WO2018019201A1 - 一种泡沫陶瓷过滤器及其制造方法 - Google Patents

一种泡沫陶瓷过滤器及其制造方法 Download PDF

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Publication number
WO2018019201A1
WO2018019201A1 PCT/CN2017/094065 CN2017094065W WO2018019201A1 WO 2018019201 A1 WO2018019201 A1 WO 2018019201A1 CN 2017094065 W CN2017094065 W CN 2017094065W WO 2018019201 A1 WO2018019201 A1 WO 2018019201A1
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WIPO (PCT)
Prior art keywords
slurry
ceramic foam
zirconia
filter
foam filter
Prior art date
Application number
PCT/CN2017/094065
Other languages
English (en)
French (fr)
Inventor
祝建勋
刘敬浩
杨淑金
Original Assignee
济南圣泉倍进陶瓷过滤器有限公司
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Publication date
Application filed by 济南圣泉倍进陶瓷过滤器有限公司 filed Critical 济南圣泉倍进陶瓷过滤器有限公司
Priority to KR1020197005205A priority Critical patent/KR102155075B1/ko
Priority to BR112019001489-6A priority patent/BR112019001489B1/pt
Priority to JP2019504937A priority patent/JP6756900B2/ja
Priority to ES17833504T priority patent/ES2863729T3/es
Priority to EP17833504.8A priority patent/EP3495337B1/en
Priority to US16/320,305 priority patent/US10994234B2/en
Publication of WO2018019201A1 publication Critical patent/WO2018019201A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2068—Other inorganic materials, e.g. ceramics
    • B01D39/2093—Ceramic foam
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/481—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing silicon, e.g. zircon
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    • C04B35/486—Fine ceramics
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    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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    • C04B35/632—Organic additives
    • C04B35/636—Polysaccharides or derivatives thereof
    • C04B35/6365—Cellulose or derivatives thereof
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • C22B9/023—By filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/10—Filtering material manufacturing
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9676—Resistance against chemicals, e.g. against molten glass or molten salts against molten metals such as steel or aluminium

Definitions

  • the present invention relates to the field of manufacturing high temperature filters for the foundry industry, and more particularly to a ceramic foam filter for filtering molten metal and a method of manufacturing the same.
  • the filter device for metal liquid purification is mainly a ceramic filter, which can effectively intercept harmful impurities in the molten metal and change the molten metal from turbulent flow to laminar flow, eradicate large inclusions in the molten metal, and remove the molten metal. Fine inclusions improve the structure of the structure, effectively reduce the gases and harmful elements in the molten metal, and purify and homogenize the molten metal.
  • Chinese patent application CN101164655A relates to a silicon carbide foam ceramic filter with silicon carbide (60% to 65%), aluminum oxide (30% to 35%), silicon oxide (2% to 5%), talc (0.5%). ⁇ 2.5%), water, and carboxymethyl cellulose, polyvinyl alcohol and silica sol as a binder to prepare a slurry, an oxide bonded silicon carbide ceramic filter was prepared.
  • Chinese patent CN101708402B (Patent No. 200910227626.5) prepared a multiphase silicon nitride bonded silicon carbide filter.
  • the silicon nitride bonded silicon carbide filter has excellent properties such as high thermal stability and strong oxidation resistance. However, it can also be infiltrated and eroded by molten materials such as magnesium, nickel-chromium alloy and stainless steel.
  • the filter prepared by the Chinese patent CN102173856A (Application No. 201010596190.X) has a mullite phase content of not less than 50% by weight, a chemical composition of 40 to 80% by weight of Al 2 O 3 , 10 to 50% by weight of SiO 2 and 1 to 10% by weight of an alkaline earth metal oxide.
  • CN102173856A can only handle molten metal below 1550 °C.
  • Chinese patent CN102503520B (application No. 201110371525.2) is 100 parts by weight of SiC; 5-8 parts by weight of silica powder; 10-13 parts by weight of alumina powder; 10-15 parts by weight of lithium bentonite; 5-20 parts by weight; 40 to 55 parts by weight of water; immersing the activated ceramic carrier in the slurry and sufficiently absorbing the slurry; drying the ceramic carrier sufficiently absorbing the slurry to remove excess slurry Thereby forming a green body; and drying and sintering the green body to produce a SiC foam ceramic filter.
  • Citride CN100536987C provides a zirconia foam ceramic filter, which is zirconia (75% ⁇ 80%), alumina (10 ⁇ 15%), calcium oxide (5% ⁇ 10%), yttrium oxide (0.5 % ⁇ 2%) consisting of ceramic powder, adding methyl cellulose, polyvinyl alcohol and water to prepare slurry, using soft polyurethane foam as carrier, impregnating the above slurry, extruding into blank, drying after 1700 ⁇ 1800°C High temperature sintering gives a zirconia foam ceramic filter. Among them, calcium oxide and cerium oxide are added as a volume stabilizer to stabilize the crystal form.
  • the tetragonal zirconia and the addition of calcium oxide and cerium oxide form a cubic solid solution, which can be maintained after cooling, and no crystal form reversible. Conversion, so there is no volume effect, avoiding cracking during firing.
  • the filter for filtering the molten metal generally uses silicon carbide, alumina, zirconia, carbon or the like.
  • the former two cannot meet the filtration of molten steel, and the latter two are more expensive. It is therefore necessary to develop a filter that is moderately priced and can filter molten steel.
  • a first object of the present invention is to provide a ceramic foam filter which has the advantages of high temperature resistance, low cost and the like.
  • One aspect of the invention relates to a ceramic foam filter comprising: by weight: the ceramic foam filter comprises:
  • Silicon carbide 20% to 50%, zirconia 20% to 55%, and silicon oxide 10% to 36%;
  • silicon carbide is 25% to 45%
  • zirconia is 25% to 50%
  • silicon oxide is 14% to 30%
  • Both are based on the total weight of the ceramic foam filter.
  • the foamed ceramic filter has a porosity of from 78% to 90%, preferably from 80% to 85%, as measured according to the national standard GB/T25139-2010.
  • the sum of the weight percentages of silicon carbide, zirconium oxide and silicon oxide is greater than or equal to 90%, greater than or equal to 95%, preferably greater than or equal to 96%, more preferably greater than or equal to 97%, and more preferably greater than or equal to 90% by weight based on the total weight of the ceramic foam filter. 98%, most preferably 99% or more.
  • the zirconia or zirconia precursor is one or more of stabilized zirconia, zircon powder, zirconium silicate.
  • the silica is fused silica or silicon micropowder.
  • the binder is silica sol, aluminum sol, phosphate, sulfate, water glass, silicate, borate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl fiber, hydroxypropyl fiber Or one or more of hydroxypropyl methylcellulose, cellulose ether, lignin, natural or synthetic resin, gum arabic, polyvinyl alcohol, polyvinyl butyral.
  • the admixture is one or more of a dispersant, a wetting agent, an antifoaming agent, a rheological agent, and a surfactant.
  • a second object of the present invention is to provide a method of making a ceramic foam filter comprising the steps of:
  • the open cell organic foam is a polyurethane foam, a polyvinyl chloride foam, a polystyrene foam, a latex foam or a cellulose foam.
  • the sintering temperature is from 1000 to 1600 ° C, preferably from 110 to 1 450 ° C.
  • the foam ceramic filter of the invention has good high temperature performance, can filter steel liquid, and is also suitable for filtering molten metal such as iron, copper, aluminum, etc., does not pollute the alloy, has good through-hole ratio, and oxidizes inclusions in the metal solution.
  • the flux is mixed with good filtration and adsorption capacity, good filtration and purification effect, high temperature strength, thermal shock stability and chemical resistance.
  • the preparation process of the invention is simple, and a filter product with a larger size can be prepared.
  • the current silicon carbide filter is a silicon carbide, aluminum oxide, and silicon oxide system.
  • the present invention improves the high temperature performance of the product by changing the material system.
  • a typical material-bonded silicon carbide filter cannot filter molten steel.
  • a method for manufacturing the above filter is provided, so that the filter has good sintering and comprehensive physical properties and has good thermal shock stability.
  • the present inventors have surprisingly found that the use of silicon carbide, zirconia and silica to provide a high temperature resistant metal impact, thermal stability filter for filtering high melting point molten metals such as molten steel.
  • the ceramic foam filter of the present invention is capable of The zirconia content is low (for example, the zirconia content is 20% to 55%, preferably 25% to 50%, for example, 30% to 45%, such as 35% to 40%), and high temperature resistance is achieved.
  • One aspect of the invention relates to a ceramic foam filter, particularly a ceramic foam filter for filtering molten metal, such as molten steel, comprising: silicon carbide, zirconia, and silica.
  • the ceramic foam filter of the present invention comprises:
  • Silicon carbide 20 to 50 parts by weight, preferably 25 to 45 parts by weight, more preferably 30 to 40 parts by weight, such as 35 parts by weight;
  • Zirconium oxide 20 to 55 parts by weight, preferably 25 to 50 parts by weight, more preferably 30 to 45 parts by weight, such as 35 to 40 parts by weight;
  • Silica 10 to 36 parts by weight, preferably 14 to 30 parts by weight, more preferably 15 to 25 parts by weight, for example, 20 parts by weight.
  • the ceramic foam filter of the present invention by weight, comprises:
  • Silicon carbide 20% to 50%, preferably 25% to 45%, more preferably 30% to 40%, such as 35%;
  • Zirconia 20% to 55%, preferably 25% to 50%, more preferably 30% to 45%, such as 35% to 40%;
  • Silica 10% to 36%, preferably 14% to 30%, more preferably 15% to 25%, for example 20%;
  • Both are based on the total weight of the ceramic foam filter.
  • the content of silicon carbide in the ceramic foam filter is: 20% to 50%, preferably 25% to 45%, more preferably 30% to 40%, such as 35%;
  • the content of zirconia in the ceramic foam filter is: 20% to 55%, preferably 25% to 50%, more preferably 30% to 45%, such as 35% to 40% by weight;
  • the content of silica in the ceramic foam filter is from 10% to 36%, preferably from 14% to 30%, more preferably from 15% to 25%, for example 20% by weight.
  • the ceramic foam filter of the present invention comprises: 20% to 50% of silicon carbide, 20% to 55% of zirconia, and 10% to 36% of silicon oxide; both are based on foam ceramic filtration. The total weight of the device.
  • the ceramic foam filter of the present invention comprises: 25% to 45% by weight of silicon carbide, 30% to 45% of zirconia, and 14% to 30% of silicon oxide; both are based on foam ceramic filtration. The total weight of the device.
  • the ceramic foam filter of the present invention comprises: 30% to 40% of silicon carbide, 30% to 45% of zirconia, and 15% to 25% of silicon oxide; both are based on foam ceramic filtration.
  • the total weight of the device is: 30% to 40% of silicon carbide, 30% to 45% of zirconia, and 15% to 25% of silicon oxide; both are based on foam ceramic filtration. The total weight of the device.
  • the sum of the weight percentages of silicon carbide, zirconium oxide and silicon oxide is greater than or equal to 90% based on the total weight of the ceramic foam filter, It is 95% or more, preferably 96% or more, more preferably 97% or more, more preferably 98% or more, and most preferably 99% or more.
  • the ceramic foam filter is composed of silicon carbide, zirconium oxide and silicon oxide.
  • the ceramic foam filter of the present invention is resistant to temperatures above 1600 ° C, preferably to temperatures above 1610 ° C.
  • the temperature of the high temperature resistance means that the filter having a size of 50 ⁇ 50 ⁇ 15 mm filters at least 50 kg of molten steel at this temperature without cracking.
  • the foamed ceramic filter of the present invention has a bulk density of 0.40 to 0.50 g/cm3, for example 0.45 g/cm3, as measured according to the national standard GB/T25139-2010.
  • the foamed ceramic filter of the present invention has a normal temperature compressive strength of ⁇ 1.5 MPa, preferably ⁇ 1.6 MPa, more preferably ⁇ 1.7 MPa, as measured according to the national standard GB/T25139-2010.
  • the high temperature (1200 ° C) compressive strength of the ceramic foam filter of the present invention is ⁇ 1 MPa, preferably ⁇ 1.1 MPa, as measured according to the national standard GB/T25139-2010.
  • the thermal shock resistance (1200 ° C - room temperature air cooling) of the ceramic foam filter of the present invention is greater than or equal to 3 times, preferably greater than or equal to 4 times, as measured according to the national standard GB/T 25139-2010.
  • the ceramic foam filter of the present invention has a porosity of from 78% to 90%, preferably from 80% to 85%, as measured according to the national standard GB/T25139-2010.
  • the ceramic foam filter of the present invention is made from a slurry comprising the following materials:
  • Silicon carbide zirconia or zirconia precursors, silica or silica precursors, binders, optional admixtures, optional rheological agents (such as thickeners), and liquid carriers.
  • the slurry comprises a silicon carbide, zirconia or zirconia precursor, a silica or silica precursor, a binder, an optional admixture, an optional rheological agent such as a thickener, and a liquid carrier.
  • the slurry comprises, by weight:
  • Silicon carbide 15 to 40%, preferably 20 to 35%, more preferably 25 to 30%;
  • Zirconium oxide or zirconia precursor 15 to 50%, preferably 20 to 40%, more preferably 30 to 35%;
  • Silica or silicon oxide precursor 5 to 25%, preferably 8 to 20%, more preferably 10 to 17%;
  • Binder 0.5 to 20%, preferably 1 to 15%, more preferably 5 to 10%;
  • Optional admixture 0 to 10%, such as 0.001 to 10%, such as 0.01 to 8%, preferably 0.1 to 5%, more preferably 0.2 to 3%;
  • Liquid carrier 5 to 30%, preferably 10 to 25%, more preferably 10 to 15%, still more preferably the balance of the liquid carrier;
  • Both are based on the total weight of the slurry.
  • the silicon carbide may have a particle size of from 100 to 400 mesh, preferably from 200 to 325 mesh, more preferably from 250 to 325 mesh.
  • the particle size of silicon carbide is generally 200 mesh. In order to facilitate the molding of the product, 325 mesh can be further used.
  • the zirconia precursor refers to a substance capable of being converted into zirconia by heating under an oxygen atmosphere (for example, under sintering conditions).
  • the zirconia or zirconia precursor is one or more of stabilized zirconia, zircon powder, zirconium silicate.
  • Zirconium oxide can be stabilized or unstable zirconia, and its production method is not limited, and it can be produced by electrofusion or chemical method.
  • the zirconia in the present invention may also be derived from zircon powder.
  • the zirconia or zirconia precursor has a particle size of from 50 to 400 mesh, preferably from 100 to 400 mesh, more preferably from 200 to 325 mesh.
  • the particle size of the zirconia or zirconia precursor is generally 325 mesh or even finer.
  • the silica precursor refers to a substance which can be converted into silicon oxide by heating under an oxygen-containing atmosphere (for example, under sintering conditions).
  • the silicon oxide is fused silica or silicon fine powder.
  • the silica or silica precursor may have a particle size of from 0.1 to 100 microns, preferably from 5 to 80 microns, more preferably from 10 to 60 microns, and most preferably from 5 to 44 microns.
  • the silica has a particle size of from 44 micrometers to several micrometers.
  • the silica is derived from fused silica, zirconium-containing silicon micropowder collected by fused zirconia, silicon micropowder collected by the ferroalloy plant, and by-products produced by melting metal silicon. Quartz can also be used.
  • the processed microsilica powder is preferably added in the form of a nanomaterial.
  • the silica precursor can be a silicate such as zirconium silicate.
  • the binder includes an inorganic binder and an organic binder.
  • the inorganic binder includes, but is not limited to, one or more of a silica sol, an aluminum sol, a phosphate, a sulfate, a water glass, a silicate (eg, sodium, potassium silicate), and a borate.
  • a silica sol an aluminum sol, a phosphate, a sulfate, a water glass, a silicate (eg, sodium, potassium silicate), and a borate.
  • the silica sol has a silica content of from 15% to 40%, preferably from 20% to 30%, for example, 25% to 30% by weight.
  • the aluminum sol has an alumina content of 10% to 30% by weight, preferably 12% to 25%, more preferably 15% by weight. 20%, for example 15%.
  • Organic binders include, but are not limited to, one or more of the following: carboxymethyl cellulose, methyl cellulose, hydroxyethyl fibers, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cellulose ether, wood Plain, natural or synthetic resin, gum arabic, polyvinyl alcohol, polyvinyl butyral. Natural or synthetic resins include, but are not limited to, polyethylene oxide, polyacrylic compounds.
  • the binder is one or more of the following: silica sol, aluminum sol, phosphate, sulfate, water glass, silicate, borate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl Base fiber, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cellulose ether, lignin, natural or synthetic resin, gum arabic, polyvinyl alcohol, polyvinyl butyral.
  • the binder is one or more of the following: carboxymethyl cellulose, methyl cellulose, lignin, natural or synthetic resin, gum arabic, polyvinyl alcohol, polyvinyl butyral, silica sol , aluminum sol, phosphate, sulfate, water glass.
  • the admixture includes, but is not limited to, a dispersant, a wetting agent, an antifoaming agent, a rheological agent, a surfactant, and the like.
  • the admixture is one or more of a dispersant, a wetting agent, an antifoaming agent, a rheological agent, and a surfactant.
  • Dispersing agents include sodium hexametaphosphate, sodium tripolyphosphate, polyacrylamide or sulfonic acids (such as sodium alkyl sulfonate, sodium methylene dinaphthalene sulfonate).
  • the dispersant is added in an amount of a few tenths of a percent by weight based on the total weight of the solids, for example from 0.1% to 8%, preferably from 0.2% to 1%, more preferably from 0.3% to 0.8%, so that the powder can be dispersed into the water during the agitation.
  • the wetting agent can be, for example, SILCO WET from Silcona GmbH & CO. KG; GLYDOL N193 from Sima, Germany.
  • the antifoaming agent may be a mineral oil defoaming agent, a silicone defoaming agent, and a polyether antifoaming agent.
  • the antifoaming agent may be a silicone oil defoaming agent or the like.
  • the most commonly used silicone defoamer is polydimethylsiloxane, also known as dimethicone.
  • the rheological agent can be a thickener.
  • some thickeners such as xanthan gum, polyvinyl alcohol, bentonite (for example, sodium-based or lithium-based bentonite), kaolin, and the like may be added.
  • the liquid carrier is typically water, and may be other liquids such as organic solvents such as methanol, ethanol and isopropanol.
  • the resin binder is usually an organic solvent.
  • the liquid carrier is water or an organic solvent such as methanol, ethanol and isopropanol.
  • the organic foam is an open mesh material to ensure that the ceramic slurry can penetrate freely, adhere to each other, and form a porous skeleton after firing.
  • the organic foam is hydrophilic to be strongly adsorbed with the ceramic slurry.
  • the organic foam is typically a polymeric sponge prepared by a foaming process.
  • the material of the organic foam may be polyurethane, polyvinyl chloride, polystyrene, latex or cellulose.
  • the organic foam is a polyurethane foam, preferably a flexible polyurethane foam sponge.
  • a second object of the present invention is to provide a method for producing a ceramic foam filter, which comprises preparing a slurry of silicon carbide, silicon oxide, a zirconium-containing material, a binder, an admixture, and a liquid carrier (for example, water).
  • a liquid carrier for example, water.
  • An open-cell organic foam for example, a flexible polyurethane foam sponge
  • the slurry is immersed, dried, and sintered at, for example, 1100 to 1450 ° C in an oxygen-containing atmosphere (for example, an air atmosphere) to obtain a foam ceramic filter for filtering the molten metal.
  • an oxygen-containing atmosphere for example, an air atmosphere
  • Another aspect of the invention relates to a method of manufacturing a ceramic foam filter comprising the steps of:
  • a slurry for example, a slurry comprising a silicon carbide, zirconium oxide or zirconia precursor, a silica or silica precursor, a binder, an optional admixture, and a liquid carrier;
  • the foam ceramic filter manufacturing method of the present invention comprises: providing silicon carbide: 20 to 35%; zirconia: 20 to 40%; silicon oxide: 10 to 20%; binder: 1 to 10 %; admixture: 0.1 to 5%; the above materials are added to the water by high-speed mixing and stirring to prepare a slurry of a certain viscosity, coated on a polyurethane sponge, and fired in an air atmosphere.
  • a method for fabricating a ceramic foam filter comprising the following steps:
  • a slurry can be formulated.
  • a high-efficiency mixer can be used to solidify the slurry.
  • the body and the liquid are mixed.
  • the slurry is at least 70% solids, no more than 30% liquid, more preferably at least 75% solids, no more than 25% liquid; even at least 80% solids, and no more than 20% liquid.
  • the slurry can be composed of 80% solids and 20% liquid.
  • the organic foam (e.g., polyurethane foam) is cut into a block or other desired shape in a certain size.
  • the organic foam can be pretreated prior to coating. For example, the organic foam is heated or hydrolyzed to remove the blind film, ensuring unobstructed voids and increasing porosity. After hydrolysis, the mixture was repeatedly rinsed with water and allowed to dry.
  • the organic foam is subjected to repeated extrusion to remove air prior to impregnation of the slurry, followed by slurry impregnation (coating).
  • the slurry impregnation (coating) may be an atmospheric pressure adsorption method, a vacuum adsorption method, a mechanical rolling method or a manual crucible method.
  • the slurry is impregnated (coated) by roll pressing (coating).
  • the formulated slurry is applied by roll pressing onto a cut polyurethane foam sponge to form at least one refractory coating.
  • the slurry impregnation can be carried out once, twice or more times. Preferably, the slurry impregnation is repeated a plurality of times until the internal air is completely excluded.
  • the impregnated organic foam is extruded, and the excess ceramic slurry is extruded to uniformly coat the slurry on the network structure of the foam, and the excess slurry is extruded to form a green body.
  • the coated porous body needs to be dried. Drying can be carried out using dry, hot air, infrared or microwave.
  • the coated material is dried at a relatively high temperature, such as between 100 and 200 ° C (e.g., about 150 ° C) to remove any residual volatiles.
  • the moisture after drying is controlled to be within 1% by weight, preferably within 0.5% by weight.
  • the sintering temperature is from 1000 to 1600 ° C, preferably from 1050 to 1500 ° C, more preferably from 110 to 1,450 ° C, for example, 1,300 ° C.
  • Sintering is carried out under an oxygen-containing atmosphere, for example, under an air atmosphere.
  • Sintering can generally be carried out in a kiln such as a shuttle kiln or a pusher kiln.
  • the filter size may be, for example, 30 to 80 x 30 to 80 x 8 to 25 mm, preferably 40 to 60 x 40 to 60 x 10 to 20 mm, more preferably 45 to 55 x 45 to 55 x 12 to 18 mm, and most preferably 50 x 50. ⁇ 15mm.
  • the foam ceramic filter of the invention has good high temperature performance in steel, iron, copper and aluminum solution, does not pollute the alloy, has good through-hole ratio, and has good filtering and adsorption on oxidation inclusions and flux inclusions in the metal solution.
  • the ability, filtration and purification effect is good, hot melt is small, high temperature strength, thermal shock stability and chemical resistance are excellent.
  • the manufacturing process of the invention is simple, and a product with a large size can be prepared.
  • Silicon carbide powder 325 mesh
  • Zirconia powder 400 mesh
  • Zircon powder (zirconia 65%; silica 33%): 400 mesh;
  • Silica powder 1 to 3 microns
  • Aluminum sol 15% alumina
  • Aluminium phosphate solution containing 7.5% aluminum phosphate.
  • Silicon carbide powder 25%; zircon powder: 40%; silica: 10%; calcium lignosulfonate: 4%; aluminum phosphate solution (containing aluminum phosphate 7.5%) 15%.
  • the above materials are all commercially available materials, and the ratios are all by weight.
  • the slurry is made by mixing the powder and water with a high-efficiency mixer.
  • the slurry is used to coat polyurethane foam. After the foam was applied to the slurry, the plugging holes were removed by air, placed in a microwave drying oven, and kept at 100-120 ° C for 1 hour, and then placed in a sintering furnace, followed by sintering at 1450 ° C.
  • polyurethane foam is also a commercially available material.
  • the filter made according to this formulation has a size of 50 x 50 x 15 mm and a porosity of 82%. 50 kg of molten steel was filtered at 1610 ° C, with the result that the filter withstood the test conditions and the molten steel was filtered as required.
  • the chemical composition of the prepared filter was (calculated): silicon carbide 33%; zirconia 34%; silicon oxide 31%; other 2%.
  • Silicon carbide powder 20%; zirconia powder: 40%; silica: 17%; aluminum sol: 10%.
  • the above materials are all commercially available materials, and the ratios are all by weight. In the above powder, it is necessary to add 1% of bentonite and 12% of water.
  • the slurry is made by mixing the powder and water with a high-efficiency mixer. The slurry is used to coat polyurethane foam. Foam finish After the slurry, the plugging holes were removed by air, placed in a hot air drying oven, and kept at 100-120 ° C for 2 hours, and then placed in a sintering furnace, followed by sintering at 1300 ° C.
  • polyurethane foam is also a commercially available material.
  • the filter made according to this formulation has a size of 50 x 50 x 15 mm and a porosity of 83%. 50 kg of molten steel was filtered at 1610 ° C, with the result that the filter withstood the test conditions and the molten steel was filtered as required.
  • the chemical composition of the prepared filter was (calculated): silicon carbide 25.5%; zirconia 51%; silica 21.5%, alumina 1%, other 1%.
  • Silicon carbide powder 35%; zirconia powder: 30%; silica: 10%; silica sol: 10%.
  • the above materials are all commercially available materials, and the ratios are by weight. In the above powder, 15% of water needs to be added.
  • the slurry is made by mixing the powder and water with a high-efficiency mixer. The slurry is used to coat polyurethane foam. After the foam was applied to the slurry, the plugging holes were removed by air, placed in a hot air drying oven, and kept at 100-120 ° C for 1 hour, and then placed in a sintering furnace, followed by sintering at 1100 ° C.
  • polyurethane foam is also a commercially available material.
  • the filter made according to this formulation has a size of 50 x 50 x 15 mm and a porosity of 84%. 50 kg of molten steel was filtered at 1610 ° C, with the result that the filter withstood the test conditions and the molten steel was filtered as required.
  • the chemical composition of the resulting filter was (calculated): silicon carbide 45%; zirconia 38%; silicon oxide 17%.
  • Silicon carbide powder 40%; zirconia powder: 34.9%; silica: 8%; silica sol: 8%; xanthan gum 0.1%.
  • the above materials are all commercially available materials, and the ratios are by weight. In the above powder, it is necessary to add 9% of water.
  • the slurry is made by mixing the powder and water with a high-efficiency mixer. The slurry is used to coat polyurethane foam. After the foam was applied to the slurry, the plugging holes were removed by air, placed in a hot air drying oven, and kept at 100-120 ° C for 2 hours, and then placed in a sintering furnace, followed by sintering at 1250 ° C.
  • polyurethane foam is also a commercially available material.
  • the filter made according to this formulation has a size of 50 x 50 x 15 mm and a porosity of 83%. 50 kg of molten steel was filtered at 1610 ° C, with the result that the filter withstood the test conditions and the molten steel was filtered as required.
  • the chemical composition of the resulting filter was (calculated): silicon carbide 47%; zirconia 27%; silicon oxide 26%.
  • the filter made according to this formulation has a size of 50 x 50 x 15 mm and a porosity of 80%. 50 kg of molten steel was filtered at 1610 ° C, with the result that the filter withstood the test conditions and the molten steel was filtered as required.
  • the chemical composition of the resulting filter was (calculated): silicon carbide 46%; zirconia 34%; silicon oxide 20%.
  • the filter made according to this formulation has a size of 50 x 50 x 15 mm and a porosity of 85%. 50 kg of molten steel was filtered at 1610 ° C, with the result that the filter withstood the test conditions and the molten steel was filtered as required.
  • the chemical composition of the prepared filter was (calculated): silicon carbide 20%; zirconia 42%; silica 36%; other 2%.
  • the filter made according to this formulation has a size of 50 x 50 x 15 mm and a porosity of 84%. 50 kg of molten steel was filtered at 1610 ° C, with the result that the filter withstood the test conditions and the molten steel was filtered as required.
  • the chemical composition of the resulting filter was (calculated): silicon carbide 37%; zirconia 49%; silicon oxide 14%.
  • Silicon carbide powder 36.5%; alumina powder: 31.2%; silica: 10.4%; silica sol: 10.4%; polyvinyl alcohol 4.2%.
  • the above materials are all commercially available materials, and the ratios are by weight. In the above powder, it is necessary to add 7.3% water.
  • the slurry is made by mixing the powder and water with a high-efficiency mixer. The slurry is used to coat polyurethane foam. After the foam was applied to the slurry, the plugging holes were removed by air, placed in a hot air drying oven, and kept at 100-120 ° C for 1 hour, and then placed in a sintering furnace, followed by sintering at 1100 ° C.
  • polyurethane foam is also a commercially available material.
  • the filter made according to this formula has a size of 50 ⁇ 50 ⁇ 15mm, and can only filter 30kg of molten steel at 1610°C. If it exceeds 30kg, the filter will rupture and cannot meet the requirements for use. Only 50 kg of molten steel can be filtered at 1550 °C.
  • Silicon carbide powder 35.9%; chrome ore powder: 30.8%; silica: 10.3%; silica sol: 10.3%; polyvinyl alcohol 4.1%.
  • the above materials are all commercially available materials, and the ratios are by weight. In the above powder, it is necessary to add 8.7% of water based on the total weight of the slurry.
  • the slurry is made by mixing the powder and water with a high-efficiency mixer. The slurry is used to coat polyurethane foam. After the foam is applied to the slurry, the plugging holes are removed by air, then placed in a hot air drying oven, and incubated at 100-120 ° C for 1-2 hours, then placed in a sintering furnace, and then sintered at 1100 ° C.
  • polyurethane foam is also a commercially available material.
  • the filter made according to this formulation has a size of 50 x 50 x 15 mm. At 1610 ° C, 35 kg of molten steel can be filtered, and if it exceeds 35 kg, the filter will rupture and cannot meet the requirements for use. Only 50 kg of molten steel can be filtered at 1570 °C.
  • Silicon carbide powder 15%; mullite (Al 2 O 3 -SiO 2 ) 54%; silica: 8%; aluminum sol: 15%; clay 1.5%; bentonite 0.5%.
  • the above materials are all commercially available materials, and the ratios are by weight. In the above powder, it is necessary to add 6.0% of water.
  • the slurry is made by mixing the powder and water with a high-efficiency mixer. The slurry is used to coat polyurethane foam. After the foam was applied to the slurry, the plugging holes were removed by air, placed in a hot air drying oven, and kept at 100-120 ° C for 2 hours, and then placed in a sintering furnace, followed by sintering at 1300 ° C.
  • polyurethane foam is also a commercially available material.
  • the filter made according to this formula has a size of 50 ⁇ 50 ⁇ 15mm, and can only filter 20kg of molten steel at 1610°C. If it exceeds 20kg, the filter will rupture and cannot meet the requirements for use. Only 50 kg of molten steel can be filtered at 1520 °C.
  • the prepared filter has a size of 50 ⁇ 50 ⁇ 15mm, and can only filter 20kg of molten steel at 1610°C. If it exceeds 20kg, the filter will rupture and cannot meet the requirements for use. Only 50 kg of molten steel can be filtered at 1520 °C.
  • Example 1 of CN100536987C a foamed ceramic having a chemical composition (theoretical value) of 78.5% of zirconia, 13% of alumina, 6.5% of calcium oxide, and 1% of cerium oxide was obtained.
  • the prepared filter has a size of 50 ⁇ 50 ⁇ 15mm, and can only filter 40kg of molten steel at 1610°C. If it exceeds 40kg, the filter will rupture and cannot meet the requirements for use. Only 50 kg of molten steel can be filtered at 1580 °C.
  • Embodiments 1 to 7 of the present invention employ silicon carbide, zirconium oxide, and silicon oxide materials, which are capable of providing high temperature resistant metal impact and thermal stability for filtering high melting point molten metal, for example.
  • Steel water filter The ceramic foam filter of the present invention can achieve high temperature resistance at a low zirconia content (as in Examples 1 to 7), and has good thermal stability, normal temperature compressive strength, high temperature flexural strength, and resistance. Thermal shock.

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Abstract

一种泡沫陶瓷过滤器及其制造方法。按重量计，泡沫陶瓷过滤器包括：碳化硅20%～50%，氧化锆20%～55%，以及氧化硅10%～36%，均基于泡沫陶瓷过滤器的总重量。制造泡沫陶瓷过滤器的方法，包括以下步骤：(a)提供包括碳化硅、氧化锆或氧化锆前驱体、氧化硅或氧化硅前驱体、粘结剂、可选的外加剂、以及液体载体的浆料；(b)将浆料涂挂在开孔有机泡沫体上；(c)将涂挂有浆料的开孔有机泡沫体干燥，得到坯体；(d)含氧气氛下烧结坯体，得到泡沫陶瓷过滤器。

Description

一种泡沫陶瓷过滤器及其制造方法
本申请要求中国发明专利申请201610590965.X(申请日：2016年07月25日；发明名称：一种泡沫陶瓷过滤器及其制造方法)的优先权，其全部内容通过援引并入本说明书。
技术领域
本发明涉及铸造行业用高温过滤器的制造领域，更具体地，涉及一种用于过滤熔融金属的泡沫陶瓷过滤器及其制造方法。
背景技术
金属液的净化对提高铸件的力学性能起到重要作用。目前用于金属液净化的过滤装置主要为陶瓷过滤器，可有效截获金属液中的有害杂质并使金属液由紊流变为层流，根除金属液中的大块夹杂物，去除金属液中细小夹杂物，改善组织结构，有效降低金属液中的气体及有害元素，对金属液起到净化和均质作用。
中国专利申请CN101164655A涉及一种碳化硅质泡沫陶瓷过滤器，以碳化硅(60％～65％)、氧化铝(30％～35％)、氧化硅(2％～5％)、滑石(0.5％～2.5％)、水，并以羧甲基纤维素、聚乙烯醇和硅溶胶做结合剂制备泥浆，制备了氧化物结合碳化硅陶瓷过滤器。
中国专利申请CN1700948A以碳化硅(40％～60％)、胶体二氧化硅(5％～20％)结合剂以及至少10％的煅烧二氧化硅的陶瓷你将制备了氧化物结合碳化硅陶瓷过滤器。CN1700948A的陶瓷过滤器仅在1428℃进行了测试。
中国专利CN101708402B(专利号200910227626.5)制备了复相氮化硅结合碳化硅过滤器。虽然氮化硅结合碳化硅过滤器具有热稳定性高、抗氧化能力强等优良性能。但也能被镁、镍铬合金、不锈钢等熔液所浸润和侵蚀。
中国专利CN102173856A(申请号201010596190.X)制备的过滤器，主要以莫来石相含量不少于50wt％，化学组成中含有40～80wt％的Al2O3、10～50wt％的SiO2和1～10wt％的碱土金属氧化物。CN102173856A仅能处理低于1550℃的熔融金属。
中国专利CN102503520B(申请号201110371525.2)以SiC为100重量份；二氧化硅粉为5-8重量份；氧化铝粉为10-13重量份；锂基膨润土为10-15重量份；粘结剂为5-20重量份； 水为40-55重量份；将经过活化处理的陶瓷载体浸渍在所述浆料中并使其充分吸收所述浆料；对充分吸收所述浆料的陶瓷载体进行甩干以去除多余浆料从而形成坯体；以及干燥并烧结所述坯体从而制得SiC泡沫陶瓷过滤器。
中国专利CN100536987C提供了一种氧化锆质泡沫陶瓷过滤器，是以氧化锆(75％～80％)、氧化铝(10～15％)、氧化钙(5％～10％)、氧化钇(0.5％～2％)组成陶瓷粉末，再加入甲基纤维素、聚乙烯醇和水制备料浆，以软质聚氨酯泡沫塑料为载体，浸渍上述料浆，挤压制成坯料，干燥后1700～1800℃高温烧结得到氧化锆质泡沫陶瓷过滤器。其中氧化钙、氧化钇是作为体积稳定剂加入以稳定晶型，在1500℃以上，正方晶型的氧化锆与加入氧化钙、氧化钇生成立方型固溶体，冷却后仍然能保持，没有晶型可逆转化，因而没有体积效应，避免烧制时开裂。
目前过滤金属液的过滤器一般采用碳化硅质、氧化铝质、氧化锆质、碳质等。前两者不能满足钢液的过滤，后二种价格较高。因此有必要开发一种价格适中又能过滤钢水的过滤器。
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种泡沫陶瓷过滤器，本发明的泡沫陶瓷过滤器具有耐高温、成本低等优点。
本发明一方面涉及一种泡沫陶瓷过滤器，按重量计，所述泡沫陶瓷过滤器包括：
碳化硅20％～50％，氧化锆20％～55％，以及氧化硅10％～36％；
优选，碳化硅25％～45％，氧化锆25％～50％，以及氧化硅14％～30％；
更优选，碳化硅30％～40％，氧化锆30％～45％，以及氧化硅15％～25％；
均基于所述泡沫陶瓷过滤器的总重量。
优选地，按照国家标准GB/T25139-2010进行测定，所述泡沫陶瓷过滤器的孔隙率在78％～90％，优选80％～85％。
基于所述泡沫陶瓷过滤器的总重量，碳化硅、氧化锆和氧化硅重量百分比之和大于等于90％，大于等于95％，优选大于等于96％，更优选大于等于97％，更优选大于等于98％，最优选大于等于99％。
优选地，氧化锆或氧化锆前驱体为稳定氧化锆、锆英粉、硅酸锆中的一种或多种。
优选地，氧化硅为熔融石英或硅微粉。
优选地，粘结剂为硅溶胶、铝溶胶、磷酸盐、硫酸盐、水玻璃、硅酸盐、硼酸盐、羧甲基纤维素、甲基纤维素、羟乙基纤维、羟丙基纤维素、羟丙基甲基纤维素、纤维素醚、木质素、天然或人工合成树脂、***胶、聚乙烯醇、聚乙烯醇缩丁醛中的一种或多种。
优选地，外加剂为分散剂、润湿剂、消泡剂、流变剂以及表面活性剂中的一种或多种。
本发明的第二目的在于提供制造泡沫陶瓷过滤器的方法，包括以下步骤：
(a)提供包括碳化硅、氧化锆或氧化锆前驱体、氧化硅或氧化硅前驱体、粘结剂、可选的外加剂、以及液体载体的浆料；
(b)将浆料涂挂在开孔有机泡沫体上；
(c)将涂挂有浆料的开孔有机泡沫体干燥，得到坯体；
(d)含氧气氛下烧结坯体，得到泡沫陶瓷过滤器。
优选地，开孔有机泡沫体为聚氨酯泡沫、聚氯乙烯泡沫、聚苯乙烯泡沫、乳胶泡沫或纤维素泡沫。
优选地，烧结的温度为1000-1600℃，优选1100-1450℃。
本发明的泡沫陶瓷过滤器具有良好的高温性能，可以过滤钢液，也适合于过滤铁、铜、铝等金属液，不污染合金，具有良好的通孔率，对金属溶液中的氧化夹杂和熔剂夹杂有良好的过滤和吸附能力，过滤净化效果好，高温强度、热震稳定性及抗化学侵蚀性等都非常优良。同时本发明制备工艺简单，可制备尺寸较大的过滤器产品。
具体实施方式
现在的碳化硅过滤器是碳化硅、氧化铝、氧化硅体系，本发明是通过改变材料体系来提高产品的高温性能。
一般材料结合的碳化硅过滤器不能过滤钢水。本发明的目的在于提供一种高温性能更好，能够承受高温金属冲击、热稳定性更好的用于过滤高熔点熔融金属例如钢水的过滤器。同时提供一种上述过滤器的制造方法，使得过滤器具有良好的烧结和综合物理性能，并具有良好的热震稳定性。
本发明出人意料地发现，采用碳化硅、氧化锆以及氧化硅能够提供耐高温金属冲击、热稳定性更好的用于过滤高熔点熔融金属例如钢水的过滤器。本发明的泡沫陶瓷过滤器能够在 氧化锆含量较低(例如氧化锆含量20％～55％，优选25％～50％，例如30％～45％，如35％～40％)的情况下，实现耐高温性能。
I.泡沫陶瓷过滤器
本发明一方面涉及一种泡沫陶瓷过滤器，特别是用于过滤熔融金属(例如钢水)的泡沫陶瓷过滤器，包括：碳化硅、氧化锆以及氧化硅。
优选地，本发明泡沫陶瓷过滤器包括：
碳化硅：20～50重量份，优选25～45重量份，更优选30～40重量份，如35重量份；
氧化锆：20～55重量份，优选25～50重量份，更优选30～45重量份，如35～40重量份；以及
氧化硅：10～36重量份，优选14～30重量份，更优选15～25重量份，例如20重量份。
优选地，本发明泡沫陶瓷过滤器，按重量计，包括：
碳化硅：20％～50％，优选25％～45％，更优选30％～40％，如35％；
氧化锆：20％～55％，优选25％～50％，更优选30％～45％，如35％～40％；以及
氧化硅：10％～36％，优选14％～30％，更优选15％～25％，例如20％；
均基于泡沫陶瓷过滤器的总重量。
泡沫陶瓷过滤器中碳化硅的含量按重量计为：20％～50％，优选25％～45％，更优选30％～40％，如35％；
泡沫陶瓷过滤器中氧化锆的含量按重量计为：20％～55％，优选25％～50％，更优选30％～45％，如35％～40％；以及
泡沫陶瓷过滤器中氧化硅的含量按重量计为：10％～36％，优选14％～30％，更优选15％～25％，例如20％。
在一种优选的实施方式中，本发明泡沫陶瓷过滤器按重量计包括：碳化硅20％～50％，氧化锆20％～55％，以及氧化硅10％～36％；均基于泡沫陶瓷过滤器的总重量。
在一种优选的实施方式中，本发明泡沫陶瓷过滤器按重量计包括：碳化硅25％～45％，氧化锆30％～45％，以及氧化硅14％～30％；均基于泡沫陶瓷过滤器的总重量。
在一种优选的实施方式中，本发明泡沫陶瓷过滤器按重量计包括：碳化硅30％～40％，氧化锆30％～45％，以及氧化硅15％～25％；均基于泡沫陶瓷过滤器的总重量。
基于泡沫陶瓷过滤器的总重量，碳化硅、氧化锆和氧化硅重量百分比之和大于等于90％， 大于等于95％，优选大于等于96％，更优选大于等于97％，更优选大于等于98％，最优选大于等于99％。
在一种优选的实施方式中，泡沫陶瓷过滤器由碳化硅、氧化锆和氧化硅构成。
优选地，本发明的泡沫陶瓷过滤器耐1600℃以上高温，优选耐1610℃以上高温。在本发明中，耐高温性的温度是指尺寸50×50×15mm过滤器在该温度下过滤至少50kg钢水不破裂。
优选地，按照国家标准GB/T25139-2010进行测定，本发明的泡沫陶瓷过滤器的体积密度为0.40～0.50g/cm3，例如0.45g/cm3。
优选地，按照国家标准GB/T25139-2010进行测定，本发明的泡沫陶瓷过滤器的常温耐压强度≥1.5MPa，优选≥1.6MPa，更优选≥1.7MPa。
优选地，按照国家标准GB/T25139-2010进行测定，本发明的泡沫陶瓷过滤器的高温(1200℃)耐压强度≥1MPa，优选≥1.1MPa。
优选地，按照国家标准GB/T25139-2010进行测定，本发明的泡沫陶瓷过滤器的抗热震性(1200℃-室温风冷)为大于或等于3次，优选大于或等于4次。
优选地，按照国家标准GB/T25139-2010进行测定，本发明的泡沫陶瓷过滤器的孔隙率在78％～90％，优选80％～85％。
优选地，本发明的泡沫陶瓷过滤器由包括以下原料的浆料制成：
碳化硅、氧化锆或氧化锆前驱体、氧化硅或氧化硅前驱体、粘结剂、可选的外加剂、可选的流变剂(如增稠剂)以及液体载体。
II.浆料及组分
浆料包括碳化硅、氧化锆或氧化锆前驱体、氧化硅或氧化硅前驱体、粘结剂、可选的外加剂、可选的流变剂(如增稠剂)以及液体载体。
优选地，按重量计，浆料包括：
碳化硅：15～40％，优选20～35％，更优选25～30％；
氧化锆或氧化锆前驱体：15～50％，优选20～40％，更优选30～35％；
氧化硅或氧化硅前驱体：5～25％，优选8～20％，更优选10～17％；
粘结剂：0.5～20％，优选1～15％，更优选5～10％；
可选的外加剂：0～10％，如0.001～10％，例如0.01～8％，优选0.1～5％，更优选0.2～3％；
液体载体：5～30％，优选10～25％，更优选10～15％，还进一步优选余量的液体载体；
均基于浆料的总重量。
(1)碳化硅
碳化硅粒度可以为100～400目，优选200～325目，更优选250～325目。碳化硅粒度一般采用200目，为便于产品的成型，更进一步可以采用325目。
(2)氧化锆或氧化锆前驱体
氧化锆前驱体是指含氧气氛下加热(例如在烧结条件下)能够转变成氧化锆的物质。
优选地，氧化锆或氧化锆前驱体为稳定氧化锆、锆英粉、硅酸锆中的一种或多种。氧化锆可以采用稳定的或不稳定的氧化锆，其制造方法不受限制，可以采用电熔法也可以采用化学法生产。本发明中的氧化锆也可以来源于锆英粉。优选地，氧化锆或氧化锆前驱体粒度为50～400目，优选100～400目，更优选200～325目。氧化锆或氧化锆前驱体粒度一般采用325目甚至更细。
(3)氧化硅或氧化硅前驱体
氧化硅前驱体是指在含氧气氛下加热(例如在烧结条件下)能够转变成氧化硅的物质。
优选地，氧化硅为熔融石英、硅微粉。氧化硅或氧化硅前驱体粒度可以为0.1～100微米，优选5～80微米，更优选10～60微米，最优选5～44微米。优选地，氧化硅的粒度为44微米到几微米。
为保证烧成产品的强度以及降低烧结温度，氧化硅来源于熔融石英、电熔氧化锆收集的含锆硅微粉、铁合金厂收集的硅微粉以及熔炼金属硅时产生出的副产品，也可以采用石英加工后的微硅粉，优选以纳米材料形式加入。
氧化硅前驱体可以是硅酸盐，例如硅酸锆。
(4)粘结剂
粘结剂包括无机粘结剂和有机粘结剂。
优选地，无机粘结剂包括但不限于：硅溶胶、铝溶胶、磷酸盐、硫酸盐、水玻璃、硅酸盐(例如钠、钾硅酸盐)、以及硼酸盐中的一种或多种。
优选地，硅溶胶的氧化硅含量按重量计为15％～40％，优选20％～30％，例如，25％，30％。
优选地，铝溶胶的氧化铝含量按重量计为10％～30％，优选12％～25％，更优选15％～ 20％，例如15％。
有机粘结剂包括但不限于以下一种或多种：羧甲基纤维素、甲基纤维素、羟乙基纤维、羟丙基纤维素、羟丙基甲基纤维素、纤维素醚、木质素、天然或人工合成树脂、***胶、聚乙烯醇、聚乙烯醇缩丁醛。天然或人工合成树脂包括但不限于聚环氧乙烷、聚丙烯酸类化合物。
优选地，粘结剂为以下一种或多种：硅溶胶、铝溶胶、磷酸盐、硫酸盐、水玻璃、硅酸盐、硼酸盐、羧甲基纤维素、甲基纤维素、羟乙基纤维、羟丙基纤维素、羟丙基甲基纤维素、纤维素醚、木质素、天然或人工合成树脂、***胶、聚乙烯醇、聚乙烯醇缩丁醛。
优选地，粘结剂为以下一种或多种：羧甲基纤维素、甲基纤维素、木质素、天然或人工合成树脂、***胶、聚乙烯醇、聚乙烯醇缩丁醛、硅溶胶、铝溶胶、磷酸盐、硫酸盐、水玻璃。
(5)外加剂
优选地，外加剂包括但不限于分散剂、润湿剂、消泡剂、流变剂、表面活性剂等。例如，外加剂为分散剂、润湿剂、消泡剂、流变剂、以及表面活性剂中的一种或多种。
分散剂包括六偏磷酸钠、三聚磷酸钠、聚丙烯酰胺或磺酸类物质(如烷基磺酸钠、亚甲基二萘磺酸钠)。分散剂加入量为占固体总重量的零点几个百分点，例如0.1％～8％，优选0.2％～1％，更优选0.3％～0.8％，以使在搅拌过程中可以使粉末分散到水中。
润湿剂可以例如为：Silcona GmbH&CO.KG的SILCO WET；德国司马的GLYDOL N193。
消泡剂可以是矿物油类消泡剂、有机硅类消泡剂以及聚醚类消泡剂。例如，消泡剂可以为硅油消泡剂等。有机硅类消泡剂最常用的是聚二甲基硅氧烷，也称二甲基硅油。
流变剂可以是增稠剂。为改善浆料的成型性能可以加入一些增稠剂，如：黄原胶、聚乙烯醇、膨润土(例如钠基或锂基膨润土)、高岭土等。
(6)液体载体
液体载体一般是水，也可以是其它液体例如有机溶剂如甲醇、乙醇及异丙醇。树脂类粘结剂通常采用有机溶剂。优选地，液体载体为水或有机溶剂，例如甲醇、乙醇及异丙醇。
(7)有机泡沫体
有机泡沫体为开口网状材料，以保证陶瓷浆料能够自由渗透，相互粘连，烧制后能形成多孔骨架。
当液体载体为水时，有机泡沫体要具有亲水性，以与陶瓷浆料牢固吸附。
有机泡沫体通常为经过发泡工艺制备的聚合物海绵。有机泡沫体的材料可以为聚氨酯、聚氯乙烯、聚苯乙烯、乳胶或纤维素。优选地，有机泡沫体为聚氨酯泡沫，优选软质聚氨酯泡沫海绵。
III.方法及工艺步骤
本发明的第二目的在于提供一种所述的泡沫陶瓷过滤器的制造方法，以碳化硅、氧化硅、含锆材料、粘结剂、外加剂、液体载体(例如水)制备料浆，以开孔有机泡沫体(例如软质聚氨酯泡沫海绵)为载体，浸渍上述料浆，干燥后在例如1100～1450℃、含氧气氛(例如空气气氛)下烧结得到用于过滤金属液的泡沫陶瓷过滤器。
本发明另一方面涉及一种泡沫陶瓷过滤器制造方法，包括以下步骤：
(a)提供浆料，例如配制包括碳化硅、氧化锆或氧化锆前驱体、氧化硅或氧化硅前驱体、粘结剂、可选的外加剂、以及液体载体的浆料；
(b)将浆料涂挂在开孔有机泡沫体上；
(c)将涂挂有浆料的开孔有机泡沫体干燥，得到坯体；
(d)烧结坯体，得到泡沫陶瓷过滤器。
根据一些优选的实施方式，本发明的泡沫陶瓷过滤器制造方法包括：提供碳化硅：20～35％；氧化锆：20～40％；氧化硅：10～20％；粘结剂：1～10％；外加剂：0.1～5％；上述材料加入水经过高速混合搅拌制成一定黏度的浆料，涂挂于聚氨酯海绵上，在空气气氛下进行烧成。
根据本发明的一种优选实施方式，提供一种泡沫陶瓷过滤器制作方法，包括下面的步骤：
(a)提供浆料，例如将各原料、液体载体(例如水)配制成浆料；
(b)将配制好的浆料采用辊压涂挂在切割好的聚氨酯泡沫海绵上形成至少一层耐火涂层；
(c)将形成耐火涂层的开孔多孔材料烘干；
(d)在1100～1450℃下进行烧结。
本发明方法中的浆料、原料及配比如上文所述，在此不再赘述。
下面对各个工艺步骤进行具体介绍。
(a)提供浆料
对于步骤(a)，可以配制浆料。在浆料的制备过程中，可以使用高效混料器将浆料中的固 体和液体进行混合。浆料中为至少70％固体，不超过30％液体，更为可取的是至少75％固体，液体不超过25％；甚至固体至少80％，液体不超过20％。例如，浆料可以由80％固体及20％液体组成。
(b)浆料涂挂
将有机泡沫体(例如聚氨酯泡沫)按一定尺寸切割成块状或其他所需形状。在涂挂前，可以对有机泡沫体进行预处理。例如，将有机泡沫体加热或水解，去除盲孔薄膜，保证空隙畅通，提高孔隙率。水解后，反复揉搓并用水洗净，晾干备用。
通常，有机泡沫体在浸渍浆料之前需经过反复挤压以排除空气，然后进行浆料浸渍(涂挂)。浆料浸渍(涂挂)可以为常压吸附法、真空吸附法、机械辊压法或手工揉搓法。
优选地，浆料浸渍(涂挂)为辊压浸渍(涂挂)。例如，将配制好的浆料采用辊压涂挂在切割好的聚氨酯泡沫海绵上形成至少一层耐火涂层。
浆料浸渍可以进行一次、两次或更多次。优选浆料浸渍重复多次，直至完全排除内部的空气。将浸渍后的有机泡沫体进行挤压，挤出多余的陶瓷浆料，使浆料均匀地涂挂在泡沫体的网状结构上，挤出多余浆料，制成坯体。
(c)干燥
涂挂后的多孔坯体需进行干燥。干燥可以采用阴干、热风、红外或者微波进行。
涂挂后的材料最好在较高温度下干燥如，在100～200℃之间进行干燥(如约150℃)，以去掉所有残留的挥发物。按重量计，优选干燥后的水分控制在1％以内，优选在0.5％以内。
(d)烧结
优选地，烧结温度在1000-1600℃，优选1050-1500℃，更优选1100-1450℃，例如1300℃。烧结在含氧气氛下进行，例如在空气气氛下进行。烧结一般可以在梭式窑、推板窑等窑炉内进行。
过滤器尺寸例如可以为30～80×30～80×8～25mm，优选40～60×40～60×10～20mm，更优选45～55×45～55×12～18mm，最优选50×50×15mm。
本发明的泡沫陶瓷过滤器在钢、铁、铜、铝溶液中具有良好的高温性能，不污染合金，具有良好的通孔率，对金属溶液中的氧化夹杂和熔剂夹杂有良好的过滤和吸附能力，过滤净化效果好，热熔小，高温强度、热震稳定性及抗化学侵蚀性等都非常优良。同时本发明制造工艺简单，可制备尺寸大的产品。
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购买获得的常规产品。
实施例
原料
碳化硅粉：325目；
氧化锆粉：400目；
锆英粉(氧化锆65％；氧化硅33％)：400目；
氧化硅粉：1～3微米；
铝溶胶：含氧化铝15％；
硅溶胶：含氧化硅30％；
硅酸锆：400目；
磷酸铝溶液：含磷酸铝7.5％。
实施例1
碳化硅粉：25％；锆英粉：40％；氧化硅：10％；木质素磺酸钙：4％；磷酸铝溶液(含磷酸铝7.5％)15％。上述的材料都是市售材料，所述的比例都是重量百分比。在上述粉末中，需要加入0.1％的黄原胶及5.9％的水。浆料是用一个高效混料器把粉料及水混合制成的。该浆料用来涂挂聚氨酯泡沫。泡沫涂挂完浆料后，用空气除掉堵孔，然后放入微波干燥炉内，在100-120℃下保温1小时后，装入烧结炉内，然后在1450℃下进行烧结。其中的聚氨酯泡沫也是市售材料。
按此配方制成的过滤器尺寸为50×50×15mm，孔隙率：82％。在1610℃下过滤了50kg钢水，结果是该过滤器经受住了该检测条件，并且按要求对熔融钢水进行了过滤。
制成的过滤器化学组成为(计算值)：碳化硅33％；氧化锆34％；氧化硅31％；其他2％。
实施例2
碳化硅粉：20％；氧化锆粉：40％；氧化硅：17％；铝溶胶：10％。上述的材料都是市售材料，所述的比例都是重量百分比。在上述粉末中，需要加入占1％的膨润土及12％的水。浆料是用一个高效混料器把粉料及水混合制成的。该浆料用来涂挂聚氨酯泡沫。泡沫涂挂完 浆料后，用空气除掉堵孔，然后放入热风干燥炉内，在100-120℃下保温2小时后，装入烧结炉内，然后在1300℃在下进行烧结。其中的聚氨酯泡沫也是市售材料。
按此配方制成的过滤器尺寸为50×50×15mm，孔隙率：83％。在1610℃下过滤了50kg钢水，结果是该过滤器经受住了该检测条件，并且按要求对熔融钢水进行了过滤。
制成的过滤器化学组成为(计算值)：碳化硅25.5％；氧化锆51％；氧化硅21.5％，氧化铝1％，其他1％。
实施例3
碳化硅粉：35％；氧化锆粉：30％；氧化硅：10％；硅溶胶：10％。上述的材料都是市售材料，比例都是重量百分比。在上述粉末中，需要加入15％的水。浆料是用一个高效混料器把粉料及水混合制成的。该浆料用来涂挂聚氨酯泡沫。泡沫涂挂完浆料后，用空气除掉堵孔，然后放入热风干燥炉内，在100-120℃下保温1小时后，装入烧结炉内，然后在1100℃在下进行烧结。其中的聚氨酯泡沫也是市售材料。
按此配方制成的过滤器尺寸为50×50×15mm，孔隙率：84％。在1610℃下过滤了50kg钢水，结果是该过滤器经受住了该检测条件，并且按要求对熔融钢水进行了过滤。
制成的过滤器化学组成为(计算值)：碳化硅45％；氧化锆38％；氧化硅17％。
实施例4
碳化硅粉：40％；氧化锆粉：34.9％；氧化硅：8％；硅溶胶：8％；黄原胶0.1％。上述的材料都是市售材料，比例都是重量百分比。在上述粉末中，需要加入9％的水。浆料是用一个高效混料器把粉料及水混合制成的。该浆料用来涂挂聚氨酯泡沫。泡沫涂挂完浆料后，用空气除掉堵孔，然后放入热风干燥炉内，在100-120℃下保温2小时后，装入烧结炉内，然后在1250℃在下进行烧结。其中的聚氨酯泡沫也是市售材料。
按此配方制成的过滤器尺寸为50×50×15mm，孔隙率：83％。在1610℃下过滤了50kg钢水，结果是该过滤器经受住了该检测条件，并且按要求对熔融钢水进行了过滤。
制成的过滤器化学组成为(计算值)：碳化硅47％；氧化锆27％；氧化硅26％。
实施例5
制备步骤与实施例1相同，具体配方和条件见表1。
按此配方制成的过滤器尺寸为50×50×15mm，孔隙率：80％。在1610℃下过滤了50kg钢水，结果是该过滤器经受住了该检测条件，并且按要求对熔融钢水进行了过滤。
制成的过滤器化学组成为(计算值)：碳化硅46％；氧化锆34％；氧化硅20％。
实施例6
制备步骤与实施例2相同，具体配方和条件见表1。
按此配方制成的过滤器尺寸为50×50×15mm，孔隙率：85％。在1610℃下过滤了50kg钢水，结果是该过滤器经受住了该检测条件，并且按要求对熔融钢水进行了过滤。
制成的过滤器化学组成为(计算值)：碳化硅20％；氧化锆42％；氧化硅36％；其他2％。
实施例7
制备步骤与实施例1相同，具体配方和条件见表1。
按此配方制成的过滤器尺寸为50×50×15mm，孔隙率：84％。在1610℃下过滤了50kg钢水，结果是该过滤器经受住了该检测条件，并且按要求对熔融钢水进行了过滤。
制成的过滤器化学组成为(计算值)：碳化硅37％；氧化锆49％；氧化硅14％。
对比例1
碳化硅粉：36.5％；氧化铝粉：31.2％；氧化硅：10.4％；硅溶胶：10.4％；聚乙烯醇4.2％。上述的材料都是市售材料，比例都是重量百分比。在上述粉末中，需要加入7.3％的水。浆料是用一个高效混料器把粉料及水混合制成的。该浆料用来涂挂聚氨酯泡沫。泡沫涂挂完浆料后，用空气除掉堵孔，然后放入热风干燥炉内，在100-120℃下保温1小时后，装入烧结炉内，然后在1100℃在下进行烧结。其中的聚氨酯泡沫也是市售材料。
按此配方制成的过滤器尺寸为50×50×15mm，在1610℃下仅能过滤30kg钢水，超过30kg过滤器则发生破裂，无法达到使用要求。仅能在1550℃下过滤50kg钢水。
对比例2
碳化硅粉：35.9％；铬矿粉：30.8％；氧化硅：10.3％；硅溶胶：10.3％；聚乙烯醇4.1％。上述的材料都是市售材料，比例都是重量百分比。在上述粉末中，需要加入占浆料总重量8.7％的水。浆料是用一个高效混料器把粉料及水混合制成的。该浆料用来涂挂聚氨酯泡沫。泡沫涂挂完浆料后，用空气除掉堵孔，然后放入热风干燥炉内，在100-120℃下保温1-2小时后，装入烧结炉内，然后在1100℃在下进行烧结。其中的聚氨酯泡沫也是市售材料。
按此配方制成的过滤器尺寸为50×50×15mm。在1610℃下能过滤35kg钢水，超过35kg过滤器则发生破裂，无法达到使用要求。仅能在1570℃下过滤50kg钢水。
对比例3
碳化硅粉：15％；莫来石(Al2O3-SiO2)54％；氧化硅：8％；铝溶胶：15％；黏土1.5％；膨润土0.5％。上述的材料都是市售材料，比例都是重量百分比。在上述粉末中，需要加入6.0％的水。浆料是用一个高效混料器把粉料及水混合制成的。该浆料用来涂挂聚氨酯泡沫。泡沫涂挂完浆料后，用空气除掉堵孔，然后放入热风干燥炉内，在100-120℃下保温2小时后，装入烧结炉内，然后在1300℃下进行烧结。其中的聚氨酯泡沫也是市售材料。
按此配方制成的过滤器尺寸为50×50×15mm，在1610℃下仅能过滤20kg钢水，超过20kg过滤器则发生破裂，无法达到使用要求。仅能在1520℃下过滤50kg钢水。
对比例4
按照CN102173856A的实施例1制备，得到含86.7％莫来石(Al2O3-SiO2)、7.0％的方英石，化学组成为氧化铝62.2wt％、二氧化硅31.5wt％、氧化钙2.2wt％、氧化镁1.2wt％的泡沫陶瓷。
制成的过滤器尺寸为50×50×15mm，在1610℃下仅能过滤20kg钢水，超过20kg过滤器则发生破裂，无法达到使用要求。仅能在1520℃下过滤50kg钢水。
对比例5
按照CN100536987C的实施例1制备，得到化学组成(理论值)为氧化锆78.5％、氧化铝13％、氧化钙6.5％、氧化钇1％的泡沫陶瓷。
制成的过滤器尺寸为50×50×15mm，在1610℃下仅能过滤40kg钢水，超过40kg过滤器则发生破裂，无法达到使用要求。仅能在1580℃下过滤50kg钢水。
性能测试
(1)体积密度：按照国家标准GB/T25139-2010进行测定。
(2)常温耐压强度：按照国家标准GB/T25139-2010进行测定。
(3)高温抗折强度：按照国家标准GB/T25139-2010进行测定。
(4)抗热震性：按照国家标准GB/T25139-2010进行测定。
(5)孔隙率：按照国家标准GB/T25139-2010进行测定。
表1
Figure PCTCN2017094065-appb-000001
表2
Figure PCTCN2017094065-appb-000002
表3
项目 常用过滤器 本发明过滤器
最高使用温度，℃ 1500 1610
体积密度，g/cm3 0.40-0.50 0.40-0.50
常温耐压强度，MPa ≥1.2 ≥1.5
高温抗折强度，MPa(1200℃) ≥0.8 ≥1.0
抗热震性(次)，1200℃-室温风冷 2-4 2-4
由表1和表2中的数据能够看出，采用氧化锆的本发明的实施例1至7的过滤器，与采用氧化铝的对比例1、采用铬矿粉的对比例2、采用莫来石的对比例3和对比例4，耐压强度、高温抗折强度以及抗热震性均更好。
如表1和表2中数据所示，本发明实施例1至7采用碳化硅、氧化锆以及氧化硅材料，能够提供耐高温金属冲击、热稳定性更好的用于过滤高熔点熔融金属例如钢水的过滤器。本发明的泡沫陶瓷过滤器能够在氧化锆含量较低(如实施例1至7)的情况下，实现耐高温性能，同时具有良好的热稳定性、常温耐压强度、高温抗折强度、抗热震性。
与采用碳化硅、氧化锆和氧化硅材料的本发明实施例1至7相比，采用碳化硅、氧化铝和氧化硅的比较例1，采用碳化硅、铬矿粉和氧化硅的比较例2，采用碳化硅、莫来石(Al2O3-SiO2)和氧化硅的对比例3，采用氧化铝、氧化硅为主要成分的对比例4，采用氧化锆(78.5％)、氧化铝(13％)、氧化钙、氧化钇的对比例5，具有较差的耐高温性、常温耐压强度、高温抗折强度、抗热震性。
尽管本文中披露以典型的原料和典型的制备方式制备出若干样品，并取得了预期效果，但是本领域技术人员可以预期，用其他的原料也可能制备出本发明的产品，甚至取得了优于本发明的技术效果，这些均涵盖在权利要求书所限定的范围之内。
尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。

Claims (10)

  1. 一种泡沫陶瓷过滤器，其特征在于，按重量计，所述泡沫陶瓷过滤器包括：
    碳化硅20％～50％，氧化锆20％～55％，以及氧化硅10％～36％；
    优选，碳化硅25％～45％，氧化锆25％～50％，以及氧化硅14％～30％；
    更优选，碳化硅30％～40％，氧化锆30％～45％，以及氧化硅15％～25％；
    均基于所述泡沫陶瓷过滤器的总重量。
  2. 根据权利要求1所述的泡沫陶瓷过滤器，其特征在于，按照国家标准GB/T25139-2010进行测定，所述泡沫陶瓷过滤器的孔隙率在78％～90％，优选80％～85％。
  3. 根据权利要求1所述的泡沫陶瓷过滤器，其特征在于，基于所述泡沫陶瓷过滤器的总重量，碳化硅、氧化锆和氧化硅重量百分比之和大于等于90％，或大于等于95％，优选大于等于96％，更优选大于等于97％，进一步优选大于等于98％，最优选大于等于99％。
  4. 根据权利要求1至3任一项所述的泡沫陶瓷过滤器，其特征在于，所述泡沫陶瓷过滤器由浆料烧结制成，所述浆料包括碳化硅、氧化锆或氧化锆前驱体、氧化硅或氧化硅前驱体、粘结剂、可选的外加剂、以及液体载体。
  5. 根据权利要求4所述的泡沫陶瓷过滤器，其特征在于，所述氧化锆或氧化锆前驱体为稳定氧化锆、锆英粉、硅酸锆中的一种或多种；所述氧化硅为熔融石英或硅微粉。
  6. 根据权利要求4所述的泡沫陶瓷过滤器，其特征在于，所述粘结剂为硅溶胶、铝溶胶、磷酸盐、硫酸盐、水玻璃、硅酸盐、硼酸盐、羧甲基纤维素、甲基纤维素、羟乙基纤维、羟丙基纤维素、羟丙基甲基纤维素、纤维素醚、木质素、天然或人工合成树脂、***胶、聚乙烯醇、聚乙烯醇缩丁醛中的一种或多种。
  7. 根据权利要求4所述的泡沫陶瓷过滤器，其特征在于，所述外加剂为分散剂、润湿剂、消泡剂、流变剂以及表面活性剂中的一种或多种。
  8. 制造根据权利要求1至7任一项所述的泡沫陶瓷过滤器的方法，其特征在于，包括以下步骤：
    (a)提供包括碳化硅、氧化锆或氧化锆前驱体、氧化硅或氧化硅前驱体、粘结剂、可选的外加剂、以及液体载体的浆料；
    (b)将所述浆料涂挂在开孔有机泡沫体上；
    (c)将涂挂有所述浆料的所述开孔有机泡沫体干燥，得到坯体；
    (d)含氧气氛下烧结所述坯体，得到泡沫陶瓷过滤器。
  9. 根据权利要求8所述的方法，其特征在于，所述开孔有机泡沫体为聚氨酯泡沫、聚氯乙烯泡沫、聚苯乙烯泡沫、乳胶泡沫或纤维素泡沫。
  10. 根据权利要求8所述的方法，其特征在于，所述烧结的温度为1000-1600℃，优选1100-1450℃。
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