CA2753932A1

CA2753932A1 - Manufacture and use of engineered carbide and nitride composites

Info

Publication number: CA2753932A1
Application number: CA2753932A
Authority: CA
Inventors: Giang Biscan; Hamid Hojaji; David Leslie Melmeth; Thinh Pham; Mark G. Stevens; Huagang Zhang
Original assignee: James Hardie Technology Ltd
Current assignee: James Hardie Technology Ltd
Priority date: 2009-03-05
Filing date: 2009-03-05
Publication date: 2010-09-10
Also published as: AU2009341562A1; WO2010101572A1

Abstract

Carbides and nitrides are provided containing a controlled amount of pre-determined diluents and methods for their manufacture and use are disclosed. The carbides and nitrides with pre-determined diluents are formed by optionally pyrolyzing a precursor material to form a carbonaceous mixture and heat treating the carbonaceous mixture for a pre-determined time and at an elevated temperature during which carbon and/or nitrogen reacts with silica in the mixture to form carbides and/or nitrides and controlled amounts of pre-determined diluents. The carbides and nitrides disclosed herein may be used as blowing agents in a glass, ceramic, or metal forming processes or for promoting dispersion of the carbides and nitrides throughout a glass, ceramic, or metal composite.

Description

MANUFACTURE AND USE OF ENGINEERED CARBIDE

AND NITRIDE COMPOSITES
BACKGROUND
[0001] The present invention relates generally to carbide and nitride composite materials, the manufacture of such composites, and their use in the glass making process.

[0002] Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.

[0003] 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%.

[0004] Another known use for carbides and nitrides is as blowing agents in foamed glass, ceramic or metal manufacturing processes. When carbide is used as a blowing agent, the carbons combine with oxygen under high temperature conditions to form CO and CO2 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 NOX gases that can be used to expand softened glass, ceramic or metal articles.

[0005] Despite the known utility of carbides and nitrides, their widespread use in glass and ceramic manufacturing has been limited to a large extent by their production cost.
Even the technical grade products, which are generally less expensive than commercial grade products, are still costly when compared to conventional oxides such as silica and alumina used in the glass and ceramic industries. The high cost is attributable in part to the high cost of manufacturing.

[00061 It is also known that many composites containing silicon carbide are formed by dispersing pure silicon carbide particles, whiskers or fibers into a ceramic or glass forming material or metal (or metal alloy) and processing the mixture to form a composite.
Homogeneous dispersion of silicon carbide in these composites is often problematic, requiring one or more processing steps to increase dispersion, yet still requires subsequent quality control checks. What is needed is a means of improving the dispersability of silicon carbide in glass, ceramic or metal composites.

[00071 From the foregoing, it will be appreciated that producing carbides and nitrides at a low cost and in a state that facilitates dispersability can have significant advantages in the glass, ceramic or metal composite industry where the carbides and nitrides are used extensively to improve the hardness, abrasion resistance, thermal stability or dimensional stability of such composites or where there are used as blowing agents to reduce the density of said composites. There is thus a need for an efficient process that significantly reduces the manufacturing costs of carbides and nitrides and provides them in a form that is amenable to further processing.
SUMMARY
[00081 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.
100091 According to one embodiment, 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. In one embodiment, the glass forming materials are silicates, aluminosilicates, borosilicates, borates, and phosphates. According to another embodiment, the glass network modifiers are either alkali earth oxides, alkali oxides or transition metal oxides, or any of a number of other metal oxides. In some embodiments, 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. In some embodiments, the diluent comprises between about 20% and 99 wt.% of the composite.
[0010] According to another embodiment of the invention 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 S. 10, 20, 40, 50, 80, or more of the blowing agent even up to about 99%. The diluent is preferably silica, carbon, alumina, boron o)dde, 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. According to some embodiments, the binder may be alkali metal silicates, alkali metal borates, alkali metal phosphates, polymer emulsions, polyvinyl alcohol emulsions, cellulose ethers, metbylcellulose, or sugar.
[00111 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. Additionally, 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. Optionally, the pyrolyzing step is performed in a vacuum and may be performed in a non-oxidizing atmosphere. The pyrolyzing temperature may be between about 150 and 600 C, and in some embodiments, the reacting step occurs by heat treatment at a temperature of between about 800 to.1800 C. The heat treatment time can be between about 1 to 500 minutes.
Moreover, RECTIFIED SHEET (RULE 91) 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, fiuran resin, epoxy or phenoxy resin, oils, greases, glycerin, glycols, paraffin, or mixtures thereof. In some embodiments, 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.
[00121 According to yet another embodiment, 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.

[00131 Preferred embodiments of the present invention provide a silicon carbide composite comprising silicon carbide dispersed within a solid diluent.
Preferably, 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.
Thus, the silicon carbide composite may be incorporated as part of a glass, metal or ceramic composite structure. Alternatively, 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.

100141 For example, in one embodiment the diluent is a glass-forming material including but not limited to silicates, aluminosilicates, phosphates, or borosilicates material or combinations thereof. In another embodiment 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.
In another embodiment 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 [00151 In another embodiment 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. In another embodiment, the diluent is silicon, carbon, germanium or other semiconductor material or combination thereof. Preferably, 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.%.

[00161 According to yet another embodiment, 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. In some embodiments, the silicon carbide comprises about 1 wt.% of the precursor material. Optionally 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.
BRIEF DESCRIPTION OF THE FIGURES

[00171 For more complete understanding of the features and advantages of the inventions described herein, reference is now made to a description of the invention along with accompanying figures, wherein:

[00181 FIG. i shows the XRD pattern of a sample as described herein;

[00191 FIG. 2 shows the weight change of another sample described herein as a function of temperature;

[00201 FIG. 3 shows thermogravimetric analysis (TGA) on carbon (graphite), silicon oxide and silicon carbide in air; and 100211 FIG. 4 shows X-ray diffraction analysis (XRD) pattern for a sample as described herein, together with patterns for a-SiC, and 0- SiC.

DETAILED DESCRIPTION

[00221 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.
Thus, 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.

[00231 Moreover, it has been found that carbides and nitrides with predetermined diluents are able to promote dispersion of the carbide and nitride throughout a glass, ceramic, or metal composite.

100241 As used herein, 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.
Likewise, 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.

[00251 The term 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. As exemplary embodiments described below, certain diluents are mixed with silicon carbide to form a silicon carbide composite comprising silicon carbide and at least one other material. One such embodiment is silicon carbide containing unreacted carbon and/or silica.

[00261 As used herein, 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.
[00271 The term "cellulate" or "cellulating" 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.
[00281 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.

[00291 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.

[00301 In some embodiments, certain oxides and carbon are advantageously used as a diluent material. For example, 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.

100311 Alternatively, the carbide and/or nitride dispersed in diluent may be directly sintered or melted into shaped bodies or articles. In another embodiment, 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.

[00321 In addition, 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. In some embodiments, the diluents may comprise the entirety of the glass or ceramic components. The preferred embodiments also provide a method of formulating precursor materials to manufacture the carbide or nitride within a diluent matrix.
[0033) In certain preferred embodiments, the precursor material is formed by mixing at least one silicate material and at least one carbon bearing material In one embodiment, 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, disilane, chlorosilane, silane tetrachloride, ebloroalkylsilane, aminosilane and the like, or mixtures thereof.
[0034] In one embodiment, the precursor material is formed by mixing a silicate material with a carbon bearing material, with or without a liquid and a binder. When it is desired to form a slurry, 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 mum, and more preferably less than about 500 m, or less than 250 m4 more preferably less than about 100 gm, 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 times are required for finer particles as is described in greater detail below.
[0035] Alternatively, if 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. In another embodiment, the precursor material is formed by grinding together a silicate material and a carbon bearing material, thereby promoting intimate mixing between the materials.
[0036] After mixing, 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.
[0037) Pyrolysis is the thermal decomposition of the carbon bearing material in a vacuum or non-oxidizing atmosphere to form carbon in its elementary form and/or short chain hydrocarbons. The agglomerated particles in the precursor material are preferably pyrolyzed in it suitable reactor either under vacuum and/or non-oxidizing atmosphere induced RECTIFIED SHEET IR T TT R 01\

by purging one or more inert or non-oxidizing gases into the heated reactor.
Oxidization is generally undesirable because it causes loss of the formed elementary carbon to carbon monoxide or dioxide gas [0038] In one embodiment, 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. Advantageously, 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 C.
Preferably, 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.
[00391 In another preferred embodiment, where the carbon bearing material is in a gas phase, there is no preparation of a precursor material needed. The carbon bearing material is simply present as a part of or whole of the pyrolyzing and reaction atmosphere. Notably, where 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.

[00401 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 C, and is almost complete at about 600 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. When a rotating calciner is used, 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. Preferably, 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. Without wishing to be bound by theory, it is believed that during pyrolysis sugar WO 2010/101572 PCT[US2009/036187 is converted to ultra fine reactive carbon particles forming a uniform carbon coating around each individual siliceous grain. Pyrolysis can be carried out in a single step, or may be performed during multiple steps. When the carbon bearing material is carbon itself, for example in the form of carbon black or graphite, the pyrolysis step is not required.
[0041] 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 beat treatment temperatures and duration are controlled in order to produce carbide with predetermined diluents.
[0042] Subsequently, 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. In the presence of nitrogen, either in the precursor material or the atmosphere, silicon nitride also forms as a part of the reaction. In one preferred embodiment, 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 the surrounding environment.

[0043] The pyrolyzed feed materials are preferably heated at a rate within the range of from about 1 C to about 1000 C per minute, and more preferably within the range of from about 10 C to about 100 C per minute, and in one preferred embodiment, the pyrolyzed feed materials are heated at a rate of 30 C per minute.

[0044] In embodiments in which the economy is a major driver, the heat treatment time and temperature versus product quality are optimized for minimum energy usage. In other embodiments, 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.
[0045] The preferred heat treatment temperature range is from about 1000 C to about 1700 C, more preferably from about 1050 C to about 1500 C. The beat treatment time is preferably from about I to 500 minutes, more preferably from about 10 to 100 minutes, more preferably from about 15 to 60 minutes. Preferably, the heat treatment is done in a non-oxidizing atmosphere that does not contain any additional oxygen containing gas RECTIFIED SHEET (RULE 91) 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.

(0046) In another embodiment, the non-oxidizing atmosphere contains nitrogen gas and gases formed during heat treatment. In another embodiment, 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.

[0047] In one preferred embodiment, 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.

[0048) The use of carbides and nitrides as blowing agents is discussed in greater detail in the inventors' own copending U.S. Patent Application having Serial Number 10/787,894, filed on February 25, 2004, entitled "METHODS AND FORMULATIONS FOR
PRODUCING LOW DENSITY PRODUCTS," the entirety of which is expressly incorporated herein by reference.

[0049) In another embodiment, 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.

[00503 In another embodiment, the diluent is a glass-forming material including but not limited to silicates, alumuinosilicates or borosilicates or combinations thereof. In another embodiment 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.

RECTIFIED SHEET (RULE 91) WO 2010/101572 PCT[US2009/036187 [0051] In another embodiment 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 In another embodiment, the diluent is silicon, carbon, germanium or other semiconductor material or combinations thereof.
[0052] Preferably, 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.%. However, 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.
[0053] As another approach to forming foamed materials by utilizing carbides and nitrides as cellulawng agents is to provide the glass or ceramic forming materials and to form the carbide or nitride in situ, thereby creating a precursor material having a blowing agent in a single step. As an example of single-step precursor formation, 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. In many embodiments, 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.
[0054] The following specific examples should not be construed as limiting the scope of the invention, but are used to illustrate certain embodiments within the present scope.
Example I
[0055] Example 1 illustrates a method of manufacturing a mostly amorphous silicon carbide product by using a pyrolyzed carbonaceous source and a siliceous source.
[0056] A mixture was made from I 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.

RECTIFIED SHEET (RULE 91) [00571 An enclosed graphite crucible was filled with the precursor powder and heated at 200 C for 1 hour, and then at 400 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.

[00581 A sample of the powder formed in the crucible was then subjected to X-ray Diffraction analysis (XRD). 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.

[0059} Another sample of the powder of Example 1 was subjected to a constant heating rate thermogravimetric analysis (TGA) in air. The TGA utilized a heating rate of 6 C per min, from room temperature to 1500 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 600'C to about 890'C, followed by weight gain from 890 C.

[00601 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 C, showing a weight loss. Silicon carbide when heated in the air is oxidized from 880 C, to form silicon oxide, accounting for the weight gain.

[00611 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 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.

[0062) With each unit of weight of silicon carbide oxidized to form silicon oxide, there is a weight gain of half a unit. The weight gain from 890 C to 1500 C for the sample was approximately 2% of the original sample weight. At T=1500 C when this experiment was stopped, the data shows that there was at least 4% by weight of amorphous silicon carbide present in the sample. From the inclining tendency of FIG. 2 with increased temperature, it is clear that that further weight gain will continue if the sample is subjected to additional heating.
Example 2 [00631 Example 2 illustrates the use of a binder with siliceous and carbonaceous starting materials used to produce silicon carbide in a crystallite form.

[00641 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 C for 4 hours, and then allowed to cool to room temperature.
100651 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.
[00661 The powder formed in the crucible was then subjected to XRD analysis.
FIG. 4 shows the XRD pattern for the sample, together with the patterns for a-SiC, and [3-SiC available commercially. Distinct peaks of SiC at 35.7', 41.58, 45.3' and 72" 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 [00671 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 I 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 C. The pellets were subsequently heated at 1200 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 [00681 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 simultaneously spray dried and pyrolyzed in air using a conventional spray drier to form round beads with an average diameter of 10 microns. The spray drier outlet temperature was maintained at 275 C. The pellets were subsequently heated at 950 C in nitrogen to form beads of sodium silicate having a substantial amount of silicon carbide dispersed therein.
This SIC rich material is suitable for addition to ceramics or glasses using sodium silicate as a raw material, such as, for example, to make foamed glasses.
(0069) 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.
In the oxygen releasing applications, 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 C. For example, 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 co form CO or CO2 gases which in turn will cellulate the matrix. Cooling of the matrix results in a raulticellular foamed metal composite.
(00701 The advantageous results achieved by the presently disclosed materials and methods are that 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. Finally, by selecting appropriate raw materials, 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.
(0071] Although the foregoing description of preferred embodiments of the present invention have shown, described and pointed out the fundamental novel features of the invention, it will be understood that various omissions, substitutions, and changes in the form of the detail of the preferred embodiments of the invention may be made by those skilled in the art, without departing from the spirit and scope of the invention.
Consequently, the scope of the invention should not be limited to the foregoing discussion, but should be defined by a fair reading of the following claims.

RECTIFIED SHEET (RULE 91)

Claims

1. A silicon carbide composite, comprising:
silicon carbide making up greater than 40 wt.% of the formed composite, and a diluent that makes up at least about 10% by weight of the silicon carbide composite, and wherein the diluent comprises at least a silica compound and another element at an amount greater than 0.1 wt %.

2. The composite of Claim 1, wherein said diluent is selected from the group consisting of silica fume, silica gel, glass sand, a silane and mixtures thereof.

3. The composite of Claim 1, wherein said silica compound includes a metal oxide component that acts as the diluent.

4. The composite of Claim 1, wherein said diluent acts as a flux or binder.

5. The composite of Claim 1, wherein said silicon carbide composite is formed from a carbonaceous mixture that has undergone pyrolysis, wherein the carbonaceous mixture includes of the silica compound and. at least one carbon containing material.

6. The composite of Claim 1, wherein said silica compound is a glass forming material.

7. The coniposite of Claim 2, wherein said diluent comprises between about 20%

and 99 wt.% of the composite.

8. A blowing agent comprising a carbide and/or nitride composite containing a diluent, wherein said diluent is a functional component of a glass, ceramic, or metal composite.

9. The glass blowing agent of Claim 8, wherein said diluent comprises at least about 5 wt.% of the blowing agent.

10. The glass blowing agent of Claim 9, wherein said diluent comprises at least about 10 wt.% of the blowing agent.

11. The glass blowing agent of Claim 10, wherein said diluent comprises at least about 20 wt.% of said blowing agent.

12. The glass blowing agent of Claim 11, wherein said diluent comprises at least about 40 wt.% of said blowing agent.

13. The glass blowing agent of Claim 12, wherein said diluent comprises at least about 50 wt.% of said blowing agent.

14. The glass blowing agent of Claim 13, wherein said diluent comprises at least about 80 wt.% of said blowing agent.

15. The glass blowing agent of Claim 8, wherein said diluent comprises a natural component of glass or ceramic.

16. The glass blowing agent of Claim 15, wherein said diluent is one or more components selected from the group consisting of silica, carbon, alumina, boron oxide, calcium oxide, magnesium oxide, alkali metal oxides, iron oxide, titanium oxide, zirconium oxide, and combinations thereof.

17. The glass blowing agent of Claim 8, further comprising a binder.

18. The glass blowing agent of Claim 17, wherein said binder is an alkali metal containing binder and comprises greater than about 3 wt.% of the blowing agent.

19. The glass blowing agent of Claim 17, wherein said binder is selected from the group consisting of alkali metal silicates, alkali metal borates, alkali metal phosphates, polymer emulsions, polyvinyl alcohol emulsions, cellulose ethers, methylcellulose, and sugar.

20. A method of forming a silicon carbide composite material, comprising:
forming a precursor material comprising at least one silicate material and at least one carbon bearing material;
pyrolyzing said precursor to form a carboneous mixture; and reacting carbons in said carboneous mixture with silicon from said silicate material in the presence of nitrogen 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 coniposite material.

21. The method of Claim 20, further comprising the step of drying said precursor material prior to pyrolysis.

22. The method of Claim 20, wherein forming said precursor material comprises the steps of intimately mixing said silica bearing material with said carbon bearing material to form a slurry and drying said slurry and forming particles or aggregates.

23. The method of Claim 22, wherein said particles or aggregates have a particle size of less than about 1000 microns.

24. The method of Claim 20, wherein said pyrolyzing step is performed in a vacuum.

25. The method of Claim 20, wherein said pyrolyzing step is performed in a non-oxidizing atmosphere.

26. The method of Claim 20, wherein said pyrolyzing step is performed at a temperature of between about 150 and 600 °C.

27. The method of Claim 20, wherein said pyrolyzing step is performed in multiple stages.

28. The method of Claim 20, wherein said reacting step occurs by heat treatment at a temperature of between about 800 to 1800 °C.

29. The method of Claim 28, wherein the heat treatment time is between about 1 to 500 minutes.

30. The method of Claim 28, wherein the heat treatment is carried out in a single or multiple stages.

31. The method of Claim 20, wherein said carbon bearing material comprises a material selected from the group consisting of carbon black, coke, graphite, 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, 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.

32. The method of Claim 20, wherein said silicate material is a silicon bearing material selected from the group consisting of silica fume, silica gel, glass sand, a silane including silane, disilane, chlorosilane, silane tetrachloride, chloroalkylsilane, aminosilane, or mixtures thereof.

33. A method of cellulating glass, comprising the steps of:
providing a silicon carbide composite material having silicon carbide, a predetermined diluent, and a binder containing alkali oxide wherein said 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 cellulates the glass; and wherein said predetermined diluent is compatible with the glass forming material.

34. The method of cellulating glass of Claim 33, wherein said diluent is selected such that it is incorporated into the glass matrix.

35. The method of cellulating glass of Claim 33, wherein said diluent comprises at least about 10 wt.% of the silicon carbide composite material.

36. The method of cellulating glass of Claim 33, wherein said diluent is selected from the group consisting of silica, carbon, alumina, boron oxide, calcium oxide, magnesium oxide, alkali metal oxides, iron oxide, titanium oxide, zirconium oxide, and combinations thereof.

37. The method of cellulating glass of Claim 33, wherein the diluent makes up the majority of the glass forming material.

38. The method of cellulating glass of Claim 33, wherein the composite material is sintered to form a cellulating body.

39. The method of cellulating glass of Claim 33, wherein the composite material is melted to form a cellulating body.

40. A method of forming a precursor material, comprising:
providing glass forming materials containing at least one carbon source and at least one silica source;
heating said glass forming materials to form a quantity of silicon carbide in situ;
cooling the glass forming materials thus fowling a precursor material having a quantity of silicon carbide therein.

41. The method of Claim 40, further comprising the step of adding a binder material to the glass forming materials.

42. The method of Claim 41, wherein the binder material is an alkali metal containing binder.

43. The method of Claim 41, wherein the binder is selected from the group consisting of alkali metal silicates, borates, phosphates, polymer emulsions, polyvinyl alcohol emulsions, cellulose ethers, methylcellulose, and sugar.

44. The method of Claim 40, wherein the silicon carbide makes up about 1 wt.%
of the precursor material.

45. A silicon carbide composite, comprising:
at least one silicate material; and at least one carbon bearing material in a mixture forming a carbonaceous mixture, wherein the carbonaceous mixture includes another element at an amount greater than 0.1 wt %, wherein the mixture is heated to form the silicon carbide composite, wherein heating is in the presence of a diluent, wherein the diluent makes up at least about 10% by weight of the silicon carbide coniposite, wherein silicon carbide makes up greater than 40 wt.% of the formed composite.

46. The coniposite of Claim 45, wherein the diluent is one or more components selected from the group consisting of silica, carbon, alumina, boron oxide, calcium oxide, magnesium oxide, alkali metal oxides, iron oxide, titanium oxide, zirconium oxide, and combinations thereof.

47. The composite of Claim 45, further including a binder.

48. The composite of Claim 47, wherein the binder is an alkali metal containing binder and comprises greater than about 3 wt.% of the formed composite.

49. The composite of Claim 47, wherein the binder is an alkali metal.

50. The composite of Claim 47, wherein the binder is selected from one or more of the group consisting of alkali metal silicate, alkali metal borate, alkali metal phosphate, polymer emulsion, polyvinyl alcohol emulsion, cellulose ether, methylcellulose, and sugar.

51. The composite of Claim 45, wherein the carbon bearing material is a material selected from the group consisting of carbon black, coke, graphite, a hydrocarbon with straight or branch chain containing up to 1000 carbon atoms, a cyclic or heterocyclic hydrocarbon compound, a carbohydrate, a resin and combinations thereof.

52. The composite of Claim 51, wherein the carbohydrate is selected from the group consisting of one or more sugars, starches, corn syrup, fructose, sucrose, natural fibers and combinations thereof.

53. The composite of Claim 51, wherein the resin is selected from the group consisting of phenol resin, furan resin, epoxy resin, phenoxy resin, oil, greas, glycerin, glycol, paraffin and combinations thereof.

54. The composite of Claim 45, wherein the silicate material is selected from the group consisting of silica fume, silica mineral, ash, diatomaceous earth, silica gel, glass, sand, a silane and combinations thereof.

55. The composite of Claim 54, wherein the silane is selected from the group consisting of disilane, chlorosilane, silane tetrachloride, chloroalkylsilane, aminosilane, and derivations and combinations thereof.

56 A coniposite, comprising:
silicon carbide making up less than 3 wt.% of the formed composite, and a diluent that makes up at least about 10% by weight of the silicon carbide composite, and wherein the diluent comprises at least a silica compound and another element at an amount greater than 0.1 wt %.

57. The composite of Claim 56, wherein said diluent is selected from the group consisting of silica fume, silica gel, glass sand, a silane and mixtures thereof.

58. The composite of Claim 56, wherein said silica compound acts as the diluent.

59. The composite of Claim 56, wherein said diluent acts as a flux or binder.

60. The composite of Claim 56, wherein said silicon carbide composite is formed from a carbonaceous mixture that has undergone pyrolysis, wherein the carbonaceous mixture includes of the silica compound and at least one carbon containing material.

61. The composite of Claim 56, wherein said silica compound is a glass forming material.

62. The composite of Claim 57, wherein said diluent comprises between about 20% and 99 wt.% of the composite.

63. A composite, comprising:
at least one silicate material; and at least one carbon bearing material in a mixture forming a carbonaceous mixture, wherein the carbonaceous mixture includes another element at an amount greater than 0.1 wt %, wherein the mixture is heated to form the silicon carbide composite, wherein heating is in the presence of a diluent, wherein the diluent makes up at least about 10% by weight of the silicon carbide composite, wherein silicon carbide makes up less than 3 wt.% of the formed composite.

64. The composite of Claim 63, wherein the diluent is one or more components selected from the group consisting of silica, carbon, alumina, boron oxide, calcium oxide, magnesium oxide, alkali metal oxides, iron oxide, titanium oxide, zirconium oxide, and combinations thereof.

65. The composite of Claim 63, further including a binder.

66. The coniposite of Claim 65, wherein the binder is an alkali metal containing binder and comprises greater than about 3 wt.% of the formed composite.

67. The composite of Claim 65, wherein the binder is an alkali metal.

68. The composite of Claim 65, wherein the binder is selected from one or more of the group consisting of alkali metal silicate, alkali metal borate, alkali metal phosphate, polymer emulsion, polyvinyl alcohol emulsion, cellulose ether, methylcellulose, and sugar.

69. The composite of Claim 63, wherein the carbon bearing material is a material selected from the group consisting of carbon black, coke, graphite, a hydrocarbon with straight or branch chain containing up to 1000 carbon atoms, a cyclic or heterocyclic hydrocarbon compound, a carbohydrate, a resin and combinations thereof.

70. The composite of Claim 69, wherein the carbohydrate is selected from the group consisting of one or more sugars, starches, corn syrup, fructose, sucrose, natural fibers and combinations thereof.

71. The composite of Claim 69, wherein the resin is selected from the group consisting of phenol resin, furan resin, epoxy resin, phenoxy resin, oil, greas, glycerin, glycol, paraffin and combinations thereof.

72. The composite of Claim 63, wherein the silicate material is selected from the group consisting of silica fume, silica mineral, ash, diatomaceous earth, silica gel, glass, sand, a silane and combinations thereof.

73. The composite of Claim 72, wherein the silane is selected from the group consisting of disilane, chlorosilane, silane tetrachloride, chloroalkylsilane, aminosilane, and derivations and combinations thereof.