# US 5,350,637 A · Microlaminated composites and method > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,350,637 A - Document ID: US5350637A - Status: Granted - Kind: A - Application number: 07/968,667 - Filed: 1992-10-30 - Granted: 1994-09-27 - Earliest claimed: 1992-10-30 - Assignees: Corning Incorporated - Inventors: Thomas D. Ketcham; Leroy S. Share; Dell J. St. Julien - Web page: https://patentgrep.com/patent/US5350637A ## CPC - B32B 18/00: Layered products essentially comprising ceramics, e.g. refractory products - B32B 15/04: comprising metal as the main or only constituent of a layer, {which is} next to another layer of {the same or of} a {different material (next to a bituminous or tarry layer B32B11/08; next to a water-setting substance layer B32B13/06; next to a glass layer B32B17/061; next to a cellulosic plastic layer B32B23/042)} - C04B 35/645: Pressure sintering - C04B 37/005: {consisting of glass or ceramic material} - C04B 37/006: {consisting of metals or metal salts} - C04B 37/021: {in a direct manner, e.g. direct copper bonding [DCB]} - C04B 2235/6562: Heating rate - C04B 2235/6565: Cooling rate - C04B 2235/6567: Treatment time - C04B 2235/6581: Total pressure below 1 atmosphere, e.g. vacuum - C04B 2237/068: based on refractory oxides, e.g. zirconia - C04B 2237/10: Glass interlayers, e.g. frit or flux - C04B 2237/121: based on aluminium - C04B 2237/122: based on refractory metals - C04B 2237/123: based on iron group metals, e.g. steel - C04B 2237/124: based on copper - C04B 2237/16: Silicon interlayers - C04B 2237/34: Oxidic - C04B 2237/341: Silica or silicates - C04B 2237/343: Alumina or aluminates - C04B 2237/346: Titania or titanates - C04B 2237/348: Zirconia, hafnia, zirconates or hafnates - C04B 2237/36: Non-oxidic - C04B 2237/365: Silicon carbide - C04B 2237/368: Silicon nitride - C04B 2237/402: Aluminium - C04B 2237/403: Refractory metals - C04B 2237/405: Iron metal group, e.g. Co or Ni - C04B 2237/406: Iron, e.g. steel - C04B 2237/407: Copper - C04B 2237/567: made of metal - C04B 2237/62: Forming laminates or joined articles comprising holes, channels or other types of openings - C04B 2237/66: Forming laminates or joined articles showing high dimensional accuracy, e.g. indicated by the warpage - C04B 2237/68: Forming laminates or joining articles wherein at least one substrate contains at least two different parts of macro-size, e.g. one ceramic substrate layer containing an embedded conductor or electrode - C04B 2237/704: of one or more of the ceramic layers or articles - C04B 2237/706: of one or more of the metallic layers or articles - C04B 2237/708: of one or more of the interlayers - C04B 2237/72: Forming laminates or joined articles comprising at least two interlayers directly next to each other - C04B 2237/76: Forming laminates or joined articles comprising at least one member in the form other than a sheet or disc, e.g. two tubes or a tube and a sheet or disc - C04B 2237/82: Two substrates not completely covering each other, e.g. two plates in a staggered position - F05C 2201/0448: Steel - Y10S 264/36: Processes of making metal-ceramics - Y10S 264/57: Processes of forming layered products - Y10T 428/12007: Component of composite having metal continuous phase interengaged with nonmetal continuous phase - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - 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 - F05C: INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract Microlaminated composite articles are made by combining one or more sheets of flexible sintered crystalline ceramic foil with one or multiple inorganic substrate layers, e.g., of metal foil, to form a stack which is then heated below the melting temperatures of the foil and substrate layers, and under slight or moderate pressure, to provide a well-bonded composite article which is essentially free of interlaminar cementing or sealing materials. ## Claims ### Claim 1 A method for making a microlaminated composite article which essentially consists the steps of: providing at least one sheet of flexible sintered crystalline ceramic foil; providing at least one inorganic substrate layer of a metal, intermetallic compound or crystalline ceramic material; stacking the ceramic foil on the substrate layer; and heating the stack under pressure at a temperature and for a time at least sufficient to obtain permanent bonding of the ceramic foil sheet directly to the inorganic substrate layer. ### Claim 2 A method for making a microlaminated composite article which essentially consists the steps of: providing a plurality of sheets of flexible sintered crystalline ceramic foil; providing one or a plurality of inorganic substrate layers of a metal, intermetallic compound or crystalline ceramic material; forming a sheet stack wherein at least some of the sheets of ceramic foil are in contact with one or more of the inorganic substrate layers; and heating the sheet stack under pressure to a temperature and for a time at least sufficient to obtain permanent bonding of the ceramic foil sheets directly to the one or more inorganic substrate layers in contact therewith. ### Claim 3 (depends on 2) A method in accordance with claim 2 wherein the substrate layers are sheets of flexible metal, intermetallic or ceramic foil, and wherein the sheet stack is characterized by at least some alternate interleaving of the first sheets and the second sheets or layers. ### Claim 4 (depends on 1) A method in accordance with claim 1 wherein the pressure does not exceed about 500 kPa. ### Claim 5 A method for making a composite article which essentially consists the steps of: providing one or more sheets of a flexible sintered crystalline ceramic foil; providing one or more inorganic substrate sheets of metallic or intermetallic composition; forming the sheets of foil and substrate sheets into a sheet stack wherein one or more sheets of the ceramic foil are positioned adjacent one or more of the inorganic substrate sheets; heating the ceramic foil and substrate sheets to a temperature in the range from about 300 .degree. C. below the lowest sintering temperature of the ceramic foil and inorganic substrate sheets to just below lowest melting temperature of the ceramic foil and inorganic substrate sheets; while applying pressure to the sheet stack, said pressure being at least sufficient to insure full surface contact between the foil and substrate sheets; said heating being continued for a time at least sufficient to obtain direct physical bonding of the ceramic foil to the inorganic substrate sheets. ### Claim 6 (depends on 5) A method in accordance with claim 5 wherein a plurality of sheets of ceramic foil and a plurality of inorganic substrate sheets are provided, wherein the inorganic substrate sheets include sheets of metallic or intermetallic foil, and wherein at least some of the ceramic foil sheets are interleaved with the sheets of metallic or intermetallic foil. ### Claim 7 (depends on 6) A method in accordance with claim 6 wherein the ceramic foil has a composition selected from the group consisting of zirconia, stabilized or partially stabilized zirconia, hafnia, alumina, silica, titania, mullite, spinel, chromium oxide, sialon, hasicon, silicon carbide, titanium carbide, silicon nitride, titanium nitride, zircon, zirconium carbide, titanium diboride, and combinations thereof. ### Claim 8 (depends on 7) A method in accordance with claim 7 wherein the ceramic foil has a composition selected from the group consisting of stabilized zirconia and partially stabilized zirconia, and wherein the zirconia includes at least one stabilizer selected from the group consisting of alkaline earth oxides, rare earth oxides, and combinations thereof. ### Claim 9 (depends on 7) A method in accordance with claim 7 wherein the ceramic foil has a thickness in the range of about 10-100 micrometers. ### Claim 10 (depends on 9) A method in accordance with claim 9 wherein the ceramic foil has a thickness in the range of about 25-50 micrometers. ### Claim 11 (depends on 5) A method in accordance with claim 5 wherein the inorganic substrate sheets are metal foil sheets having a composition selected from the group consisting of ferrous metals, copper, aluminum, nickel, nickel-based alloys, titanium, molybdenum, niobium, tungsten, tantalum, chromium, and chromium-based alloys. ### Claim 12 (depends on 11) A method in accordance with claim 11 wherein the pressure applied to the foil sheets is in the range of 1-50 kPa. ### Claim 13 A microlaminated composite article comprising: a plurality of layers of ceramic foil partly or wholly interleaved by a plurality of metallic or intermetallic substrate layers, wherein: the layers of ceramic foil are directly bonded to the substrate layers in contact therewith at ceramic foil-substrate interfaces therebetween; the layers of ceramic foil and the substrate layers have thicknesses not exceeding about 250 micrometers, and at least one dimension of length or breadth in excess of 1 cm; the ceramic foil layers and metallic substrate layers are essentially free of pin-hole defects the ceramic foil-substrate interfaces are essentially free of added adhesive interlayer material. ### Claim 14 (depends on 13) A composite article in accordance with claim 13 wherein the ceramic foil has a composition selected from the group consisting of zirconia, stabilized or partially stabilized zirconia, hafnia, alumina, silica, titania, mullite, spinel, chromium oxide, sialon, nasicon, silicon carbide, titanium carbide, silicon nitride, titanium nitride, zircon, zirconium carbide, titanium diboride, and combinations thereof. ### Claim 15 (depends on 13) A composite article in accordance with claim 13 wherein the ceramic foil has a composition selected from the group consisting of stabilized zirconia and partially stabilized zirconia, and wherein the zirconia includes at least one stabilizer selected from the group consisting of alkaline earth oxides, rare earth oxides, and combinations thereof. ### Claim 16 (depends on 14) A composite article in accordance with claim 14 wherein the ceramic foil has a thickness in the range of about 10-100 micrometers. ### Claim 17 (depends on 16) A composite article in accordance with claim 16 wherein the ceramic foil has a thickness in the range of about 25-50 micrometers. ### Claim 18 (depends on 14) A composite article in accordance with claim 14 wherein the inorganic substrate sheets are metal foil sheets having a composition selected from the group consisting of ferrous metals, copper, aluminum, nickel, nickel-based alloys, titanium, molybdenum, niobium, tungsten, tantalum, chromium, and chromium-based alloys.