CN100384778C - Preparation method of bauxite-based Ca-alpha-Sialon/beta-Sialon - Google Patents

Preparation method of bauxite-based Ca-alpha-Sialon/beta-Sialon Download PDF

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CN100384778C
CN100384778C CNB2006101069989A CN200610106998A CN100384778C CN 100384778 C CN100384778 C CN 100384778C CN B2006101069989 A CNB2006101069989 A CN B2006101069989A CN 200610106998 A CN200610106998 A CN 200610106998A CN 100384778 C CN100384778 C CN 100384778C
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sialon
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CN1923754A (en
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钟香崇
张海军
叶方保
孟录
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Zhengzhou University
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Abstract

The invention discloses a preparing method of alumina base Ca-alpha-sialon/beta-sialon, which comprises the following steps: adopting high-alumina as raw material; making metal aluminium powder and silicon powder as reducer; adding connecting agent; adopting nitriding reducing reaction technology to prepare the product.

Description

The preparation method of alumina base Ca-α-Sialon/ beta-Sialon
Technical field:
The present invention relates to the preparation method of a kind of pottery, refractory materials powder, be specifically related to a kind of preparation method by the synthetic alumina base Ca-α of alumine reduction nitridation reaction-Sialon/ beta-Sialon.
Background technology:
Sialon is meant Si 3N 4In Si atom and by Al or (Al+M) general name of (M is a metal ion, as Mg, Lg, Y, rare earth etc.) and O atomic substitutions formed one big class sosoloid of N atomic component ground.Wherein beta-Sialon and molten metal have extraordinary consistency, are difficult for being etched, and have the highest room temperature fracture toughness property in various single-phase Sialon.α-Sialon is with α-Si 3N 4Be the sosoloid of base, α-Sialon is celebrated with its hardness height, can remain on to have outstanding wear resistance under the high-temperature very much.
Along with industrial expansion, people have proposed more and more higher requirement to the performance of material, and the performance of single-phase Sialon material can not satisfy harsh application conditions, so complex phase Sialon material and Sialon matrix material obtain people's attention gradually.
α-Sialon/ beta-Sialon composite diphase material utilizes the high rigidity of α-Sialon by the principle of mutual reinforcement, mutual supplement with each other's advantages, and the high strength of beta-Sialon, toughness improve the over-all properties of material.For single-phase Sialon material, the most tangible advantage of alpha-beta-Sialon matrix material is exactly to carry out the random cutting of material, by adjusting the different ratios of α-Sialon, beta-Sialon, can obtain being applicable to the different differing materials that require.
The over-all properties of α-Sialon/ beta-Sialon composite diphase material is better, except having higher relatively hardness, intensity and toughness, also has good heat-shock resistance and oxidation-resistance.These characteristics make α-Sialon/ beta-Sialon material be suitable for using under high temperature, corrosive atmospheres such as metallurgy, chemical industry, also can utilize simultaneously its characteristics such as high strength, high rigidity to use as cutter or bearing.
In decades, research about Sialon material aspect is very many, and its practical application still is restricted, this is because the various technologies of at present synthetic Sialon powder, complex process, require high temperature (about 1700 ℃), with high costs, otherwise impurity is mutually more in the synthetic product, impurity level is big, be difficult to control etc.
The self-propagating high temperature synthesis preparation method of a kind of low cost alpha-Sialon powder is provided in the Chinese invention patent application of publication number for CN1521141, and the raw material of employing is silica flour, metallic aluminium powder, slag or some natural mineral or their mixture and Sai Long powder.
Provide a kind of self propagating high temperature to synthesize the preparation method of low-cost complex phase α/beta-Sialon powder in the Chinese invention patent application of application number for CN03115422.0, the raw material of employing is silica flour, metallic aluminium powder, slag or some natural mineral or their mixture.
What the stable α of a kind of rare earth ion-Sialon powder was provided in the Chinese invention patent application of application number for CN200410015999.3 spreads synthetic method certainly.The raw material that adopts is that mass percent is not less than 99.0% silicon nitride (Si 3N 4) powder, aluminium nitride (AlN) powder, rare earth oxide (RE 2O 3, RE=Ce, Pr and Eu) and yttrium oxide (Y 2O 3) and mass percent be not less than 98.0% aluminium (Al) powder and silicon (Si) powder, by the synthetic α of self-propagating high-temperature burning process-Sialon powder.
A kind of method of low-cost synthesizing sialon ceramic powder is provided in the Chinese invention patent application of application number for CN01126758.5.Utilize metallurgical slag or Wingdale or flyash industrial waste, or cheap natural mineral is raw material, obtains single-phase α-Sialon powder through handling again through self-propagating high-temperature technology is synthetic by adding metallic aluminium powder, silica flour and part crystal seed.
The characteristics of above patent are to utilize self-propagating high-temperature technology, this complex process equipment, requirement condition height, and cost is higher, is difficult to realize scale operation.Low melting point in the while synthetic materials is as K 2O, Na 2O equal size height is not suitable for using in the hot industry field.
Application number is for providing a kind of composite ceramics and preparation method in 95111718 the Chinese invention patent application, with the general formula Y of α-Sialon M/3Si 12-(m+n)Al M+nO nN 16-nIn m, n value as the significant parameter of design composite ceramics principal crystalline phase α-Sialon, beta-Sialon content.The first 20MPa single shaft moulding of batching back is the 200MPa cold isostatic compaction then, and biscuit is at 1800 ℃, 1 normal atmosphere N 2After air-flow is incubated pressureless sintering in 2 hours down, depress in 1.5-3.0 hour sintering of 1900-2000 ℃ of insulation at the high nitrogen of 1MPa again, be characterized in that high temperature burns till.
A kind of alpha-Sialon ceramic material and preparation method with high IR transmitance is provided in the Chinese invention patent application of application number for CN200310109016.8.Its raw material is a high-purity Si 3N 4Powder, AlN powder, Al 2O 3Powder and rare earth oxide M 2O 3(M=Dy, Y, Gd, Yb, Nd) powder, raw material prepares fine and close single-phase α-Sialon at 1700 ℃ of-1850 ℃ of hot pressing 1-5h after the ball milling oven dry.
It is raw material that above patent all requires to adopt high-purity nitride, high temperature (>1800 ℃) sintering, and cost is higher.
The method of the synthetic high-purity Si alon material of a kind of Coaseries kaolin is provided in the Chinese invention patent application of application number for CN200410009293.6.Employing is raw material with the coal series kaolinite, by the high-purity beta-Sialon material of carbothermal reduction-nitridation method one step preparation.
Provide a kind of α-Sialon/ beta-Sialon composite diphase material and preparation technology thereof in the Chinese invention patent application of application number for CN200510011508.2.Selecting coal gangue and natural alumina (or silica sand) for use is raw material, is reductive agent with carbon, and carbothermal reduction-nitridation prepares β-Sai Long and α-Sai Long composite diphase material.Its temperature of reaction is up to 1650 ℃.
More than 2 patents all to adopt carbon be reductive agent, reaction process is wayward, and can't avoid in the building-up process gas-phase reaction of oxide compound in the carbon and system, so the products therefrom void content is higher, is unfavorable for further application.
Still do not retrieve with alumina and CaCO at present 3For raw material, with metallic aluminium, silicon is the open patent of invention that reductive agent prepares alumina base Ca-α-Sialon/ beta-Sialon aspect.
China has abundant alumine raw material resources.But because raw materials quality is stable inadequately, composition is even inadequately, and kind is single, not only can't satisfy the demand of special refractories, and the selling price on the world market is also far below countries such as Guyana, Brazil.If with its (alumine) is raw material, add suitable reductive agent, technology through suitable is translated into Ca-α-Sialon/ beta-Sialon, to satisfy the demand of domestic and international pyrotic smelting key position, not only can reduce production costs significantly, reduce the consumption costs of hot industry, but also can improve the added value of alumina greatly, be reasonable development China alumine resource with refractory materials, increase foreign exchange earnings from exports, good condition is provided.
Summary of the invention:
Problem for the complex manufacturing that overcomes Ca-α-Sialon/ beta-Sialon, production cost height, poor product quality the purpose of this invention is to provide a kind of with alumine and CaCO 3Being raw material, is that reductive agent prepares Ca-α-Sialon/ beta-Sialon, this technology is simple with Si, Al, the preparation method of Ca-α-Sialon/ beta-Sialon that preparation cost is low, product performance are high, added value is high.
Technical scheme of the present invention realizes in the following manner:
The preparation method of a kind of alumina base Ca-α-Sialon/ beta-Sialon is with alumine, CaCO 3Being main raw material, is reductive agent with metallic aluminium powder, silica flour, adopts reduction-nitridation technology, it is characterized in that:
A. with parts by weight the alumine of 20-35%, the CaCO of 20-30% 3, the silica flour of 40-55%, the metallic aluminium powder of 4-7%, α-Si of 1-5% 3N 4The Y of crystal seed, 2-4% 2O 3Or Fe 2O 3Or TiO 2Or NH 4After F mixes, be mixed into pug, or the piece material is pressed or be squeezed into to machine;
B. place nitriding furnace to carry out nitrogenize in the piece material after the moulding, under flowing nitrogen atmosphere, in 14-26 hour, be warming up to 1500-1550 ℃ stage by stage;
C. be cooled to 100-800 ℃, close nitrogen, after continuing to be cooled to room temperature, promptly get product.
Described heat up stage by stage be with or type after the piece material place nitriding furnace to carry out nitrogenize, under flowing nitrogen atmosphere, be warming up to 790-820 ℃ earlier, insulation; Be warming up to 1050-1150 ℃ again, insulation; Continue to be warming up to 1250-1300 ℃, insulation; Be warming up to 1500-1550 ℃ of insulation at last.
Heat up stage by stage in described and be: place nitriding furnace to carry out nitrogenize in the piece material after the moulding, under flowing nitrogen atmosphere, be warming up to 790-820 ℃, be incubated 1 hour with 60-300 ℃/hour speed; Continue to be warming up to 1050-1150 ℃ with 30-100 ℃/hour speed, be incubated 2 hours; Continue to be warming up to 1250-1300 ℃, temperature rise rate is 20-100 ℃/hour, is incubated 3 hours; Be warming up to 1500-1550 ℃ at last, temperature rise rate is 60-300 ℃/hour, is incubated 8-20 hour;
Used alumine is raw material or light-burned material, the Al after its igloss 2O 3Mass percent is 80-88%, SiO 2Mass percent 5-15%;
Described wedding agent is that dextrin, polyvinyl alcohol, xylogen, carboxymethyl cellulose are or/and one or more in the resol.
The pressure of described mechanical pressing is 10-150MPa.
The pressure of described extrusion molding is 1-10MPa.
The invention has the advantages that:
1, preparation technology is simple, need not complicated processing unit and technological process, simultaneously with profuse alumine of Chinese reserves and CaCO 3Be raw material, reduced the manufacturing cost of Ca-α-Sialon/ beta-Sialon widely.
2, owing to α-Sialon, beta-Sialon all are Si 3N 4Sosoloid, its solid solubility can change within the specific limits, does not influence the acquisition of final α-Sialon/ beta-Sialon when material component changes slightly.Therefore this technology is lower to the requirement of raw material, is fit to suitability for industrialized production.
3, the product thing after synthetic is compared purely with the present invention, does not have other dephasign substantially, and nitrogen content is 30-40Wt%.
4, alumine is after handling this transition, and its value can improve 10-20 doubly.
Embodiment:
Below in conjunction with embodiment the present invention is further described, but is not limited to the following example.
Embodiment 1
Light-burned (650 ° of processing) alumine (composition such as table 1), CaCO with Dengfeng City, Henan Province 3, metallic aluminium powder, silica flour be raw material, other adds a small amount of α-Si 3N 4Be crystal seed.
The light-burned alumine chemical constitution of Dengfeng City, table 1 Henan Province
Component Al 2O 3 SiO 2 Other
wt% 81.40 13.76 4.84
With weight fraction is 25.2% light-burned alumine, and weight fraction is 23.1% CaCO 3, weight fraction is 46.9% silica flour, weight fraction is 4.7% metallic aluminium powder, added weight mark 4%Y 2O 3With 3% Si 3N 4Crystal seed is positioned in the ball grinder, dried be mixed even; Taking out mixed powder, is wedding agent with the dextrin of batch mixing weight 2%, adds and mixes, and machine is pressed into the piece material under the 100MPa pressure, and is dry under the 80-110 ℃ of temperature.
Above-mentioned forming blocks material is put into atmosphere sintering furnace, under nitrogen atmosphere, be warming up to 800 ℃, be incubated 1 hour with 100 ℃/hour speed; Continue to be warming up to 1050 ℃ with 80 ℃/hour speed again, be incubated 2 hours; Continue to be warming up to 1250 ℃, temperature rise rate is 30 ℃/hour, is incubated 3 hours; Be warming up to 1550 ℃ at last, temperature rise rate is 100 ℃/hour, is incubated 16 hours.
The atmosphere sintering furnace temperature is reduced to 700 ℃, close nitrogen, continue to be cooled to room temperature and take out, obtain Ca-α-Sialon/ beta-Sialon powder.
Through XRD analysis, the product principal crystalline phase is a beta-Sialon, and paracrystalline phase is Ca-α-Sialon, does not have other dephasign.If be approximately the content of each thing phase with the integral area of various thing phase highest peaks, the relative content of Ca-α-Sialon is 45%, and the relative content of beta-Sialon is 55%.
Embodiment 2
Use raw material and prescription with embodiment 1.
The piece material is put into atmosphere sintering furnace, under nitrogen atmosphere, be warming up to 800 ℃, be incubated 1 hour with 100 ℃/hour speed; Continue to be warming up to 1050 ℃ with 80 ℃/hour speed again, be incubated 2 hours; Continue to be warming up to 1250 ℃, temperature rise rate is 30 ℃/hour, is incubated 3 hours; Be warming up to 1500 ℃ at last, temperature rise rate is 100 ℃/hour, is incubated 10 hours and obtains Ca-α-Sialon/ beta-Sialon powder.Through XRD analysis, the product principal crystalline phase is a beta-Sialon, and paracrystalline phase is Ca-α-Sialon, does not have other dephasign.Be approximately the content of each thing phase with the integral area of various thing phase highest peaks, the relative content of Ca-α-Sialon is 11%, and the relative content of beta-Sialon is 89%.
Embodiment 3
Use raw material and prescription with embodiment 1.
The piece material is put into atmosphere sintering furnace, under nitrogen atmosphere, be warming up to 800 ℃, be incubated 1 hour with 100 ℃/hour speed; Continue to be warming up to 1050 ℃ with 80 ℃/hour speed again, be incubated 2 hours; Continue to be warming up to 1250 ℃, temperature rise rate is 30 ℃/hour, is incubated 3 hours; Be warming up to 1550 ℃ at last, temperature rise rate is 100 ℃/hour, is incubated 8 hours and obtains Ca-α-Sialon/ beta-Sialon powder.Through XRD analysis, the product principal crystalline phase is a beta-Sialon, and paracrystalline phase is Ca-α-Sialon, does not have other dephasign.Be approximately the content of each thing phase with the integral area of various thing phase highest peaks, the relative content of Ca-α-Sialon is 25%, and the relative content of beta-Sialon is 75%.
Embodiment 4
Raw materials used and nitriding process system is with embodiment 1.
The pressure of raw material extrusion molding is 8MPa; Used wedding agent is an xylogen, and consumption is 5% of a raw material.
With raw material mix, after the moulding, drying, the stage is warming up to 1550 ℃, is incubated nitrogenize in 20 hours.The gained powder is through XRD analysis, and the product principal crystalline phase is a beta-Sialon, and paracrystalline phase is Ca-α-Sialon, does not have other dephasign.
Embodiment 5
The raw material that uses, nitriding process system are with embodiment 1.With weight fraction is 32.1% light-burned alumine, and weight fraction is 20.0% CaCO 3, weight fraction is 43.3% silica flour, weight fraction is 4.6% metallic aluminium powder, added weight mark 4%Y 2O 3With 3% Si 3N 4Be positioned in the ball grinder, dried be mixed even; Taking out mixed powder, is wedding agent with the resol of batch mixing weight 2%, adds and mixes, and the 80MPa machine is pressed into the piece material, with raw material drying, after the stage intensification nitrogenize.The gained powder is through XRD analysis, and principal crystalline phase is a beta-Sialon, and paracrystalline phase is Ca-α-Sialon.
Embodiment 6
The raw material that uses is with embodiment 1.Weight fraction is 25.2% light-burned alumine, and weight fraction is 23.1% CaCO 3, weight fraction is 46.9% silica flour, weight fraction is 4.7% metallic aluminium powder, added weight mark 4%TiO 2With 3% Si 3N 4Be positioned in the ball grinder, dried be mixed even; Taking out mixed powder, is wedding agent with the resol of batch mixing weight 2%, adds and mixes, and machine is pressed into the piece material under the pressure of 80MPa, behind raw material drying, under nitrogen atmosphere, is warming up to 810 ℃ with 200 ℃/hour speed, is incubated 1 hour; Continue to be warming up to 1100 ℃ with 100 ℃/hour speed again, be incubated 2 hours; Continue to be warming up to 1300 ℃, temperature rise rate is 50 ℃/hour, is incubated 3 hours; Be warming up to 1550 ℃ at last, temperature rise rate is 50 ℃/hour, is incubated 12 hours.The gained powder is through XRD analysis, and principal crystalline phase is a beta-Sialon, and paracrystalline phase is Ca-α-Sialon.
Embodiment 7
The raw material that uses, nitriding process system are with embodiment 6.Weight fraction is 25.2% light-burned alumine, and weight fraction is 23.1% CaCO 3, weight fraction is 46.9% silica flour, weight fraction is 4.7% metallic aluminium powder, added weight mark 2%Fe 2O 3With 3% Si 3N 4Be positioned in the ball grinder, dried be mixed even; Taking out mixed powder, is wedding agent with the resol of batch mixing weight 2%, adds and mixes, and machine is pressed into the piece material under the pressure of 80MPa, with raw material drying, after the stage intensification nitrogenize.The gained powder is through XRD analysis, and principal crystalline phase is a beta-Sialon, and paracrystalline phase is Ca-α-Sialon.
Embodiment 8
The raw material that uses, nitriding process system are with embodiment 6.Weight fraction is 25.2% light-burned alumine, and weight fraction is 23.1% CaCO 3, weight fraction is 46.9% silica flour, weight fraction is 4.7% metallic aluminium powder, added weight mark 3%NH 4F and 3% Si 3N 4Be positioned in the ball grinder, dried be mixed even; Taking out mixed powder, is wedding agent with the resol of batch mixing weight 2%, adds and mixes, and machine is pressed into the piece material under the pressure of 80MPa, with raw material drying, after the stage intensification nitrogenize.The gained powder is through XRD analysis, and principal crystalline phase is a beta-Sialon, and paracrystalline phase is Ca-α-Sialon.
Embodiment 9
The raw material that uses, nitriding process system are with embodiment 1.
With weight fraction is 25.2% light-burned alumine, and weight fraction is 23.1% CaCO 3, weight fraction is 46.9% silica flour, weight fraction is 4.7% metallic aluminium powder, added weight mark 4%Y 2O 3With 1% Si 3N 4Crystal seed is positioned in the ball grinder, dried be mixed even; Taking out mixed powder, is wedding agent with the carboxymethyl cellulose of batch mixing weight 4%, adds and mixes, and machine is pressed into piece, dry back nitrogenize under the pressure of 100MPa.The gained powder is through XRD analysis, and the product principal crystalline phase is a beta-Sialon, and paracrystalline phase is Ca-α-Sialon, does not have other dephasign.
Embodiment 10
With light-burned (650 ° of processing) alumine (composition such as table 2), CaCO 3, metallic aluminium powder, silica flour be raw material, other adds a small amount of α-Si 3N 4Be crystal seed.
The light-burned alumine chemical constitution of Dengfeng City, table 2 Henan Province
Component Al 2O 3 SiO 2 TiO 2 Fe 2O 3
wt% 86.66 5.39 4.26 2.15
With weight fraction is 21.3% light-burned alumine, and weight fraction is 20.6% CaCO 3, weight fraction is 52% silica flour, weight fraction is 6.1% metallic aluminium powder, added weight mark 4%Y 2O 3With 3% Si 3N 4Crystal seed is positioned in the ball grinder, dried be mixed even; Taking out mixed powder, is wedding agent with the dextrin of batch mixing weight 2%, adds and mixes, and machine is pressed into the piece material under the pressure of 100MPa, and is dry under the 80-110 ℃ of temperature.
Above-mentioned forming blocks material is put into atmosphere sintering furnace, under nitrogen atmosphere, be warming up to 820 ℃, be incubated 1 hour with 300 ℃/hour speed; Continue to be warming up to 1150 ℃ with 100 ℃/hour speed again, be incubated 2 hours; Continue to be warming up to 1300 ℃, temperature rise rate is 50 ℃/hour, is incubated 3 hours; Be warming up to 1550 ℃ at last, temperature rise rate is 200 ℃/hour, is incubated 16 hours.The atmosphere sintering furnace temperature is reduced to 700 ℃, close nitrogen, continue to be cooled to room temperature and take out, obtain Ca-α-Sialon/ beta-Sialon powder.Through XRD analysis, the product principal crystalline phase is a beta-Sialon, and paracrystalline phase is Ca-α-Sialon, does not have other dephasign.

Claims (6)

1. the preparation method of alumina base Ca-α-Sialon/ beta-Sialon is with alumine, CaCO 3Being main raw material, is reductive agent with metallic aluminium powder, silica flour, adopts reduction-nitridation technology, it is characterized in that:
A. with weight percent content the alumine of 20-35%, the CaCO of 20-30% 3, the silica flour of 40-55%, the metallic aluminium powder of 4-7%, α-Si of 1-5% 3N 4The Y of crystal seed, 2-4% 2O 3Or Fe 2O 3Or TiO 2Or NH 4After F mixes, be mixed into pug, the piece material is pressed or be squeezed into to machine;
B. place nitriding furnace to carry out nitrogenize in the piece material after the moulding, under flowing nitrogen atmosphere, in 14-26 hour, heat up stage by stage; Heating up stage by stage is to be warming up to 790-820 ℃ earlier, insulation; Be warming up to 1050-1150 ℃ again, insulation; Continue to be warming up to 1250-1300 ℃, insulation; Be warming up to 1500-1550 ℃ of insulation at last
Figure C2006101069980002C1
C. be cooled to 100-800 ℃, close nitrogen, after continuing to be cooled to room temperature, promptly get product.
2. the preparation method of alumina base Ca-α according to claim 1-Sialon/ beta-Sialon, it is characterized in that: place nitriding furnace to carry out nitrogenize in the piece material after the moulding, under flowing nitrogen atmosphere, be warming up to 790-820 ℃ with 60-300 ℃/hour speed, be incubated 1 hour; Continue to be warming up to 1050-1150 ℃ with 30-100 ℃/hour speed, be incubated 2 hours; Continue to be warming up to 1250-1300 ℃, temperature rise rate is 20-100 ℃/hour, is incubated 3 hours; Be warming up to 1500-1550 ℃ at last, temperature rise rate is 60-300 ℃/hour, is incubated 8-20 hour.
3. the preparation method of alumina base Ca-α according to claim 2-Sialon/ beta-Sialon is characterized in that: used alumine is raw material or light-burned material, the Al after its igloss 2O 3Mass percentage content is 80-88%, SiO 2Mass percentage content 5-15%.
4. the preparation method of alumina base Ca-α according to claim 3-Sialon/ beta-Sialon, it is characterized in that: add the wedding agent of raw material total amount 1-5% in the batching China and foreign countries, used wedding agent is one or more in dextrin, polyvinyl alcohol, xylogen, carboxymethyl cellulose, the resol.
5. the preparation method of alumina base Ca-α according to claim 4-Sialon/ beta-Sialon, it is characterized in that: the pressure of mechanical pressing is 10-150MPa.
6. the preparation method of alumina base Ca-α according to claim 4-Sialon/ beta-Sialon, the pressure that it is characterized in that extrusion molding is 1-10MPa.
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CN1535933A (en) * 2003-04-28 2004-10-13 郑州大学 Preparation method of alumyte base beta-sialon
CN1623956A (en) * 2004-11-05 2005-06-08 郑州大学 Process for preparing alumine based O'-Sialon
CN1686922A (en) * 2005-03-29 2005-10-26 郑州大学 Method for preparing composite material combined with corundum based on bauxite beta-Sialon

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Publication number Priority date Publication date Assignee Title
JP2003246676A (en) * 2002-02-26 2003-09-02 National Institute Of Advanced Industrial & Technology Sialon ceramic porous body and manufacturing method thereof
CN1521142A (en) * 2003-02-14 2004-08-18 中国科学院上海硅酸盐研究所 Process for preparation of self-spread high-temperature synthesizing low-cost diphase alpha/beta-sialon powder
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CN1623956A (en) * 2004-11-05 2005-06-08 郑州大学 Process for preparing alumine based O'-Sialon
CN1686922A (en) * 2005-03-29 2005-10-26 郑州大学 Method for preparing composite material combined with corundum based on bauxite beta-Sialon

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