 1 wherein the ceramic fibre is subjected to chemical vapour deposition as a separate step or integrated with the pyrolysis. ### Claim 43 (depends on 1) A method according to claim 1 wherein the product of pyrolysis is thereafter annealed at a lower temperature. ### Claim 44 (depends on 1) The method of claim 1 wherein said fiber forming pre-ceramic polymers are spun without a separate organic polymer carrier or separate organometallic ceramic precursor being present in any of the components. ### Claim 45 A method of making a composite ceramic fibre comprising forming a self-supporting composite polymeric fibre by the conjugate spinning of at least two dissimilar pre-ceramic polymers to form a composite core-sheath fibre having a continuous core and a surrounding sheath respectively formed from said dissimilar polymers, wherein each of said polymers includes repeating units containing a ceramic-forming element other than carbon and oxygen, and thereafter pyrolysing the spun fibre to form a composite ceramic fibre having regions with dissimilar ceramic compositions derived from the respective dissimilar polymers, and wherein said spun core-sheath fibre is chopped before pyrolysis by pressing together the opposite sides of the sheath in such a way that the continuous core polymer is interrupted, and the sheath polymer is closed and sealed over the parted core polymer ends, before the sheath polymer is cut to separate the individual short fibres. ### Claim 46 A method of making a composite ceramic fibre comprising forming a self-supporting composite polymeric fibre by the conjugate spinning of at least two dissimilar pre-ceramic polymers, wherein each of said polymers includes repeating units containing a ceramic-forming element other than carbon and oxygen, and thereafter pyrolysing the spun fibre to form a composite ceramic fibre having regions with dissimilar ceramic compositions derived from the respective dissimilar polymers, and wherein the pyrolysis step is performed by passing the spun pre-ceramic fibre to a controlled atmosphere furnace, and pyrolysing the fibre in the furnace, and wherein the spun fibre is pyrolysed in a continuous helical groove on a rotating refractory cylinder.