WO1998051981A1 - Compositions de moulage en ceramique renforcees par des fibres de verre - Google Patents

Compositions de moulage en ceramique renforcees par des fibres de verre Download PDF

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Publication number
WO1998051981A1
WO1998051981A1 PCT/US1998/009649 US9809649W WO9851981A1 WO 1998051981 A1 WO1998051981 A1 WO 1998051981A1 US 9809649 W US9809649 W US 9809649W WO 9851981 A1 WO9851981 A1 WO 9851981A1
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WIPO (PCT)
Prior art keywords
ceramic
glass fibers
weight
percent
composition
Prior art date
Application number
PCT/US1998/009649
Other languages
English (en)
Inventor
Martin C. Flautt
Yadi Delaviz
Gary Gao
Original Assignee
Owens Corning
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Owens Corning filed Critical Owens Corning
Priority to AU74812/98A priority Critical patent/AU7481298A/en
Publication of WO1998051981A1 publication Critical patent/WO1998051981A1/fr

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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
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Definitions

  • the present invention relates to the manufacture of noncementitious ceramic articles. More particularly, the present invention relates to the inclusion of glass fibers in the moldable ceramic-forming composition used in the manufacture of such articles to improve the strength and fracture toughness of the green body before and during firing, and the resultant ceramic body after firing.
  • the process is useful in a wide range of applications relating to the production of traditional ceramic articles such as whiteware, including wash basins and toilets ("sanitary ware"), tiles, dinner ware, and electrical porcelain, and finer texture ceramics used in electrical, biological/biochemical, magnetic, optical, nuclear and high temperature/high strength applications.
  • the invention relates to a process for coating glass fibers with metals or metal oxides to impart properties desirable for specific applications, including the reinforcement of ceramics, and to an apparatus for dispersing the glass fibers into the ceramic molding compositions.
  • Noncementitious ceramics are well known and widely used as the material of choice for a variety of traditional ceramic products such as, porcelain (for figurines, vases, etc.), white ware (dinner ware, sanitary ware, floor tile, etc.), and structural products (brick, tile, terra cotta, etc.) as well as more advanced fine ceramics used in applications requiring specific electrical, magnetic or optical characteristics as well as high thermal resistance and mechanical strength. Ceramics exhibit many useful properties including good mechanical strength, chemical durability, and hardness.
  • molding casting or extruding
  • a ceramic-forming slurry or paste containing from about 15 to 75 percent water to form a ceramic "green body” which is then dried and fired to form the ceramic article.
  • the objects are often either molded directly from the ceramic-forming molding composition, or carved or machined from a molded green body.
  • one of the more common molding techniques for directly forming the desired article, slip casting relies upon using a porous mold and a ceramic slip which may consist of a wide variety of powdered ball clay, kaolin, nonplastics and other silica and silicon compounds, as well as various metal oxides, mixed with water in such a way that the mixture attains a suitable low viscosity for pouring or pumping into the mold.
  • the porous mold is typically formed of gypsum which absorbs some of the water from the slip causing solid matter in the slip to form a cake on the mold's surface that exhibits the proper molded shape.
  • the volume of liquid slip remaining in the mold after it has "set up" in the foregoing manner is drained from the mold and the mold is then removed to provide the green body.
  • ceramic articles can be formed from higher viscosity molding compositions containing greater amounts of organic plasticizers and less water. Such articles are often formed by standard compression or injection molding or extrusion techniques, or by machining a molded ceramic green body.
  • the resulting green body is then dried to remove excess water and fired at an elevated temperature in an oven to cure the ceramic.
  • the drying and firing processes can be complex, and if not performed properly, can cause the piece to crack or break.
  • the present invention provides a means for manufacturing noncementitious ceramic articles with reduced drying time requirements and a reduced incidence of deformation or breakage of the ceramic green body. Accordingly, the present invention provides a more efficient process for the manufacture of ceramic articles through increased productivity, less scrap and reduced wall thickness requirements.
  • the above goals are obtained by the incorporation of chopped glass fibers into the ceramic molding or ceramic glaze composition prior to molding. Dispersion of the glass fibers throughout the resulting green body imparts strength and toughness to the green body and facilitates drying of the green body.
  • the addition of appropriately sized glass fibers through the ceramic molding composition in amounts sufficient to provide these beneficial attributes can alter the rheology of the molding composition and affect its moldability.
  • the invention further encompasses the inclusion of additional water, gelation agents or deflocculating agents that counteract the rheoiogical effect of fiber addition and maintain the molding composition's rheoiogical properties at a level suitable for molding. By combining glass fibers and gelation or deflocculating agents, the rheology of the molding composition can be controlled to provide optimum molding characteristics.
  • the present invention provides a method and apparatus for dispersing the chopped glass fibers into the ceramic molding composition, and maintaining the fibers in such a dispersed state until molding of the composition occurs.
  • the invention provides a high shear mixer that can be mounted within existing storage tanks to disperse the fibers throughout the ceramic molding composition contained within the tank.
  • the invention includes a detached high shear mixer connected to the storage tank via suitable plumbing to allow the ceramic molding composition to be withdrawn from the tank, pass through the high shear mixer to have glass fibers dispersed throughout, and returned to the storage tank.
  • the glass fibers can first be dispersed in water or other liquid media and subsequently added to the ceramic molding composition.
  • the present invention provides a process for coating glass fibers with metals or metal oxides to impart specific physical properties desirable for specific applications.
  • the invention includes a process for coating glass fibers with certain metal oxides that increase the high temperature stability of the fibers and which may prevent fluxing of the fibers at the temperatures encountered during firing of the ceramic bodies. Consequently, such coated fibers may retain their identity in the cured ceramic products and provide improved fracture toughness to the ceramic articles. Such increases in fracture toughness may allow the wall thickness of the ceramic article to be reduced and provide a savings in raw material costs.
  • Figure 1 is a cross-sectional view of a ceramic molding composition storage tank containing a high shear mixer for dispersing glass fibers throughout the molding composition contained in the tank.
  • Figure 2 is a graph showing increases in green body flexural strength or modulus of rupture (MOR) as a function of fiber length at glass fiber loadings of 0.5 and 1.0 percent by weight.
  • MOR modulus of rupture
  • Figure 3 is a graph showing increases in green body fracture toughness as a function of fiber length at a glass fiber loading of 0.5 percent by weight.
  • Figure 4 is a graph showing green body fracture toughness or work of fracture (WOF) as a function of fiber loading for glass fibers of various lengths.
  • Figure 5 is a graph showing the reduction in linear shrinkage that occurs during drying/firing of ceramic compositions containing 0.5 percent by weight glass fibers.
  • the flexural strength and fracture toughness of the green body is increased by the incorporation of glass fiber reinforcement.
  • fibers are concentrated near the surface because of the diffusion of water towards the outer part surface and into the porous mold.
  • fibers tend to align parallel to the surface due to the flow front and shear forces at the wall of the mold.
  • Fibers may also be concentrated at and parallel to the surface by adding them directly to the glaze coating.
  • the enriched concentration of fibers near the surface of the part provides added benefit in the surface toughness. This reduces the sensitivity of the part to surface defects incurred during molding or handling and preferentially improves toughness in the surface region where tensile stresses are highest.
  • the inclusion of the glass fibers within the ceramic molding composition facilitates drying of the green body as the glass fiber network tends to diffuse moisture to the surface which both increases the drying rate, and helps eliminate moisture differentials within the green body to provide a more uniform water content. As a result, less differential shrinkage occurs during drying/firing of the green body which reduces the occurrence of stress related cracks in the article during the drying/firing process. Moreover, the fiber network tends to reduce the amount of linear shrinkage of the green body that occurs during drying/firing.
  • inclusion of the glass fibers within the ceramic molding composition decreases the drying time of the green body prior to firing, reduces linear shrinkage of the green body during drying/firing, helps eliminate moisture differentials that can result in crack formation, and provides the green body with increased strength and fracture toughness, all of which lead to a more efficient molding process with a reduced percentage of defective or broken parts resulting in scrap.
  • glass fibers also has the potential to reduce stresses in the fired microstructure. In some ceramic compositions, this is accomplished by enrichment in the composition by the glass fibers which flux into the ceramic body during firing. Localized compositional modifications may also modify the coefficient of thermal expansion which can blunt or deflect the propagation of cracks through the part, thereby improving toughness in the fired body.
  • the incorporation of fibers can toughen regions with stress risers such as sharp corners or double to single wall dropoffs.
  • chopped glass fiber segments are dispersed throughout the ceramic molding composition prior to its introduction into the mold.
  • the glass fiber segments can be made by any method known in the art that will provide chopped glass fibers in a form capable of being dispersed as individual filaments throughout the ceramic-forming composition.
  • the fiber segments are formed by "wet-chopping" a fiber strand (chopping the fiber strand after the application of an aqueous sizing composition) and maintaining the fiber segments in a wet state until they are added to the ceramic composition. Preparing the fibers in this manner reduces the filament to filament adherence that results when the sizing composition is allowed to dry, and enhances the dispersability of the fibers.
  • the fiber segments added to the ceramic composition have a moisture content of from about 0.5 to 30 percent by weight to aid dispersability of the fibers. More preferably, the moisture content of the fiber segments is from about 5 to 25 percent, with glass fibers having a moisture content of from about 8 to 12 percent being generally preferred.
  • the ceramic molding composition can be of any formulation known to the art to be useful in molding noncementitious ceramic articles.
  • Exemplary formulations may comprise, on a weight percent basis, from about 20 to 35% ball clay, 20-35% kaolin and 30-60% nonplastic materials.
  • the ceramic molding composition may be formulated in various ways. For example, a dry mixture of glass fibers and ceramic-forming powders may be prepared that can be dry pressed or that can be hydrated to form a moldable composition. To this end, the glass fibers may be dry blended with the other ingredients of the ceramic-forming composition, or the fibers may be added to a ceramic slurry and spray dried to form the dry composition.
  • the glass fibers are added directly to a ceramic slurry to form the moldable ceramic composition.
  • a ceramic slurry may contain from about 5 to 75 percent water by weight, depending on the technique intended to be used to shape the composition. Any conventional equipment that will disperse the glass fiber substantially homogeneously throughout the ceramic molding composition may be used to accomplish this.
  • the glass fibers are dispersed throughout the molding composition by a high shear mixing apparatus.
  • dispersion of the glass fibers throughout the composition can be accomplished by cycling the molding composition in the storage tank through a high shear mixer with the glass fibers, and returning the glass fiber containing ceramic-forming composition to the tank.
  • the high shear mixing also cleans cations from the particle surface according to the Hofmeister series: H>Ca>Mg>Na>K. Accordingly, the divalent calcium and magnesium cations will be cleaned from the particle surface first which helps to reduce coagulation during the fiber dispersion.
  • the low speed high torque tank mixer will maintain the glass fibers in a dispersed state.
  • high shear mixer 10 can be located remotely from the storage tank containing the molding composition, and the molding composition pumped through suitable piping from the tank to the mixer and back to the tank, a particularly preferred high shear mixing apparatus for dispersing the glass fibers is one designed to be mounted within the storage tank as depicted in Figure 1.
  • inclusion of high shear mixer 10 within storage tank 20 provides the tank with a two- stage mixing system comprising a high speed high shear mixer 10 to initially disperse the chopped fiber in the ceramic-forming composition, and a low speed high torque mixer 30 to maintain the fibers and colloidal ceramic-forming particles in a dispersed state.
  • High speed mixer 10 is formed of a cylindrical chamber 11 with open ends 12 and 13.
  • chamber 11 is mounted near the side of tank 20 at a height such that open end 12 is above the level of the molding composition in the tank 40 and open end 13 is below the level of the molding composition.
  • from about 50 to 80 percent of the chamber is submerged within the ceramic molding composition contained in the tank.
  • glass fiber is introduced into the mixing chamber through open end 12, and the ceramic molding composition enters the chamber through open end 13.
  • a high shear mixing blade 14 disperses the glass fiber throughout the ceramic molding composition and imparts a flow to the mixer contents that forces a portion of the mixed composition back out through open end 13.
  • mixing chamber 11 may have additional openings located adjacent the mixing blade to improve egress of the mixed composition from the chamber.
  • Mixing blade 14 is rotationally driven by motor 15 and drive means 16 at high speeds, preferably from about 350 to 500 revolutions per minute, to shear the glass fibers into the molding composition.
  • low speed high torque mixer 30 maintains the glass fiber ceramic particle dispersion.
  • Mixer 30 can be of any design capable of performing this function.
  • mixer 30 has blades or paddles 31 rotationally driven by motor 32 and drive means 33 at low speeds, preferably from about 14 to 20 revolutions per minute.
  • mixer 30 preferably has multiple blades or paddles to induce flow vertically as well as circularly within the tank, and is located within tank 20 so as to create an upward flow of the molding composition at open end 13 of mixing chamber 11 to ensure a good flow of molding composition through the high shear mixer.
  • the glass fiber segments used in the molding process of the invention may be of any size that will disperse substantially homogeneously throughout the ceramic molding composition and not deleteriously effect the moldability of the composition.
  • the chopped glass fibers are from about 0.5 to 10 mm in length and from about 5 to 20 microns in diameter. More preferably, the fibers are from about 1 to 6 mm in length and 9 to 14 microns in diameter.
  • the glass fibers may be incorporated into the molding composition in any amount that will impart the desired physical properties to the resulting green body or final ceramic article, but not interfere with the molding process.
  • inclusion of the glass fibers in the molding composition typically raises the viscosity of the composition. This can be problematic if not taken into account, especially in the molding of articles having complex shapes. If the viscosity of the molding composition becomes too high, incomplete filling of the mold may occur or other defects in the formed article may result. Moreover, as the viscosity of the composition rises, obtaining a substantially homogeneous dispersion of the fibers becomes more difficult.
  • the amount of fiber added to the composition must be balanced with the viscosity necessary to obtain good fiber dispersion and molding characteristics for the desired article.
  • the addition of glass fibers in an amount of from about 0.1 to 2.0 % of the dry weight of the molding composition provides compositions exhibiting enhanced green body strength and toughness, reduced shrinkage and improved drying characteristics.
  • the amount of glass fiber added to the molding composition is from about 0.5 to 1.0 % of the molding composition's dry weight. As illustrated in Figures 2 through 5, the inclusion of glass fibers in such amounts can significantly increase the flexural strength and fracture toughness of the green body, as well as decrease the differential and linear shrinkage of the green body upon drying.
  • the rheology of the ceramic molding composition may be largely controlled by the size distribution of the colloidal particles and the plasticity of the dispersion from cationic exchange.
  • the surface of the ceramic particles is primarily electronegative; thus by altering the ionic concentration of the aqueous suspension by adding compounds that are monovalent and compatible with the molding composition and the molding process, deflocculation of the ceramic particles occurs. This deflocculation lowers the viscosity of the molding composition. Consequently, the increase in viscosity that accompanies the addition of glass fibers with surface cations is at least partially offset by the deflocculation of the ceramic particles.
  • Useful deflocculating agents include sodium silicate, sodium polyacrylate and sodium carbonate, or other materials appropriate for the specific composition and colloidal distribution and cationic exchange relative to the Hofmeister series.
  • the particular deflocculating agent to be added to the ceramic molding composition, and the amount used depends upon a number of factors, such as the size and type of the ceramic-forming particles in the molding composition, the amount of fiber added, the type of molding being performed, and the complexity of the part being molded.
  • the defiocculants may be added to the ceramic composition before, after or together with the glass fibers, however, adding the defiocculants before the glass fibers is generally preferred.
  • gelation or thixotropic agents may be added.
  • Useful gelation or thixotropic agents include calcium sulfate, calcium carbonte, magnesium sulfate, calcium chloride and hydrochloric acid.
  • Suitable fibers include those made from compositions comprising, on a weight percent basis, from about 50 to 85% silica (Si0 2 ), 5 to 25% alumina (Al 2 0 3 ), 0 to 12% magnesia (MgO), 0 to 25% calcium oxide (CaO), 0 to 10% boron oxide (B 2 0 3 ), 0 to 15% sodium oxide (Na 2 0) and potassium oxide (K 2 0), and trace amounts of other oxides.
  • the glass fibers used in the process of the invention preferably withstand temperatures up to approximately 1200°C, the temperature at which essentially all shrinkage has occurred during the drying/firing process, without melting and fusing into the ceramic body.
  • Preferred glass fibers include glass fibers comprising from about 65 to 85% by weight silica (Si0 2 ), 15 to 25% by weight alumina (Al 2 0 3 ), and 0 to 12% by weight magnesia (MgO).
  • the fibers comprise from about 65 to 72% silica, 18 to 25% alumina, and 4 to 12% magnesia. Such fibers maintain their integrity during firing temperatures up to about 1000°C to 1500°C, thereby minimizing warpage and surface defects.
  • Exemplary glass compositions include:
  • Suitable metal oxides include zirconia, titania, tin oxide, vanadia, silicon carboxynitride and aluminosilicates.
  • the preferred metal oxides include zirconia, titania and tin oxide, with the most preferred being tin oxide.
  • Suitable phosphate containing compounds, or metal phosphates include pyrophosphate and polyphosphate compounds which include metals of groups I, II and III of the periodic table.
  • These coatings can be applied to the fibers by liquid or vapor deposition, or by incorporating the metal oxide or phosphate, or precursor thereof into the sizing composition coated on the fibers during the fiber-forming operation, or the precursor can be applied separately to sized fibers in-line during the fiber-forming operation or off-line after fiber formation by any technique known in the art.
  • the metal oxide or metal phosphate coatings are generated on the surface of sized fibers in an off-line deposition process that facilitates the uniform coating of filaments throughout a fibrous tow.
  • coating the fibers off-line (1) affords more time for the deposition to be completed (a period of several minutes rather than milliseconds); (2) can be performed in a variety of atmospheres, including vacuum; and (3) minimizes or eliminates human exposure to any toxic chemicals.
  • the fibers are coated with the metal oxide or its precursor and heated to a suitable temperature in an oven or reactor.
  • the deposition reactant can be in the form of solid powders, a liquid, or even a gas at room temperature.
  • the reactant may be added to the fiber strand as it enters the reactor or prior thereto, or the reactant may be applied to the fibers previously as a component of the sizing or a separate coating.
  • the reactant laden sized fiber strands are deposited into the reactor and the reactor is heated to the appropriate temperature for reaction. This temperature is typically between 200-500°C.
  • the reactant is preferably dosed into the reactor after the reactor has been evacuated and heated to the appropriate reaction temperature.
  • compositions have been deposited onto glass fiber strands by such process:
  • the process can be used to coat glass fibers with any compound that will react or decompose to form a metal, metal oxide, or metal phosphate on the glass fiber surface.
  • a variety of properties may be imparted to the glass strands.
  • such coatings may affect or improve electrical conductivity, thermal conductivity, refractive index, heat capacity, color, coupling to polymer matrix, abrasion resistance, handlability, modulus or strength of the glass fibers.
  • glass filaments coated with copper have exhibited significantly better abrasion resistance than uncoated filaments.
  • coatings to multifilament strands by this process advantageously permeates the strand and imparts a substantially uniform coating of the material to each filament. Moreover, such coatings do not aggressively bond the filaments of the strand together. To the contrary, strands coated by this process can typically be filamentized easily, often times simply by bending or flexing the strand. As such, the coating method is particularly useful for coating multifilament strands intended to be chopped and separated into discrete filaments and dispersed throughout a matrix to provide reinforcement.
  • the fibers are coated with tin oxide according to the following procedure.
  • the fibers are coated with an organotin precursor to tin oxide.
  • organotin compounds include tetra-n-butyltin, tetra-methyltin, di-n-butyltin diacetate and di-n-butyltin dichloride.
  • a preferred organotin compound is typically monobutyl trichlorotin (MBTC), which is applied neat or via an aqueous solution.
  • the precursor may be applied using an applicator as the fibers are formed, or by running the strand through a bath containing the solution.
  • the precursor-coated strands are then collected into a collection can, or wound onto a stainless steel core.
  • the can or wound package is then placed into an oven and heated to a temperature of from about 300°C to 500°C, preferably about 400°C, for approximately 10 to 60 minutes, preferably about 30 minutes, in air.
  • the MBTC reacts with oxygen and water to produce a tin oxide coating on the surface of the filaments.
  • the process is believed to be, in part, a chemical vapor deposition (CVD), because the precursor may become volatile and subsequently react at surface sites on the glass fibers within the strands.
  • the tin oxide coated fiber strands can then be pulled directly from the can or wound package and chopped to the desired length for use in the fabrication of ceramic articles.
  • the glass fibers may be coated by feeding chopped, uncoated glass fiber strands into a fluidized bed reactor which is heated to a temperature of from about 300° to 500°C, preferably about 400°C, and applying a mixture of MBTC and water into the fluidized bed.
  • the ensuing CVD reaction should yield the formation of a tin oxide coating on the surface of the chopped glass filaments.
  • the glass fibers used in the invention By coating the glass fibers used in the invention with tin oxide, it appears possible to reduce the loss in fiber tensile strength which occurs upon exposure of the fibers to the high temperatures encountered during firing.
  • the fibers When uncoated glass fibers are incorporated into a ceramic component (such as sanitary ware), the fibers typically flux and dissolve into the ceramic matrix during firing at temperatures of from about 1150 to 1200°C.
  • S glass ZenTronTM fibers glass fibers composed of about 70% Si0 2 , 20% Al 2 0 3 and 10% MgO, obtained from Owens-Corning) minimizes crystallization of the fiber when exposed to temperatures of 1200°C for 150 minutes.
  • Uncoated ZenTronTM fibers demonstrate extreme crystallization when heated to 1200°C for 150 minutes; Whereas, the tin oxide coated ZenTronTM fibers show little crystallization or other morphological changes after heating to 1200°C for 150 minutes. Accordingly, it is believed that tin oxide coatings on glass fibers may mitigate fluxing of the glass fiber during sintering of the ceramic. By retaining the fibrous morphology of the coated glass, the ceramic body may demonstrate enhanced fracture toughness. However, the desirability of such coatings are limited by their compatibility with the end use of the ceramic article. For example, such coatings may be undesirable for ceramic articles used as piezo electrics. Moreover, in some ceramic systems, the mullite enrichment that results from fluxing of the fibers during firing may be desirable.
  • the glass fibers used in the process of the invention are typically coated with a sizing composition to protect the glass fibers from being weakened as a result of abrasion during processing, as well as to facilitate the wetting of the coated fibers by the ceramic molding composition to enhance both the dispersability of the fibers throughout the composition and the coupling between the dried/cured ceramic material and the glass fibers.
  • a sizing composition to protect the glass fibers from being weakened as a result of abrasion during processing, as well as to facilitate the wetting of the coated fibers by the ceramic molding composition to enhance both the dispersability of the fibers throughout the composition and the coupling between the dried/cured ceramic material and the glass fibers.
  • the zeta potential of the sizing composition is similar to the isoelectric point and pH of the ceramic-forming slurry to aid in dispersing the fibers throughout the slurry.
  • Exemplary sizing compositions for glass fibers to be used as reinforcement for ceramic materials are set forth in Table I, wherein the amounts indicated are the respective
  • compositions may be applied to the glass fibers during the fiber forming operation, or subsequent thereto, by any method known in the art
  • a suitable quantity of appropriately size-coated glass fibers of suitable length and diameter are sheared into a ceramic molding composition in such a manner that the glass fibers are dispersed substantially homogeneously throughout the composition If the viscosity of the molding composition increases to an unacceptable level as a result of the fiber addition, suitable quantities of an appropriate deflocculating agent may be added to reduce the viscosity to an acceptable level.
  • the molding composition is supplied to a mold and formed into a green body of a desired shape. The green body is then dried and fired at elevated temperatures to fuse the ceramic particles and transform them into a ceramic material.
  • glass fibers in the ceramic green bodies have been found to reduce drying times by as much as 50 to 90%, increase the impact or fracture toughness of the green body by as much as 3600%, increase the flexural strength of the green body by as much as 80%, and reduce the differential and linear shrinkage of the green body during drying/firing by as much as 45%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

Cette invention concerne une composition de moulage en céramique contenant des fibres de verre, ainsi qu'un procédé de moulage d'articles en céramique avec cette composition. Ce procédé de moulage confère aux corps moulés non durcis des caractéristiques améliorées de solidité, de séchage et de rétrécissement.
PCT/US1998/009649 1997-05-15 1998-05-12 Compositions de moulage en ceramique renforcees par des fibres de verre WO1998051981A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU74812/98A AU7481298A (en) 1997-05-15 1998-05-12 Glass fiber reinforced ceramic molding compositions

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US85688097A 1997-05-15 1997-05-15
US08/856,880 1997-05-15

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2406564A (en) * 2003-10-03 2005-04-06 United Colour Ltd Coated refractory fibres
US7887917B2 (en) 2005-06-30 2011-02-15 Unifrax I Llc Inorganic fiber
US7985269B2 (en) 2006-12-04 2011-07-26 3M Innovative Properties Company Nonwoven abrasive articles and methods of making the same
US9556063B2 (en) 2014-07-17 2017-01-31 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US9567256B2 (en) 2013-03-15 2017-02-14 Unifrax I Llc Inorganic fiber
US9708214B2 (en) 2014-07-16 2017-07-18 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US9919957B2 (en) 2016-01-19 2018-03-20 Unifrax I Llc Inorganic fiber
US10023491B2 (en) 2014-07-16 2018-07-17 Unifrax I Llc Inorganic fiber
WO2020086247A1 (fr) * 2018-10-26 2020-04-30 Ocv Intellectual Capital, Llc Fibres de verre coupées pour céramiques
US10882779B2 (en) 2018-05-25 2021-01-05 Unifrax I Llc Inorganic fiber
US11203551B2 (en) 2017-10-10 2021-12-21 Unifrax I Llc Low biopersistence inorganic fiber free of crystalline silica

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US3076324A (en) * 1961-03-17 1963-02-05 Owens Corning Fiberglass Corp Production of coated fibers
US3736162A (en) * 1972-02-10 1973-05-29 Ceskoslovenska Akademie Ved Cements containing mineral fibers of high corrosion resistance
US3859106A (en) * 1971-03-23 1975-01-07 Nat Res Dev Autoclaved materials
US4090882A (en) * 1973-03-30 1978-05-23 Dyckerhoff Zementwerke Aktiengesellschaft Glassy calcium silicate fibers made from phosphorus slag
US4144195A (en) * 1974-09-24 1979-03-13 Volkswagenwerk Aktiengesellschaft High temperature resistant, heat insulating ceramic material
US4787125A (en) * 1986-03-24 1988-11-29 Ensci, Inc. Battery element and battery incorporating doped tin oxide coated substrate
US5470658A (en) * 1993-07-22 1995-11-28 Vetrotex France Glass fibers for reinforcing organic matrices

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3076324A (en) * 1961-03-17 1963-02-05 Owens Corning Fiberglass Corp Production of coated fibers
US3859106A (en) * 1971-03-23 1975-01-07 Nat Res Dev Autoclaved materials
US3736162A (en) * 1972-02-10 1973-05-29 Ceskoslovenska Akademie Ved Cements containing mineral fibers of high corrosion resistance
US4090882A (en) * 1973-03-30 1978-05-23 Dyckerhoff Zementwerke Aktiengesellschaft Glassy calcium silicate fibers made from phosphorus slag
US4144195A (en) * 1974-09-24 1979-03-13 Volkswagenwerk Aktiengesellschaft High temperature resistant, heat insulating ceramic material
US4787125A (en) * 1986-03-24 1988-11-29 Ensci, Inc. Battery element and battery incorporating doped tin oxide coated substrate
US5470658A (en) * 1993-07-22 1995-11-28 Vetrotex France Glass fibers for reinforcing organic matrices

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2406564A (en) * 2003-10-03 2005-04-06 United Colour Ltd Coated refractory fibres
US7887917B2 (en) 2005-06-30 2011-02-15 Unifrax I Llc Inorganic fiber
US7985269B2 (en) 2006-12-04 2011-07-26 3M Innovative Properties Company Nonwoven abrasive articles and methods of making the same
US9919954B2 (en) 2013-03-15 2018-03-20 Unifrax I Llc Inorganic fiber
US9567256B2 (en) 2013-03-15 2017-02-14 Unifrax I Llc Inorganic fiber
US10023491B2 (en) 2014-07-16 2018-07-17 Unifrax I Llc Inorganic fiber
US9708214B2 (en) 2014-07-16 2017-07-18 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US10301213B2 (en) 2014-07-16 2019-05-28 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US9926224B2 (en) 2014-07-17 2018-03-27 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US9556063B2 (en) 2014-07-17 2017-01-31 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US9919957B2 (en) 2016-01-19 2018-03-20 Unifrax I Llc Inorganic fiber
US11203551B2 (en) 2017-10-10 2021-12-21 Unifrax I Llc Low biopersistence inorganic fiber free of crystalline silica
US10882779B2 (en) 2018-05-25 2021-01-05 Unifrax I Llc Inorganic fiber
WO2020086247A1 (fr) * 2018-10-26 2020-04-30 Ocv Intellectual Capital, Llc Fibres de verre coupées pour céramiques
CN113056444A (zh) * 2018-10-26 2021-06-29 欧文斯科宁知识产权资产有限公司 用于陶瓷的截切玻璃纤维

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