CN102424585A - Zirconia-mullite multiphase refractory raw material and preparation method thereof - Google Patents
Zirconia-mullite multiphase refractory raw material and preparation method thereof Download PDFInfo
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- CN102424585A CN102424585A CN2011102598247A CN201110259824A CN102424585A CN 102424585 A CN102424585 A CN 102424585A CN 2011102598247 A CN2011102598247 A CN 2011102598247A CN 201110259824 A CN201110259824 A CN 201110259824A CN 102424585 A CN102424585 A CN 102424585A
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- zirconia
- mullite
- complex phase
- phase fire
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Abstract
The invention relates to a zirconia-mullite multiphase refractory raw material and a preparation method thereof, belonging to the technical field of preparation of high temperature resistant multiphase materials. The invention is characterized in that: the zirconia-mullite multiphase refractory raw material is prepared through an in-situ reaction between zircon and different aluminum sources (e.g., alpha-Al2O3, gamma-Al2O3, Al(OH)3, etc.) at high temperature. The prepared zirconia-mullite multiphase refractory raw material mainly comprises m-ZrO2, t- ZrO2, mullite, etc. The novel method for preparing the zirconia-mullite multiphase refractory raw material in the invention has the remarkable advantages of low process cost, small energy consumption, convenience for large scale production and the like, and provides a novel technical approach for high efficiency value-added utilization of zirconium-containing silicate minerals like zircon.
Description
Technical field:
The present invention relates to a kind of zirconia-mullite complex phase fire raw material and preparation method thereof, belong to high temperature resistant composite diphase material preparing technical field.
Background technology:
Zircon is a kind of crucial zirconium nonmetalliferous ore mineral that contain, and it all has very at numerous areas such as refractory materials, ceramic industry, building materials industry, electronic industry and nuclear industries uses widely.The staple of zircon is a zirconium silicate, and it mainly originates in grouan, basic rocks or the pegmatite and postmagmatic ore deposit relevant with these rocks, also has zircon to exist in rock, sedimentogeneous rock and some extrusive rock on the turn in addition.
Mullite material is made up of mullite single crystal or polycrystalline; Have high Young's modulus, creep resistance, thermal-shock resistance and hot strength; Chemicalstability is good; Can be in the etch of opposing molten metal and non-oxidized substance more than 1000 ℃, the while has satisfactory stability property and mechanical property, lower thermal conductivity and excellent electric insulation property under the high temperature oxidation condition, and it is widely used in the research of high-temperature structural material.
Composite diphase material has better physicochemical property than monophase materials; Therefore intend and under hot conditions, react the mechanical property that the zirconia-mullite multiple phase refractory material that burns till acquisition can significantly improve single-material through zircon and aluminum oxide; Make it have more excellent mechanical property, thermal shock resistance and erosion-resisting characteristics; Raw material or high-temperature structural material as refractory materials are widely used in numerous areas such as metallurgy, machinery, chemical industry, smelting iron and steel.
Traditional method for preparing zirconia-mullite complex phase raw material often adopts zirconium white or zirconium silicate fine powder and mullite fine powder to carry out compound as main raw material.Like Tang Shao fur coat etc. with ZrSiO
4And Al
2O
3Synthesized the zirconia-mullite diphase ceramic material and inquired into reaction in mechanism for the main raw material original position, prepared material has mechanical property preferably.Zhao Shike etc. are with ultra-fine ZrSiO
4And Al
2O
3The reaction sintering product for combining phase, be that aggregate has been prepared the zirconia-mullite composite refractory with high-compactness, good heat-shock resistance with the coarse grain mullite.This class methods technological process is comparatively simple, but the acquisition of desired raw material often need be passed through processes such as complicated fragmentation and high temperature, thereby makes production cost higher.
Except traditional high-temperature sintering process, in some researchs, adopt liquid phase synthetic method also can obtain this high performance zirconia-mullite complex phase powder body material.Adopt amorphous crystallization method to prepare high t-ZrO like the little equality of Tan
2The zirconia-mullite nano heterogeneous ceramic of content has been studied SiO simultaneously
2-2Al
2O
3-2ZrO
2The original position dominated crystallization process of system, densification and crystal grain problem such as grow up fast fully when this preparation method has solved nanometer powder reunion, high temperature sintering helps obtaining evenly, the structural ceramic material of fine and close, high reliability.Zhu Baiquan etc. are raw material with the zircon, adopt the synthetic zirconia-mullite complex phase powder of having prepared of molten-salt growth method, and this compound method makes and is reflected at the mixing that realizes atomic scale in the liquid phase, and institute's synthetic powder has pattern preferably.This type reaction is temperature required lower, and prepared material property is better, and its deficiency is to need just can obtain the synthetic title product of wanting through polystep reaction.
For reduce production costs, shortened process, seek a kind of efficiently, compound method prepares zirconia-mullite complex phase raw material cheaply, can select for use natural mineral to prepare this composite diphase material through a step high-temperature reaction process as raw material.Thermomechanical analysis shows, mixes zircon and aluminum oxide fine powder and be heated to make zircon decompose the SiO that produces more than 1500 ℃ by proper proportion
2With Al
2O
3Reaction forms mullite.Therefore adopting the natural mineral zircon is that main raw material prepares effectively save energy and cutting down the consumption of energy of zirconia-mullite composite diphase material; This technology can also realize that zircon etc. contains the efficient increment utilization of zirconium non-metallic minerals, has crucial meaning in addition.
Summary of the invention:
The preparation method who the purpose of this invention is to provide the zirconia-mullite complex phase fire raw material that a kind of technological process is simple relatively, production cost is lower, energy consumption is lower, thing phase purity is higher.
The present invention relates to a kind of novel method of zirconia-mullite complex phase fire feedstock production, it is characterized by: with zircon fine powder and aluminium source (can be α-Al
2O
3, γ-Al
2O
3And Al (OH)
3Deng) be main raw material, add the normal temperature wedding agent, and it mixed by a certain percentage, then through base, drying, burn till, technological process such as cooling prepares zirconia-mullite complex phase fire raw material.The main moity of prepared zirconia-mullite complex phase fire raw material has m-ZrO
2, t-ZrO
2With mullite etc., the mutually shared overall proportion m-ZrO of each thing
2+ t-ZrO
2+ 3Al
2O
32SiO
2Greater than 96%.This zirconia-mullite composite diphase material can be used as the raw material of refractory materials.
Said zircon fine powder is commercially available industrial raw material, its specification of quality be zircon purity greater than 90wt%, its granularity requirements is that maximum particle diameter is less than 500 μ m.
Said aluminium source fine powder is commercially available industrial raw material, can adopt α-Al
2O
3, γ-Al
2O
3And Al (OH)
3Compound in aluminium commonly used.Its specification of quality be aluminium source purity greater than 95wt%, its granularity requirements is that maximum particle diameter is less than 500 μ m.
The normal temperature wedding agent that adds in the said preparation process adopts silicon sol or industrial dextrin solution, polyvinyl alcohol solution etc., and its addition is 0.2%～15.0% of the batching total mass.
The preparation process of said zirconia-mullite composite diphase material is:
A) (can be α-Al with zircon fine powder and aluminium source
2O
3, γ-Al
2O
3And Al (OH)
3Deng) by the zircon fine powder account for 20wt%～80wt%, the aluminium source accounts for the mixed of 20wt%～80wt%; Ball milling 0.1～24h is even to the raw material thorough mixing in the mixing back adding ball mill; The mode of ball milling can be selected dry ball milling or wet ball grinding for use; Wherein ball-milling medium can be selected Ceramic Balls or agate ball etc. for use, and wet ball grinding can select for use water as ball milling liquid.
B) mixed raw material is processed base substrate through technologies such as dry-pressing formed, half-dried molded or isostatic pressings, at room temperature carry out drying treatment again.
C) drying is good base substrate places the thermal kiln furnace heating to burn till, and firing temperature is 1450 ℃～1800 ℃.Base substrate does not have particular requirement through the heat-up rate in normal temperature to the firing range; In 800 ℃～1200 ℃ TR, can be incubated certain hour; Insulation is 1～18 hour under final firing temperature, naturally cools to room temperature then and can obtain described zirconia-mullite complex phase fire raw material.
The novel method of this preparation zirconia-mullite complex phase fire raw material that the present invention relates to has that technological process is simple, preparation cost is lower, energy consumption is less and is convenient to outstanding advantage such as scale operation, and the efficient increment utilization of also being rich in the natural mineral raw of zirconium, element silicon for zircon etc. simultaneously provides a new technological approaches.
Embodiment:
Embodiment 1:
Raw material and proportioning:
Zircon (zirconium silicate content is about 98wt%) add-on is 54.30wt%, and median size is less than 1 μ m; α-Al
2O
3Add-on is 45.70wt%, and median size is less than 100 μ m.The addition that adds wedding agent (silicon sol) is 3% of batching total mass.
Batching, batch mixing:
At first with various raw materials according to the aforementioned proportion ball mill of packing into, select for use alumina balls as ball-milling medium, water is ball milling solution, wet ball grinding 6h is even with the raw material thorough mixing, granularity is less than 1 μ m, the aperture sieve screen over-size is less than 2.0wt%.
Dry, grinding:
The raw material that ball mill mixing is good takes out, and places baking oven that the moisture of raw material is fully evaporated, and raw material is poured into ground 30min in the mortar then.
Moulding:
The wedding agent silicon sol of adding 3% adopts dry pressing to make material obtain the sample of Φ 100mm * 200mm in the pressure pressed of 200MPa then in the raw material after grinding.
Burn till:
Place high-temperature electric resistance furnace to heat the base substrate of forming, maximum sintering temperature is 1600 ℃ and is incubated 3 hours.
Above-mentionedly can obtain said zirconia-mullite complex phase fire raw material after burning till the product naturally cooling.The main moity of prepared zirconia-mullite complex phase fire raw material is m-ZrO
2, t-ZrO
2And mullite, the mutually shared overall proportion m-ZrO of each thing
2+ t-ZrO
2+ 3Al
2O
32SiO
2Greater than 96%.
Embodiment 2:
Raw material and proportioning:
Zircon (zirconium silicate content is about 96wt%) add-on is 43.72wt%, and median size is less than 500 μ m; Al (OH)
3Add-on is 56.28wt%, and median size is less than 500 μ m.The addition that adds wedding agent (concentration is 10% polyvinyl alcohol solution) is 2% of batching total mass.
Batching, batch mixing:
At first with various raw materials according to the aforementioned proportion ball mill of packing into, select for use alumina balls as ball-milling medium, water is ball milling solution, wet ball grinding 10h is even with the raw material thorough mixing, granularity is less than 1 μ m, the aperture sieve screen over-size is less than 2.0wt%.
Dry, grinding:
The raw material that ball mill mixing is good takes out, and places baking oven that the moisture of raw material is fully evaporated, and raw material is poured into ground 30min in the mortar then.
Moulding:
The wedding agent polyvinyl alcohol solution of adding 2% adopts the isostatic pressing method to make material obtain the sample of Φ 100mm * 200mm in the pressure pressed of 100MPa then in the raw material after grinding.
Burn till:
Place high-temperature electric resistance furnace to heat on the sample of forming, maximum sintering temperature is 1650 ℃ and is incubated 2 hours.
Above-mentionedly can obtain said zirconia-mullite complex phase fire raw material after burning till the product naturally cooling.The main moity of prepared zirconia-mullite complex phase fire raw material is m-ZrO
2, t-ZrO
2And mullite, the mutually shared overall proportion m-ZrO of each thing
2+ t-ZrO
2+ 3Al
2O
32SiO
2Greater than 96%.
Embodiment 3:
Raw material and proportioning:
Zircon (zirconium silicate content is about 95wt%) add-on is 51.93wt%, and median size is less than 100 μ m; γ-Al
2O
3Add-on is 48.07wt%, and median size is less than 100 μ m.The addition that adds wedding agent (industrial dextrin solution) is 4% of batching total mass.
Batching, batch mixing:
At first with various raw materials according to the aforementioned proportion ball mill of packing into, select for use alumina balls as ball-milling medium, water is ball milling solution, wet ball grinding 8h is even with the raw material thorough mixing, granularity is less than 1 μ m, the aperture sieve screen over-size is less than 2.0wt%.
Dry, grinding:
The raw material that ball mill mixing is good takes out, and places baking oven that the moisture of raw material is fully evaporated, and raw material is poured into ground 30min in the mortar then.
Moulding:
The wedding agent of adding 4% industry dextrin solution adopts the isostatic pressing method to make material obtain the sample of Φ 100mm * 200mm in the pressure pressed of 150MPa then in the raw material after grinding.
Burn till:
Place high-temperature electric resistance furnace to heat on the sample of forming, maximum sintering temperature is 1550 ℃ and is incubated 4 hours.
Above-mentionedly can obtain said zirconia-mullite complex phase fire raw material after burning till the product naturally cooling.The main moity of prepared zirconia-mullite complex phase fire raw material is m-ZrO
2, t-ZrO
2And mullite, the mutually shared overall proportion m-ZrO of each thing
2+ t-ZrO
2+ 3Al
2O
32SiO
2Greater than 96%.
Claims (6)
1. zirconia-mullite complex phase fire raw material and preparation method thereof is characterized by and adopts the high-temp in-situ synthetic zirconia-mullite complex phase fire raw material of reaction down.The main moity of the zirconia-mullite complex phase fire raw material that the present invention is prepared has m-ZrO
2, t-ZrO
2With mullite etc., the mutually shared overall proportion m-ZrO of each thing
2+ t-ZrO
2+ 3Al
2O
32SiO
2Greater than 96%.This zirconia-mullite composite diphase material can be used as the raw material of refractory materials.
2. a kind of zirconia-mullite complex phase fire raw material according to claim 1 is characterized by: the preparation of said zirconia-mullite complex phase fire raw material (can be α-Al with the zircon fine powder with different aluminium sources
2O
3, γ-Al
2O
3And Al (OH)
3Deng) be main raw material; Add the normal temperature wedding agent; And account for the mixed that 20wt%～80wt%, aluminium source account for 20wt%～80wt% by the zircon fine powder, then through base, drying, burn till, technological process such as cooling prepares zirconia-mullite complex phase fire raw material.
3. a kind of zirconia-mullite complex phase fire raw material according to claim 2, it is characterized by: said zircon fine powder is commercially available industrial raw material, its specification of quality be zircon purity greater than 90wt%, its granularity requirements is that maximum particle diameter is less than 500um.
4. a kind of zirconia-mullite complex phase fire raw material according to claim 2 is characterized by: said aluminium source fine powder is commercially available industrial raw material, can adopt α-Al
2O
3, γ-Al
2O
3And Al (OH)
3Compound in aluminium commonly used.Its specification of quality be aluminium source purity greater than 95wt%, its granularity requirements is that maximum particle diameter is less than 500 μ m.
5. a kind of zirconia-mullite complex phase fire raw material according to claim 2; It is characterized by: the normal temperature wedding agent that adds in the said preparation process adopts silicon sol or industrial dextrin solution, polyvinyl alcohol solution etc., and its addition is 0.2%～15.0% of the batching total mass.
6. a kind of zirconia-mullite complex phase fire raw material according to claim 2, its preparation process is followed successively by:
A) (can be α-Al with zircon fine powder and aluminium source
2O
3, γ-Al
2O
3And Al (OH)
3Deng) mixing the back according to a certain ratio, to add in the ball mill ball milling 0.1～24h even to the raw material thorough mixing; The mode of ball milling can be selected dry ball milling or wet ball grinding for use; Wherein ball-milling medium can be selected Ceramic Balls or agate ball etc. for use, and wet ball grinding can be selected for use as ball milling liquid.
B) mixed raw material is processed base substrate through technologies such as dry-pressing formed, half-dried molded or isostatic pressings, at room temperature carry out drying treatment again.
C) drying is good base substrate places the thermal kiln furnace heating to burn till, and firing temperature is 1450 ℃～1800 ℃.Base substrate does not have particular requirement through the heat-up rate in normal temperature to the firing range; In 800 ℃～1200 ℃ TR, can be incubated certain hour; Insulation is 1～18 hour under final firing temperature, naturally cools to room temperature then and can obtain described zirconia-mullite complex phase fire raw material.
Priority Applications (1)
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|---|---|---|---|
| CN2011102598247A CN102424585A (en) | 2011-09-05 | 2011-09-05 | Zirconia-mullite multiphase refractory raw material and preparation method thereof |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104446402A (en) * | 2014-10-29 | 2015-03-25 | 安徽省皖捷液压科技有限公司 | Zircon ceramic and preparation method thereof |
| CN109311760A (en) * | 2016-06-10 | 2019-02-05 | 弗劳恩霍夫应用研究促进协会 | Zirconia ceramics, the porous material being made from it and the method for manufacturing zirconia ceramics |
| CN110194673A (en) * | 2019-05-31 | 2019-09-03 | 武汉科技大学 | A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof |
| CN113956024A (en) * | 2021-11-29 | 2022-01-21 | 上海材料研究所 | Thermal shock resistant composite ceramic material |
| CN116177989A (en) * | 2022-12-30 | 2023-05-30 | 广东东方锆业科技股份有限公司 | High-strength zirconium silicate composite ceramic grinding medium and preparation method thereof |
-
2011
- 2011-09-05 CN CN2011102598247A patent/CN102424585A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 李悦彤等: "锆英石原位合成氧化锆-莫来石复相材料的研究", 《中国非金属矿工业导刊》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104446402A (en) * | 2014-10-29 | 2015-03-25 | 安徽省皖捷液压科技有限公司 | Zircon ceramic and preparation method thereof |
| CN109311760A (en) * | 2016-06-10 | 2019-02-05 | 弗劳恩霍夫应用研究促进协会 | Zirconia ceramics, the porous material being made from it and the method for manufacturing zirconia ceramics |
| CN109311760B (en) * | 2016-06-10 | 2021-10-29 | 弗劳恩霍夫应用研究促进协会 | Zirconia ceramic, porous material made therefrom, and method for manufacturing zirconia ceramic |
| CN110194673A (en) * | 2019-05-31 | 2019-09-03 | 武汉科技大学 | A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof |
| CN113956024A (en) * | 2021-11-29 | 2022-01-21 | 上海材料研究所 | Thermal shock resistant composite ceramic material |
| CN113956024B (en) * | 2021-11-29 | 2023-02-28 | 上海材料研究所 | Thermal shock resistant composite ceramic material |
| CN116177989A (en) * | 2022-12-30 | 2023-05-30 | 广东东方锆业科技股份有限公司 | High-strength zirconium silicate composite ceramic grinding medium and preparation method thereof |
| CN116177989B (en) * | 2022-12-30 | 2023-12-12 | 广东东方锆业科技股份有限公司 | High-strength zirconium silicate composite ceramic grinding medium and preparation method thereof |
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Application publication date: 20120425 |