WO2010101572A1 - Manufacture and use of engineered carbide and nitride composites - Google Patents
Manufacture and use of engineered carbide and nitride composites Download PDFInfo
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- WO2010101572A1 WO2010101572A1 PCT/US2009/036187 US2009036187W WO2010101572A1 WO 2010101572 A1 WO2010101572 A1 WO 2010101572A1 US 2009036187 W US2009036187 W US 2009036187W WO 2010101572 A1 WO2010101572 A1 WO 2010101572A1
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- 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
- C04B35/56—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 carbides or oxycarbides
- C04B35/565—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 carbides or oxycarbides based on silicon carbide
- C04B35/573—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 carbides or oxycarbides based on silicon carbide obtained by reaction sintering or recrystallisation
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- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
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- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
Definitions
- the present invention relates generally to carbide and nitride composite materials, the manufacture of such composites, and their use in the glass making process.
- Carbides and nitrides are commonly used to form various articles that can withstand high temperature and stress without substantial deterioration. They are particularly suitable for applications in which oxidation at higher temperatures is not desirable, or in which abrasion resistance, thermal and electrical conductivity, dimensional stability, and/or excellent mechanical properties are desired.
- Typical uses for carbides and nitrides include semiconducting devices, automotive components, grinding and polishing applications, and as refractory in high temperature furnaces. These uses typically require a highly pure form of carbide in order to exhibit the desirable properties that carbides and nitrides are known for.
- Typical high purity carbide applications require a material that is greater than about 98% pure, while the commercial low grade carbides have purity levels between about 95% and 98%.
- carbides and nitrides are blowing agents in foamed glass, ceramic or metal manufacturing processes.
- carbide When carbide is used as a blowing agent, the carbons combine with oxygen under high temperature conditions to form CO and CO 2 gases. The gases in turn are used to expand the softened glass, ceramic precursor or molten metal to form low-density foamed articles having a cellular structure.
- the same principle applies to the nitrogen in nitrides, which combines with oxygen to form one or more NO x gases that can be used to expand softened glass, ceramic or metal articles.
- Preferred embodiments provide a method of manufacturing a carbide or nitride composite blowing agent that contains controlled amounts of pre-determined diluents.
- the preferred embodiments also provide a method of utilizing these blowing agents in a glass or ceramic manufacturing process in a manner such that the diluents do not interfere with the glass or ceramic foaming process.
- the preferred embodiments also provide a method of formulating precursor materials to manufacture the carbide or nitride composites.
- a silicon carbide composite comprises silicon carbide and a diluent comprising greater than about 20% by weight of the silicon carbide composite, and wherein the diluent is a functional component of a glass, metal, or ceramic composite.
- the diluent may be selected from the group consisting of at least one of carbon, silicon, nitrogen, glass forming materials, glass network modifiers, glass network intermediate oxides, ceramic forming materials, metals and metal oxides.
- the glass forming materials are silicates, aluminosilicates, borosilicates, borates, and phosphates.
- the glass network modifiers are either alkali earth oxides, alkali oxides or transition metal oxides, or any of a number of other metal oxides.
- the ceramic forming materials are either oxides of silicon, aluminum, boron phosphorous, titanium, zirconium, and oxides of alkali or alkaline earth metals or transition metal oxides.
- the metal is preferably either aluminum, nickel, copper, iron, titanium, magnesium, chromium, zinc, tin, silver, gold, and the platinum family of metals, including combinations or alloys thereof.
- the diluent comprises between about 20% and 99 wt.% of the composite.
- a blowing agent comprises carbide and/or nitride composite containing a diluent, wherein the diluent is a functional component of a glass, ceramic, or metal composite.
- the diluent may comprise, by weight percent, at least about 5, 10, 20, 40, 50, 80, or more of the blowing agent even up to about 99%.
- the diluent is preferably silica, carbon, alumina, boron oxide, calcium oxide, magnesium oxide, alkali metal oxides, iron oxide, titanium oxide, zirconium oxide, phosphorous oxide, or combinations thereof
- the blowing agent may further comprise a binder, which may be an alkali metal containing binder comprising greater than about 3 wt.% of the blowing agent.
- the binder may be alkali metal silicates, alkali metal borates, alkali metal phosphates, polymer emulsions, polyvinyl alcohol emulsions, cellulose ethers, methylcellulose, or sugar.
- Another embodiment of the present invention teaches a method of forming a silicon carbide composite material, wherein the method comprises forming a precursor material comprising at least one silicate material and at least one carbon bearing material; pyrolyzing said precursor to form a carbonaceous mixture; and reacting carbons in said carbonaceous mixture with silicon from said silicate material in the presence of nitrogen or hydrogen, inert gases, or vacuum, to form silicon carbide and a controlled amount of at least one diluent, wherein said diluent makes up at least about 10% by weight of the silicon carbide composite material.
- the method may further include the step of drying said precursor material prior to pyrolysis.
- forming the precursor material may include the steps of intimately mixing the silica bearing material with the carbon bearing material to form a slurry and drying the slurry and forming particles or aggregates.
- the particles or aggregates may have a particle size of less than about 1000 microns.
- the pyrolyzing seep is performed in a vacuum and may be performed in a non-oxidizing atmosphere.
- the pyrolyzing temperature may be between about 150 and 600 0 C, and in some embodiments, the reacting step occurs by heat treatment at a temperature of between about 800 to .1800 0 C.
- the heat treatment time can be between about 1 to 500 minutes.
- the heat treatment may be carried out in a single or multiple stages.
- the carbon bearing material may comprise either carbon black, coke, graphite, pulverized coal, coal powder, ground rubber, a hydrocarbon with straight or branch chain containing up to 1000 carbon atoms, a cyclic or heterocyclic hydrocarbon compound, a carbohydrate including sugar, starch, corn syrup, molasses, fructose, sucrose, natural fibers including cellulose, a resin including phenol resin, furan resin, epoxy or phenoxy resin, oils, greases, glycerin, glycols, paraffin, or mixtures thereof.
- the silicate material is a silicon bearing material such as silica fume, silica gel, silicate glass, clay, silicate minerals or rocks, ashes containing silica such as fly ash or rice hull ash, a silane including silane, disilane, chlorosilane, silane tetrachloride, chloroalkylsilane, aminosilane, or mixtures thereof.
- a method of cellulating glass comprises the steps of providing a silicon carbide composite material having silicon carbide, a predetermined diluent, and a binder containing alkali oxide wherein the alkali oxide comprises greater than about 3 wt.% of the silicon carbide composite material; providing a glass forming material; blending the silicon carbide composite material with said glass forming material to form a precursor; heating the precursor to a blowing temperature such that the silicon carbide reacts to give off gas and cellulate the glass; and wherein said predetermined diluent is compatible with the glass forming material.
- the diluent may be selected such that it is a functional component of the glass matrix.
- the diluent may comprise at least about 10 wt.% of the silicon carbide composite material, and may be either silica, carbon, alumina, boron oxide, calcium oxide, magnesium oxide, alkali metal oxides, iron oxide, titanium oxide, zirconium oxide, and combinations thereof.
- Preferred embodiments of the present invention provide a silicon carbide composite comprising silicon carbide dispersed within a solid diluent.
- the solid diluent is selected to also be a functional component of a glass, metal or ceramic composite such that the diluent will alloy with, dissolve into, react with, sinter with, melt with, or disperse into one or more components of the glass, metal or ceramic composite.
- the silicon carbide composite may be incorporated as part of a glass, metal or ceramic composite structure.
- the silicon carbide composite can be sintered or melted into shaped bodies or articles, or be combined with other materials to form a composite for intermediate use or further processing.
- the diluent is a glass-forming material including but not limited to silicates, aluminosilicates, phosphates, or borosilicates material or combinations thereof.
- the diluent is at least one oxide used in glass manufacturing including but not limited to alumina, borates, zirconia, titania, alkali earth oxides, alkali oxides, transition metal oxides, or other metal oxides.
- the solid diluent is a ceramic forming material including but not limited to oxides of silicon, aluminum, titanium, zirconium, oxides of alkali or alkaline earth metals, metals, or combinations thereof
- the diluent is a molten metal or metal powder such as aluminum, nickel, copper, iron, titanium, magnesium, chromium, zinc, tin silver, gold, platinum family of metals, or other transition metal, including alloys or combinations thereof.
- the diluent is silicon, carbon, germanium or other semiconductor material or combination thereof.
- the diluent comprises no greater than about 99%, of the silicon carbide composite, more preferably no greater than about 80 wt.%, more preferably no greater than about 50 wt.%, more preferably less than 20 wt.%, more preferably between about 1 wt.% and 20 wt.%.
- a precursor material is formed by providing glass forming materials containing at least one carbon source and at least one silica source; heating the glass forming materials to form a quantity of silicon carbide in situ and cooling the glass forming materials thus forming a precursor material having a quantity of silicon carbide therein.
- the silicon carbide comprises about 1 wt.% of the precursor material.
- a binder material can be added to the glass forming materials which may be an alkali metal containing binder, such as, for example, alkali metal silicates, borates, phosphates, polymer emulsions, polyvinyl alcohol emulsions, cellulose ethers, methylcellulose, and sugar.
- FIG. 1 shows the XRD pattern of a sample as described herein
- FIG. 2 shows the weight change of another sample described herein as a function of temperature
- FIG. 3 shows thermogravimetric analysis (TGA) on carbon (graphite), silicon oxide and silicon carbide in air; and
- FIG. 4 shows X-ray diffraction analysis (XRD) pattern for a sample as described herein, together with patterns for ⁇ -SiC, and ⁇ - SiC.
- TGA thermogravimetric analysis
- XRD X-ray diffraction analysis
- Embodiments of the present invention stem from the realization that carbides and nitrides are suitable as blowing agents to cellulate glass, ceramic, and metal composites, and more specifically, from the realization that highly pure forms of carbide and nitride are not necessary, especially if the carbides and nitrides are manufactured with desired diluents that are functional components of glass, ceramic, or metal composite products.
- preferred embodiments of the present invention disclose the novel concept of manufacturing carbide and nitride composites that contain a controlled amount of at least one diluent material and utilizing the composite carbides or nitrides as blowing agents in glass, ceramic, or metal forming processes.
- carbides and nitrides with predetermined diluents are able to promote dispersion of the carbide and nitride throughout a glass, ceramic, or metal composite.
- the term “carbide composite” refers to a compound comprising carbide, such as silicon carbide, boron carbide, titanium carbide, tungsten carbide, and analogous oxycarbides and a predetermined amount of a diluent.
- the term “nitride composite” refers to a compound comprising nitride, such as, for example, silicon nitride, boron nitride, aluminum nitride, titanium nitride, tungsten nitride and analogous carbonitrides, in combination with a predetermined amount of a diluent.
- diluent is a broad term and in one sense refers to a substance that lessens the force, strength, purity, or brilliance of another substance, such as by admixture or dilution.
- certain diluents are mixed with silicon carbide to form a silicon carbide composite comprising silicon carbide and at least one other material.
- silicon carbide containing unreacted carbon and/or silica is silicon carbide containing unreacted carbon and/or silica.
- the term "functional component” should be construed to mean that one substance is dissolved in, dispersed in, alloys with, reacts with, melts with, sinters with, acts as an inert filler in, or chemically modifies another substance.
- cellulate refers to introducing one or more gas pockets within a material. Unless otherwise specified herein, cellulate refers to providing one or more cells formed by releasing a gas within a material, such as by blowing, for example.
- Preferred embodiments of the present invention disclose the novel concept of manufacturing composites of carbides and nitrides dispersed within the matrix of a preselected diluent.
- the carbide or nitride composites may be used as blowing agents in glass, ceramic or metal composite manufacturing processes.
- the inventors have found that, contrary to conventional wisdom, when the silicon carbides and or nitrides are formed in-situ inside a diluent material that the diluent and carbide/nitride composite is more easily processed and dispersed within other glasses, ceramics or metals. Since the diluent is preselected to have a functional role within the glass, metal or ceramic composite, the diluent can be engineered to not interfere with the function of the carbide or nitride within the composite, or to minimize any deleterious effects the carbide or nitride may have on the composite.
- certain oxides and carbon are advantageously used as a diluent material.
- silicon carbide having excess unreacted carbon and silica provides an acceptable blowing agent for foamed glass or ceramic because carbon will function as a lower temperature blowing agent and silica is compatible with silica based glass matrices.
- Other diluents such as silicates, aluminosilicates or borosilicates, or combinations thereof may also be reacted with carbon to form silicon carbide dispersed within a diluent of silicate, aluminosilicate or borosilicate, respectively, any of which may be incorporated into a wide variety of glass or ceramic compositions.
- the carbide and/or nitride dispersed in diluent may be directly sintered or melted into shaped bodies or articles.
- the carbides or nitrides dispersed in diluent may be added to polymeric materials to form abrasives or to improve the thermal stability or dimensional stability of the polymeric materials.
- preferred embodiments provide a method of manufacturing a carbide or nitride blowing agent in-situ and dispersed within a diluent.
- the preferred embodiments also provide a method of utilizing these blowing agents to manufacture foamed glass, metal or ceramic composites in a manner such that the diluent becomes a functional part of the glass ceramic or metal composite and does not interfere with the glass or ceramic foaming process.
- the diluents may comprise the entirety of the glass 129843-2538
- the preferred embodiments also provide a method of formulating precursor materials to manufacture die carbide or nitride within a diluent matrix.
- the precursor material is formed by mixing at least one silicate material and at least one carbon bearing material
- the silicate material is a silicon bearing material such as silica fume, silica gel, silicate glass, clay, silicate minerals and rocks, ashes containing silica such as fly ash or rice hull ash, ground waste glass, diatomaceous earth, volcanic ash, or a silane- including silane, disilarte, chlorosilane, silane tetrachloride, cbloroaUsylsilane, aminosilane and the like, or mixtures thereof.
- the precursor material is formed by mixing a silicate material with a carbon bearing material, with or without a liquid and a binder.
- water is a preferred liquid.
- the slurry is either dried, preferably via a spray drying process, or solidified into fine particles or aggregates.
- the particle size of the dried material is preferably less than about 1 mm, and more preferably less than about 500 ⁇ m, or less than 250 ⁇ m, more preferably less than about 100 ⁇ ra, and in some preferred embodiments, is less than about 50 ⁇ m.
- the finer particles advantageously heat up to a pyrolysis temperature more quickly, therefore, shorter pyrolysis residence tunes are required for finer particles as is described in greater detail below.
- the slurry is anhydrous and is in a molten state, such as the mixture of silica fume in molten sugar
- the liquid can be drawn or poured into the shape of rods or fibers.
- the molten mass can optionally be poured between two counter rotating rollers to form solid ribbons or flakes.
- the precursor material is formed by grinding together a silicate material and a carbon bearing material, thereby promoting intimate mixing between the materials.
- the precursor material is subsequently pyrolyzed in which carbon bearing material in the precursor is formed into finely divided carbon particles dispersed substantially uniformly through a pyrolyzed mass, which preferably comprises non- graphitizing carbon with high surface area to unit mass ratio.
- Pyrolysis is the thermal decomposition of the carbon bearing material in a vacuum or non-oxidfcring atmosphere to form carbon in its elementary form and/or short chain hydrocarbons.
- the agglomerated particles in the precursor material are preferably pyrolyzed in a suitable reactor either under vacuum and/or non-oxidizing atmosphere induced
- Oxidization is generally undesirable because it causes loss of the formed elementary carbon to carbon monoxide or dioxide gas
- the precursor material is dried before the carbon bearing material is pyrolyzed.
- the carbon bearing material preferably comprises a material selected from the group consisting of a hydrocarbon with straight or branch chain containing up to about 1000 carbon atoms; a cyclic or heterocyclic hydrocarbon compound; a carbohydrate including sugar, starch, corn syrup, fructose, sucrose and the like; natural fibers including cellulosic fibers; cellulose derivatives such as cellulose ethers, methylcellulose, hydroxyethylcellulose and the like; a resin including phenol resin, furan resin, epoxy or phenoxy resin, or the like; oils; greases; glycerin; glycols; paraffin; and mixtures thereof.
- sugar, corn syrup, or molasses is used in some embodiments because it is a non-toxic and inexpensive carbon source which starts to pyrolyze at relatively low temperatures, such as under about 200 0 C.
- the carbon bearing material is water soluble, non-toxic, and inexpensive.
- Certain other hydrocarbons such as polyvinylchloride (PVC), rubber, and petroleum coke can also be used to form graphitizing carbon.
- the carbon bearing material is in a gas phase
- the carbon bearing material is simply present as a part of or whole of the pyrolyzing and reaction atmosphere.
- carbon is added directly, such as in the form of carbon black, coke, pulverized coal, or graphite, the pyrolysis may be omitted from the process.
- the pyrolysis temperature depends on the type of carbon bearing material in the precursor. For example, the pyrolysis of sugar starts as low as about 150 0 C, and is almost complete at about 600 0 C.
- Any of a number of reactors for pyrolysis may be used, including, without limitation, a rotating tube calciner, a fluidized bed, an inductive furnace, a plasma furnace, an infra-red furnaces, or a heated chamber such as spray dryer or spray calciner.
- a rotating calciner the contact surfaces can either be coated or lined with a non-wetting material such as graphite, carbides, polytetrafluoroethylene and the like to prevent furnace fouling.
- the rotating tube is constructed from graphite and lined from outside with a layer of steel or other appropriate metals.
- Ground coal or graphite powder may also be added to the feed material as an oxygen scavenger if needed to prevent oxidization.
- oxygen scavenger if needed to prevent oxidization.
- Pyrolysis can be carried out in a single step, or may be performed during multiple steps.
- the carbon bearing material is carbon itself, for example in the form of carbon black or graphite, the pyrolysis step is not required.
- the carbide forming furnace may be a rotary tube calciner, a spray heated reactor, a dense phase fluidized bed, or any of a number of suitable furnaces.
- the heated feed materials are maintained at the desired temperature for a predetermined amount of time based upon the initial material composition, any economic driving considerations, and the desired material composition after processing. For example, the heat treatment temperatures and duration are controlled in order to produce carbide with predetermined diluents.
- the carbonaceous mixture is preferably heated in a furnace to react the carbons with silicon present in the silicon bearing material to form carbides dispersed within a diluent matrix.
- silicon nitride also forms as a part of the reaction.
- some diluent components such as alkali metal silicates or borates, may act as a flux or binder during heat treatment that forms a glassy layer enveloping the precursor particles or particle aggregates.
- the glassy envelope creates sealed non-oxidizing micro reaction zones, where the precursor material within can react independent of me surrounding environment.
- the pyrolyzed feed materials are preferably heated at a rate within the range of from about 1"C to about 1000 0 C per minute, and more preferably within the range of from about 1O 0 C to about 100 0 C per minute, and in one preferred embodiment, the pyrolyzed feed materials are heated at a rate of 3O 0 C per minute.
- the heat treatment time and temperature versus product quality are optimized for minimum energy usage.
- the acceptable maximum diluent level is set by the minimum required blowing quality of carbide when used as a blowing agent to produce expanded glass and ceramic articles, and can be as high as 80% or greater.
- the preferred heat treatment temperature range is from about 100O 0 C to about 1700°C, more preferably from about 1050 0 C to about 150O 0 C
- the heat treatment time is preferably from about 1 to 500 minutes, more preferably from about 10 to 100 minutes, more preferably from about 15 to 60 minutes.
- the heat treatment is done in a non- oxidi ⁇ ing atmosphere that does not contain any additional oxygen containing gas or additional carbon monoxide other than that may have been naturally formed during the heat treatment due to the reactions.
- Such atmospheres include nitrogen, hydrogen, inert gasses, and vacuum.
- the non-oxidizing atmosphere contains nitrogen gas and gases formed during heat treatment.
- the heat treatment can be carried out in a single stage or multiple stages. It should be noted that the presence of an active reducing agent, such as hydrogen or methane, can promote the reaction rate and increase the final carbide yield in the product.
- the silicon bearing material contains other oxides such as alumina, boron oxide, and metal oxides. During processing, these materials convert partially to silicon carbide and the remaining oxides which do not convert to carbides form a diluent that may be incorporated into glasses, ceramics, or metal composites. When the resulting carbides are used as blowing agents, the diluents will become a part of the expanded glass, ceramic, or metal articles.
- oxides such as alumina, boron oxide, and metal oxides.
- diluents consist of at least one of carbon; minerals such as silica or alumina; metals such as silicon, iron, nickel, copper or aluminum; metal oxides including alkaline metal oxides such as sodium oxide or potassium oxide; alkaline earth metal oxides such as calcium oxide or magnesium oxide; transition metal oxides such as copper oxide, iron oxide, or nickel oxide and other metal oxides such as aluminum oxide or lead oxide; alkaline inorganic compounds such as sodium silicate, alkali phosphates, borax, and combinations thereof.
- the diluent is a glass-forming material including but not limited to silicates, aluminosilicates or borosilicates or combinations thereof.
- the solid diluent is a ceramic forming material including but not limited to oxides of silicon, aluminum, phosphorous, titanium, zirconium, oxides of alkali or alkaline earth metals, metal oxides, or combinations thereof. 129843-2538
- the diluent is a molten metal or metal powder such as aluminum, nickel, copper, iron, titanium, tin, silver, gold, one of the platinum family of metals, magnesium, chromium, zinc, or other transition metal, including alloys or combinations thereof
- the diluent is silicon, carbon, germanium or other semiconductor material or combinations thereof.
- the overall percentage of the diluent within the carbide or nitride is less than about 80 wt.%, more preferably less than about 50 wt.%, and more preferably less than about 20 wt.%.
- the diluent percentage within the carbide or nitride can be greater than 80% with acceptable results depending on the application for which the carbide or nitride is designed.
- silica fume, graphite, and sodium silicate are mixed together.
- the mixture is then heat treated for a predetermined amount of time at a desired temperature to form a quantity of silicon carbide, such as about 1, 2, 5, or 10 wt.% of the total weight of the precursor.
- the silicon carbide is thus formed in situ and can be used as a blowing agent in the precursor material in a subsequent glass foaming process.
- silicon carbide As little as 1 wt.% or less of the precursor material is silicon carbide. According to this approach, a silicon carbide composite is produced having silicon carbide and diluents wherein the silicon carbide comprises about 1 wt.% of the composite.
- Example 1 illustrates a method of manufacturing a mostly amorphous silicon carbide product by using a pyrolyzed carbonaceous source and a siliceous source.
- a mixture was made from 1 part by weight of silica fume, three parts of sugar, and sufficient water to form a slurry with a syrupy consistency.
- the slurry was dried at 105 "C to form a brittle solid cake.
- the solid cake was then coarsely ground into a precursor powder having a nominal size of 500 ⁇ m.
- An enclosed graphite crucible was filled with the precursor powder and heated at 200 0 C for 1 hour, and then at 400 0 C for 3 hours to melt and pyrolyze the sugar.
- the crucible was then heated at 1500 " C for 5 hours to allow graphite formation, and then cooled to room temperature.
- the graphite wall of the crucible acted as an oxygen scavenger and ensured a non-oxidizing atmosphere within the crucible for sugar pyrolysis and carbide formation.
- FIG. 1 shows the XRD pattern of the sample. As can be seen from FIG. 1, the powder is mostly amorphous due to the lack of a level baseline and clearly defined peaks, which would indicate a crystalline structure.
- thermogravimetric analysis (TGA) in air.
- TGA thermogravimetric analysis
- the TGA utilized a heating rate of 6 0 C per min, from room temperature to 1500 0 C.
- FIG. 2 shows the weight loss or gain of the sample as a function of temperature. As can be seen from FIG. 2, some weight loss was detected from 6O ⁇ ' C to about 890 C, followed by weight gain from 890 0 C.
- FIG. 2 is further understood by reference to FIG. 3 which shows separate results of the same TGA heating treatments for carbon (graphite), silicon oxide and silicon carbide in air. It can be seen that silicon oxide weight remains relatively constant throughout the heating period. Graphite, on the other hand, is burned off in the air from 600 0 C, showing a weight loss. Silicon carbide when heated in the air is oxidized from 880 0 C, to form silicon oxide, accounting for the weight gain.
- the plot in FIG. 3 indicates that the weight loss observed in FIG. 2 for the sample corresponds to carbon and short-chain hydrocarbons burned off in the presence of air.
- the weight gain from about 890 0 C indicates that silicon carbide was present in the sample, and was oxidized to form silicon oxide. Therefore, the XRD and TGA results show that amorphous silicon carbide was formed in Example 1.
- Example 2 illustrates the use of a binder with siliceous and carbonaceous starting materials used to produce silicon carbide in a crystallite form.
- a mixture was prepared from 3 parts by weight of a silica fume, 6 parts of graphite powder, and 1 part of sodium silicate. The mixture was then placed into an alumina crucible. An extra 3 parts of graphite powder was then placed on top of the mixture to completely fill the crucible. A lid was placed on top to enclose the crucible. The crucible was then heated at 1500 0 C for 4 hours, and then allowed to cool to room temperature.
- the extra graphite acted as an oxygen scavenger to ensure a non-oxidizing environment in the crucible during the carbide formation.
- the sodium silicate is used as a fluxing and binding agent to bind the silicon carbide and unreacted carbon and silica in a uniform mass.
- FIG. 4 shows the XRD pattern for the sample, together with the patterns for ⁇ -SiC, and ⁇ - SiC available commercially. Distinct peaks of SiC at 35.7 , 41.58 , 45.3 and 12 can be seen in the XRD pattern of the sample.
- the XRD pattern also indicates the presence of diluents, including silicon oxide in cristobalite form, and carbon in graphite form, as indicated by the peaks at 31.36 and 54.582, respectively.
- Example 3 was prepared my mixing 7.5 parts by weight of a powdered commercial montmorillonite clay containing 60% by weight silica with an average particle size of 5 microns with 1 part sugar in water to form pumpable slurry.
- the slurry was simultaneously spray dried and pyrolyzed in air using a conventional spray drier to form round pellets with an average diameter of 50 microns.
- the spray drier outlet temperature was maintained at 275 0 C.
- the pellets were subsequently heated at 1200 0 C in nitrogen to form a powdered material containing silicon carbide dispersed in a diluent of alumina and calcined montmorillonite clay. This SiC rich material is suitable for addition to ceramics or glasses using montmorillonite clays as a raw material.
- Example 4 was prepared by mixing 16 parts of sodium silicate (dry basis) with 1 part sugar in water to form a thick, pumpable solution. The solution was 129843-2538
- Silicon carbide produced by the disclosed processes and having the described diluents may be added to metals as a reinforcing agent to form a metal matrix composite, or optionally together with other powders that can release oxygen.
- the released oxygen can react with the carbide to form gas bubbles within the metal matrix.
- the foaming temperature is preferably selected at or above the oxidation temperature of carbide, e.g. above 800 0 C.
- ferric oxide, manganese dioxide, and the like can be mixed with carbide and added to an appropriate metal matrix compound and heated to a temperature that is above the oxidation temperature of carbide.
- the oxide will release oxygen that is used to form CO or CO 2 gases which in turn will cellulate the matrix. Cooling of the matrix results in a multicellular foamed metal composite.
- carbides and nitrides can be formed without the requirement of high purity, as is typically required in the carbide and nitride forming arts. Even more advantageous is an effective use for carbide and nitride composites as blowing agents in glass and ceramic forming processes.
- the diluents can be incorporated into the glass, ceramic, or metal matrix, and may even be materials commonly found in glass, ceramics, and metals composites thus avoiding any detrimental effects to the formed products.
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CA2753932A CA2753932A1 (en) | 2009-03-05 | 2009-03-05 | Manufacture and use of engineered carbide and nitride composites |
PCT/US2009/036187 WO2010101572A1 (en) | 2009-03-05 | 2009-03-05 | Manufacture and use of engineered carbide and nitride composites |
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CN105273716A (en) * | 2014-07-21 | 2016-01-27 | 中国科学院上海硅酸盐研究所 | Preparation method of rare earth ion Ce<3+> doped Y2Si4N6C yellow fluorescent powder |
CN107986798A (en) * | 2017-11-23 | 2018-05-04 | 磐石华兴汽车零部件制造有限公司 | The preparation method of casting transfer bag composite lining material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4981666A (en) * | 1985-11-27 | 1991-01-01 | Shin-Etsu Chemical Co., Ltd. | Method for the preparation of silicon carbide whiskers |
US20040081827A1 (en) * | 2002-08-23 | 2004-04-29 | Amlan Datta | Synthetic microspheres and methods of making same |
US20080095692A1 (en) * | 2004-05-14 | 2008-04-24 | Charlotte Pham | Method For Producing Fabricated Parts Based On Beta-Sic For Using In Aggressive Media |
-
2009
- 2009-03-05 WO PCT/US2009/036187 patent/WO2010101572A1/en active Application Filing
- 2009-03-05 AU AU2009341562A patent/AU2009341562A1/en not_active Abandoned
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4981666A (en) * | 1985-11-27 | 1991-01-01 | Shin-Etsu Chemical Co., Ltd. | Method for the preparation of silicon carbide whiskers |
US20040081827A1 (en) * | 2002-08-23 | 2004-04-29 | Amlan Datta | Synthetic microspheres and methods of making same |
US20080095692A1 (en) * | 2004-05-14 | 2008-04-24 | Charlotte Pham | Method For Producing Fabricated Parts Based On Beta-Sic For Using In Aggressive Media |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105273716A (en) * | 2014-07-21 | 2016-01-27 | 中国科学院上海硅酸盐研究所 | Preparation method of rare earth ion Ce<3+> doped Y2Si4N6C yellow fluorescent powder |
CN107986798A (en) * | 2017-11-23 | 2018-05-04 | 磐石华兴汽车零部件制造有限公司 | The preparation method of casting transfer bag composite lining material |
CN107986798B (en) * | 2017-11-23 | 2021-02-23 | 磐石华兴汽车零部件制造有限公司 | Preparation method of transfer ladle composite lining material for casting |
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