CN100432022C - Oxide ceramics multiple phase refractory material - Google Patents
Oxide ceramics multiple phase refractory material Download PDFInfo
- Publication number
- CN100432022C CN100432022C CNB2006100686717A CN200610068671A CN100432022C CN 100432022 C CN100432022 C CN 100432022C CN B2006100686717 A CNB2006100686717 A CN B2006100686717A CN 200610068671 A CN200610068671 A CN 200610068671A CN 100432022 C CN100432022 C CN 100432022C
- Authority
- CN
- China
- Prior art keywords
- sialon
- phase
- oxide
- beta
- mullite
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses an oxide ceramic composite phased fireproof material based on clay as raw material, which is characterized by the following: adopting clay minerals, industrial carbon powder and nitrogen as main raw material to form beta-sialon connecting phase; adding reacting accelerant, alumina or mullite particle to blend evenly; moulding; drying; aerating nitrogen in the high-temperature kiln to proceed carbon heat reducing-nitrogenizing reaction to sinter into combined beta-sialon alumina or mullite fireproof ceramic product with 10-30% beta-sialon continuous base phase and 70-90% alumina or mullite particle dispersing phase.
Description
Technical field:
The invention belongs to the refractory ceramic material technical field, relate to a kind of one of clay raw materials of utilizing through the beta cellulose of carbothermal reduction-nitridation prepared in reaction (the matrix phase bonded oxide ceramics multiple phase refractory material of β-sialon).
Technical background:
Beta cellulose (beta-Sialon) ceramic refractory that combines is the novel non-carbon special type fire stupalith that a class earns widespread respect.Usually adopt Si3N4 and aluminum oxide be main raw material when producing beta-Sialon because of its raw materials cost height, the reaction sintering temperature is high and limited its development at fire resisting material field.The synthetic beta-Sialon technology of carbothermal reduction-nitridation reaction method that utilization contains aluminium silicon class natural mineral raw be since 1976 S.Wild (J.Mater.Sci.1976p 1972 ~ 1974) utilize kaolin at first nitrogenize synthesize the mixture of beta-Sialon and aluminium nitride.J.G.Lee (Am.Ceram.Soc.Bull.1979 in 1979, No9,869 ~ 871) adopt kaolinic carbothermal reduction-nitridation reaction to synthesize the Sialon powder, mix mullite and silicon oxynitride simultaneously mutually, this reaction only is to have synthesized powdered samples under laboratory scale.Be easy to get because of this method has raw material, cost is low and be easy to advantage such as scale production, and research and development are paid attention to and obtained to the technological method of the synthetic Sialon powder of clay mineral raw material widely since then.
Related application mainly concentrates on the synthetic aspect of Sialon powder.The nitrogenizing reaction that United States Patent (USP) (USPatent) 4977113 uses silicon and aluminum oxide and the simultaneous mixture of carbon source to carry out under 1200-1450 ℃ generates presoma, and do not use natural mineral as starting raw material, and add the young crystalline substance of Sialon and promote beta-Sialon powder forming process, generate beta-Sialon in 1400-1600 ℃ of following nitrogenize more thereafter.US Patent 4977113 provides the processing method that adopts carbothermic reduction reaction to produce the Sialon powder, is characterized in utilizing fully raw mineral materials, does not add any metal oxide, and adds the young crystalline substance of Sialon and come accelerated reaction to carry out.US Patent 5814573 proposes a kind of method that adopts aluminium silicon raw material continuous production Sialon powder.Chinese patent bulletin CN1176872 proposes to utilize matchmaker's spoil, coal dust and nitrogen to be feedstock production beta-Sialon powder, has small amount of carbonized silicon (SiC) and glassy phase in the product.Chinese patent bulletin CN1374274A proposition utilizes the nitrogen nitrogenizing reaction of matchmaker's spoil, carbon dust to prepare the mixed powder of beta-Sialon and SiC.More than invention is if be used for preparing β-sialon matrix phase in conjunction with the ceramic complex phase material goods; need at first prepare β-s ialon powder, and then secondary high temperature sintering behind β-sialon powder and the ceramic dispersion particle mixing moulding is prepared beta-Sialon combine ceramic refractory.Obviously, twice pyroprocess of this method makes its complex process, the energy consumption height, and preparation cycle is long, and its large-scale promotion application is restricted.
The inventor in 1993 proposes when the carbothermic reduction-nitrogenizing reaction that utilizes the kaolin raw material prepares the beta-Sialon matrix phase SiC grain composition material combined and forms the one-step synthesis Process (Chinese patent bulletin CN1092053,1994) of beta-Sialon in conjunction with the SiC material.Its synthesis technique is simple, raw material and product cost are lower, and the high-temperature behavior of material is good, is applicable to that compressive strength requires general high temperature and liquid phase, gas phase high temperature to invade the corrosion occasion.But this invented technology need further be improved the weightless problem of reacting the goods relative density of influence of carbothermic reduction in the invented technology in conjunction with the SiC composite diphase material.
Relevant beta-Sialon combined corundum refractory ceramic material adopts two step process methods to be prepared at present mostly.Promptly at first synthesize beta-Sialon matrix phase powder, and then combine formation beta-Sialon combined corundum complex phase fire stupalith with the corundum in granules gradating material, its technological process is comparatively complicated, and energy consumption is big, and production cost is higher.It is that main raw material mixes the back fusion with brown corundum in granules material or sintering forms the grand combined corundum refractory materials of match that Chinese invention patent bulletin CN1223550C has proposed employing Pure Silicon Metal, Al alloy powder etc., its preparation process is to finish in single step reaction, but raw materials cost is higher, near aluminium, the silicon nitrogenize solid solution reaction control difficulty fusing point.And beta-Sialon does not appear in the newspapers as yet in conjunction with the mullite Multiphase refractory ceramic material.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that prior art exists; utilize the carbothermic reduction-nitrogenizing reaction of one of clay raw materials to prepare the beta-Sialon matrix phase, and simultaneously go out the beta-Sialon combined corundum or combine the oxide ceramics multiple phase refractory material of mullite with corundum in granules or mullite particle gradating material one-step synthesis prepared.
In order to realize the foregoing invention purpose, the present invention adopts clay class raw mineral materials, industrial carbon powder and nitrogen are as forming the main raw material of β-sialon in conjunction with phase, and add and react the promotion additive in right amount, and then after adding corundum or mullite particle gradating material and mixing evenly, shaping method of ceramics with routine carries out forming of green body, after drying base substrate is packed in the atmosphere high temperature kiln that is connected with nitrogen, 1300～1550 ℃ in maximum temperature interval, constant temperature carried out carbon heat reducing-nitrogenizing reaction in 3～36 hours in the hot conditions, and a reaction sintering cycle is 26～120 hours synthetic beta-Sialon combined corundum or mullite flame-proof ceramics prepared altogether.Its thing phase composite is that to account for weight percent be 10～30% to the continuous matrix phase of beta-Sialon, corundum or mullite particle disperse phase account for weight percent 70～90%, it is 5～18% that material split shed pore accounts for material volume per-cent, allows to exist silicon oxynitride, silicon nitride, the alumina high temperature refractory body phase of 0～5% weight percent.
Used one of clay raw materials comprises one or more the miscellany in kaolin, aluminium vanadine, polynite and the wilkinite among the present invention, to satisfy the requirement that forms in the target product reaction the Al/Si ratio.The chemical constitution general formula of beta-Sialon is Si
6-ZAl
ZO
ZN
8-Z, Z represents that aluminium (Al) oxygen (O) atom replaces the solid solution value of silicon (Si) nitrogen (N) atom respectively in the formula, its Z value scope is 1.5～3.0 among the present invention.The Al/Si that adjusts raw clay is than using the additional raw material that comprises SiO 2 powder, silicon ash, superfine alumina powder, calcined alumina powder.The industrial carbon dust that uses in the raw material comprises Graphite Powder 99, pure coal dust, industrial carbon black etc.
The reaction that the present invention adds when mixing raw material promotes the densification of composite diphase material promotes additive to comprise one or more among magnesium oxide, calcium oxide, yttrium oxide, zirconium white, vanadium oxide, titanium oxide and cerium oxide etc. and C, B, Si and the BN, to promote reaction to carry out and reduce sintering temperature and to improve product properties, corundum or mullite particle formed carry out three grades, level Four or size grading feed proportioning optimization continuously arbitrarily, its carse, medium and small particle weight ratio is 5～7: 1～2: 1～3.
Material thing of the present invention phase composite is pure, density is moderate, the use temperature height, and outside withstand voltage folding strength height and refractory salt, the molten metal corrosion, high-temperature oxidation resistance and thermal shock resistance are good especially.30 hours its oxidation weight gains of oxidation only are 30mg/cm in 1300 ℃ of following air
2. about, under 1250 ℃～heat shock resistance cycle index in the room temperature water can reach more than 120 times.
Embodiment:
Adopt clay class raw mineral materials during the invention process, industrial carbon powder and nitrogen are as forming the main raw material of β-sialon in conjunction with phase, and add and react the promotion additive in right amount, and then after adding the corundum or the mullite particle gradating material of 70～90% weight percents and mixing evenly, shaping method of ceramics with routine carries out forming of green body, after drying base substrate is packed in the atmosphere high temperature kiln that is connected with nitrogen, in temperature range is that constant temperature carried out carbon heat reducing one nitrogenizing reaction in 3～36 hours in 1300-1550 ℃, one reaction sintering cycle is 26～120 hours synthetic oxide ceramics multiple phase refractory material goods of preparing beta-Sialon combined corundum or mullite, its thing phase composite is that to account for weight percent be 10～30% to the continuous matrix phase of beta-Sialon, corundum or mullite particle disperse phase account for weight percent 70～90%, it is 5～18% that material split shed pore accounts for material volume per-cent, allows to exist the silicon oxynitride of 0～5% weight percent, silicon nitride, high temperature refractory body phases such as aluminum oxide.
Embodiment 1:
Choose one-level Suzhou kaolin, pure coal dust, according to chemical composition analytical results is adjusted Si with SiO 2 powder
6-ZAl
ZO
ZN
8-ZIt is 1.5 that middle silicon/aluminum ratio value reaches the Z value, and the weight percent of raw clay and powdered carbon is 1: 0.26, adds 0.7wt% zirconium white reaction sintering promotor again, it is mixed the back form base starting material.Then 6: 2: 2 by weight percentage the proportioning of corundum in granules material of 40#, 80# and 240# granularity is prepared burden, the raw material and the corundum in granules material that wherein form the beta-Sialon matrix phase mix batching once more by 2: 8 weight ratios, and add compression moulding behind conventional organic molding adhesive, slow intensification nitrogenizing reaction sintering is totally 80 hours in flowing nitrogen atmosphere, and wherein 1530 ℃ of following constant temperature of top temperature are 16 hours.It is 1.5 beta-Sialon combined corundum goods that cooling obtains the Z value.Through X one its principal crystalline phase of ray diffraction facies analysis be corundum with beta-Sialon mutually, the fire resistive material product (as brick, plate etc.) that this material can be used as under high temperature, the corrosive environment operating mode uses.
Embodiment 2:
Be to choose one-level Suzhou kaolin, wilkinite as one of clay raw materials at 9: 1 by weight percentage, according to chemical composition analytical results is adjusted Si with SiO 2 powder
6-ZAl
ZO
ZN
8-ZIt is 2 that middle sial ratio reaches the Z value.The adding industrial carbon black is a carbon source, and one of clay raw materials and sooty weight percent are 1: 0.28, add the 1wt% vanadium oxide again, it is mixed the back form base starting material.Then with the mullite particle material of 60#, 100# and 180# granularity proportion ingredient by weight 6: 1.5: 2.5, the raw material and the mullite that wherein form the beta-Sialon matrix phase mix batching once more by 2.5: 7.5 weight ratios, and add compression moulding behind conventional organic molding adhesive, slowly intensification carbothermic reduction in flowing nitrogen atmosphere-nitrogenizing reaction sintering totally 72 hours, wherein 1550 ℃ of following constant temperature of top temperature are 12 hours.Obtain the Z value after the cooling and be 2 beta-Sialon in conjunction with mullite product.Through X one its principal crystalline phase of ray diffraction facies analysis be mullite with beta-Sialon mutually, the fire resistive material product that this material can be used as under elevated temperature heat shake such as ceramic kiln refractory slab, refractory brick and the corrosive environment operating mode uses,
Embodiment 3:
Be to choose superfine Suzhou kaolin and polynite at 8: 2 as one of clay raw materials by weight percentage, according to chemical composition analytical results is adjusted Si with SiO 2 powder
6-ZAl
ZO
ZN
8-ZIt is 2.5 that middle silicon/aluminum ratio value reaches the Z value, is the ingredient requirement carbon source with the Graphite Powder 99, and the weight percent of one of clay raw materials and Graphite Powder 99 is 1: 0.27, adds 0.5wt% vanadium oxide and 0.5wt% zirconium white again, it is mixed the back form base starting material.Then with the corundum in granules material of 60#, 100# and 180# granularity proportion ingredient by weight 6.5: 1.5: 2, the raw material and the corundum that wherein form the beta-Sialon matrix phase mix batching once more by 2.2: 7.8 weight ratios, and add compression moulding behind conventional organic molding adhesive, slowly intensification carbothermic reduction in flowing nitrogen atmosphere-nitrogenizing reaction sintering totally 70 hours, wherein 1480 ℃ of following constant temperature of top temperature are 10 hours.Obtain the Z value after the cooling and be 2.5 Si alon combined corundum goods.Through X one its principal crystalline phase of ray diffraction facies analysis be corundum with beta-Sialon mutually, this material antioxidant property is excellent especially, the fire resistive material product that can be used as under high temperature, thermal shock and the well-oxygenated environment operating mode uses.
Claims (3)
1. oxide ceramics multiple phase refractory material, it is characterized in that adopting clay class raw mineral materials, industrial carbon powder and nitrogen are as forming the raw material of β-sialon in conjunction with phase, and add and react the promotion additive, and then after adding the mullite particle gradating material and mixing evenly, forming process of ceramics method with routine is carried out forming of green body, after drying base substrate being packed into, constant temperature carries out carbon heat reducing-nitrogenizing reaction in the atmosphere high temperature kiln that is connected with nitrogen, synthetic prepare beta-Sialon through a reaction sintering cycle in conjunction with the mullite flame-proof ceramic, its thing phase composite is that to account for weight percent be 10～30% to the continuous matrix phase of beta-Sialon, the mullite particle disperse phase accounts for weight percent 70～90%, it is 5～18% that material split shed pore accounts for material volume per-cent, allows to exist the silicon oxynitride of 0～5% weight percent, silicon nitride, alumina high temperature refractory body phase.
2. oxide ceramics multiple phase refractory material according to claim 1, it is characterized in that the reaction of adding promotes additive to comprise one or more among magnesium oxide, calcium oxide, yttrium oxide, zirconium white, vanadium oxide, titanium oxide, cerium oxide and C, B, Si and the BN when mixing raw material promotes the densification of composite diphase material, mullite particle formed carry out three grades, level Four or size grading feed proportioning optimization continuously, the carse, medium and small particle weight ratio of its batching is 5～7: 1～2: 1～3.
3. oxide ceramics multiple phase refractory material according to claim 1 is characterized in that adding by weight percentage 70～90% mullite particle gradating material; Carbon heat reducing-nitrogenize maximum temperature interval is 1300～1550 ℃, and the reaction times is 3～36 hours; A reaction sintering cycle is 26～120 hours altogether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100686717A CN100432022C (en) | 2006-09-04 | 2006-09-04 | Oxide ceramics multiple phase refractory material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100686717A CN100432022C (en) | 2006-09-04 | 2006-09-04 | Oxide ceramics multiple phase refractory material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1919796A CN1919796A (en) | 2007-02-28 |
| CN100432022C true CN100432022C (en) | 2008-11-12 |
Family
ID=37777672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100686717A Expired - Fee Related CN100432022C (en) | 2006-09-04 | 2006-09-04 | Oxide ceramics multiple phase refractory material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100432022C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030535B (en) * | 2010-11-29 | 2013-05-29 | 沈阳大学 | Preparation method of zirconium-nitride enhanced aluminum-oxynitride composite ceramic material |
| CN102503488A (en) * | 2011-10-28 | 2012-06-20 | 河北联合大学 | Method for preparing sialon bonded zirconium oxide refractory |
| CN103508455B (en) * | 2012-06-25 | 2015-10-28 | 中国科学院上海硅酸盐研究所 | The bar-shaped Si of oxidation-resistant ceramic 2n 2o powder and preparation method thereof |
| CN107473719A (en) * | 2017-08-24 | 2017-12-15 | 浙江科屹耐火材料有限公司 | A kind of low carbon high-strength refractory material and its preparation technology |
| CN109626977A (en) * | 2019-02-27 | 2019-04-16 | 佛山石湾鹰牌陶瓷有限公司 | The preparation method of lightweight thermal insulation brick |
| CN109627040A (en) * | 2019-02-27 | 2019-04-16 | 佛山石湾鹰牌陶瓷有限公司 | Lightweight thermal insulation brick |
| CN112028647A (en) * | 2020-08-25 | 2020-12-04 | 贵阳明通炉料有限公司 | High-performance sialon corundum plastic material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092053A (en) * | 1993-03-13 | 1994-09-14 | 山东工业陶瓷研究设计院 | Sialon combined silicon carbide refractory ceramic material |
| 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 |
-
2006
- 2006-09-04 CN CNB2006100686717A patent/CN100432022C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092053A (en) * | 1993-03-13 | 1994-09-14 | 山东工业陶瓷研究设计院 | Sialon combined silicon carbide refractory ceramic material |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| β-Si3N4结合SiC复相材料的分相抗氧化行为. 隋万美.硅酸盐学报，第31卷第9期. 2003 |
| β-Si3N4结合SiC复相材料的分相抗氧化行为. 隋万美.硅酸盐学报，第31卷第9期. 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1919796A (en) | 2007-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100586898C (en) | Manufacture method of silicon carbide refractory ceramics material | |
| CN100432022C (en) | Oxide ceramics multiple phase refractory material | |
| CN102249722B (en) | In-situ synthesized mullite whisker reinforced high-temperature ceramic roller | |
| Singh et al. | Nano mullite bonded refractory castable composition for high temperature applications | |
| Sarkar et al. | Formation and densification of mullite through solid-oxide reaction technique using commercial-grade raw materials | |
| CN110590389B (en) | Silicon nitride whisker-aluminum nitride-corundum ternary composite ceramic material using natural minerals as raw materials and preparation method thereof | |
| CN105859297B (en) | A kind of silicon carbide composite fireproof materials and preparation method thereof | |
| Lao et al. | In-situ synthesis of nitride whiskers-bonded SiAlON–Al2O3 ceramics for solar thermal storage by aluminothermic nitridation of coal-series kaolin | |
| CN100532327C (en) | Method of synthesizing AlN-SiC composite material while controlling content of carbon and nitrogen | |
| US20040222572A1 (en) | Sialon ceramics | |
| Maitra et al. | Zirconia–mullite materials prepared from semi-colloidal route derived precursors | |
| CN102391002B (en) | Magnesia-alumina spinel skinning-resistant non-amorphous refractory material for cement kiln as well as preparation method and application thereof | |
| CN101481822B (en) | Method for preparing beta-sialon crystal whisker by two-step reduction nitridation reaction | |
| GB2151607A (en) | Sialon material | |
| CN103922752B (en) | Method for preparing beta-SiAlON multiphase material by using fly ash | |
| CN1298676C (en) | Method for preparing beta-'Sailong' ceramic powder | |
| US7314593B2 (en) | Process for preparing improved silicon carbide powder | |
| CN1142115C (en) | Process for preparing 'Meialong' magnesium ceramics with natural minerals as raw materials | |
| CN100389233C (en) | Beta'-Sialon whisker gas phase reaction preparation method | |
| US6066583A (en) | Process for the production of ceramic materials | |
| CN101456740B (en) | Method for in-situ synthesis of MgAlON/beta-sialon composite ceramic material | |
| CN102718515A (en) | Nitridation firing corundum aluminium nitride precast brick | |
| Hao et al. | Synthesis of O'-Sialon/SiC ecomaterials by using non-traditional resources: Yangtze River sand | |
| CN101456738B (en) | Method for synthesizing MgAlON/beta-sialon composite ceramic material | |
| CN100439287C (en) | Method for preparing alpha/beta multi-phase sialon ceramic powder utilizing waste resistant material and slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081112 Termination date: 20100904 |