CN101486572A - Process for preparing ZrO2-Al2TiO5 composite material - Google Patents
Process for preparing ZrO2-Al2TiO5 composite material Download PDFInfo
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- CN101486572A CN101486572A CNA2009100068499A CN200910006849A CN101486572A CN 101486572 A CN101486572 A CN 101486572A CN A2009100068499 A CNA2009100068499 A CN A2009100068499A CN 200910006849 A CN200910006849 A CN 200910006849A CN 101486572 A CN101486572 A CN 101486572A
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Abstract
The invention relates to a preparation method for a composite material of ZrO2-Al2TiO5 and belongs to the field of ceramic material. The used materials and the weight percentage of the materials are as follows: 92 to 96 percent of nano zirconia, 2 to 5 percent of nano aluminum titanate as well as 2 to 3 percent of nano magnesia. The nano zirconia and nano magnesia polyvinyl alcohol liquids are mixed and pressed into blocks, dried, cracked, and screened to obtain a material the grain diameter of which is less than 0.03mm; then the nano aluminum titanate and the polyvinyl alcohol liquid are added, and mixed to prepare a blank after ageing mixture. The shaping pressure of the blank is equal to or more than 100MPa; the blank is dried for 2h at 110 DEG C after being shaped; then the composite material of ZrO2-Al2TiO5 which takes zirconia as the main component is obtained by carrying out heat preservation for 2 to 3h to the blank at the temperature between 1350 and 1400 DEG C and then sintering the blank. The composite material of ZrO2-Al2TiO5 prepared by the preparation method is remarkably improved on the thermal shock resistance than a pure ZrO2 material, and is a hopeful updating material for a steel continuous casting zirconium water gap.
Description
Technical field
The invention belongs to the stupalith field, be specifically related to a kind of ZrO
2-Al
2TiO
5The preparation method of matrix material.
Background technology
The present invention is a kind of ZrO that can be used for fields such as metallurgy, automobile, space flight of exploitation
2-Al
2TiO
5Matrix material.This matrix material is that the composite granule with nano zircite, nano barium titanate aluminium and nano magnesia is that feedstock production forms, and this matrix material has good high Warm performance, Strong degree and heat-shock resistance.
Molten steel tundish zirconium white (ZrO in the present ferrous metallurgy billet continuous casting system
2) the metering nozzle material exist be subjected to that the transient heat shock action takes place very easily that thermal shock cracking peels off, to such an extent as to aperture, the mouth of a river enlarges and causes watering the steel operation and interrupt even cause badly bleeding damage continuous casting key equipment crystallizer.Be badly in need of research and development a kind of high temperature resistant, thermal expansivity is less, the high temperature resistant structure ceramics of high-heat resistance shock resistant, substitutes existing metering nozzle zirconia material.
ZrO
2The Zr-O bond rupture can high (737.8kj/mol), fusing point height (2700 ℃), chemical stability is good, be difficult for by the wetting erosion of metallic solution, the anti-metal melt of its excellence washes away aggressiveness and obtained effect preferably in the billet continuous casting system, so present stage ZrO
2It is the preferred material that the billet continuous casting metering nozzle is made.Yet, ZrO
2The volume effect of crystal conversion is big, thermal conductivity is little (only is 0.36Wm
-1K
-1), thermal expansivity height (α=10 * 10
-6/ ℃ about), the temperature that zirconia metering nozzle waters steel when work mouth of a river is risen sharply to 1650 ℃ of liquid steel temperatures by 800 ℃ of preheating temperatures, so harsh thermal shock condition very easily causes zirconia metering nozzle to produce the thermal shock cracking.
ZrO
2Have the polymorphic transition change characteristic, the density of each crystal formation is: cubic zirconia (c-ZrO
2) 6.27g/cm
3, tetragonal zircite (t-ZrO
2) 6.10g/cm
3, monoclinic zirconia (m-ZrO
2) 5.68g/cm
3In ℃ temperature range of room temperature～2700, with temperature rising ZrO
2The order of crystal conversion is: m-ZrO
2→ t-ZrO
2→ c-ZrO
2, temperature reduces the reverse transformation of zirconium white crystal formation, all is attended by volume effect during each crystal conversion.Astable zirconium white (N-ZrO
2) m-ZrO
2With t-ZrO
2Crystal conversion has the feature of Ma Dingshi body reversible transformation, and to begin temperature be 1150 ℃ to crystal conversion during intensification, and starting temperature of transformation is 1100 ℃ during cooling.Because t-ZrO
2→ m-ZrO
2The volumetric expansion effect of crystal conversion is big, and therefore astable pure zirconia is difficult to prepare fine and close and the high sintered material of intensity.
In the zirconium white raw material, add and Z
4+Metallic cation oxide compound (CaO, MgO, Y that ionic radius is close
2O
3Deng) as stablizer, can obtain behind the high temperature sintering 2000 ℃ to room temperature can both stable existence c-ZrO
2, can prepare densified sintering product, practical zirconia material that intensity is high, but c-ZrO
2The thermal expansivity height, α=10 * 10
-6/ ℃, the thermal shock resistance during the thermal shock process of experience high temperature difference, thermal shocking is low, and thermal shock fatigue easily takes place.
In zirconia material, introduce few stable agent CaO, MgO, Y
2O
3PSZ (the P-ZrO of preparation
2) material, have tangible raising than the thermal shock resistance of astable zirconium white and fully stabilized zirconia, but by P-ZrO
2The thermal shock resistance that waters the steel metering nozzle of material preparation is still relatively poor.
Aluminium titanates (Al
2TiO
5) stupalith has high fusing point (1860 ℃), in room temperature～1000 ℃ temperature range, aluminium titanates has low thermalexpansioncoefficient (α less than zero, or approach zero), is present only low bulk, dystectic thermal shock resistant ceramic material.Obtain effect preferably by the tooth section Stainless Steel Alloy smelting pot of material of aluminum titanate preparation, non-ferrous metal aluminum smelting technology crucible, cast aluminium riser pipe, float glass flow liquid flashboard, automobile exhaust purifier carrier etc.
The present invention adopts nano material technology and complex phase ceramic modification theory, is that feedstock production is burnt till ZrO for 1350 ℃-1400 ℃ at lesser temps with the composite granule of nano zircite, nano barium titanate aluminium, nano magnesia
2-Al
2TiO
5Matrix material.Do not see that as yet the composite granule with nano zircite, nano barium titanate aluminium, nano magnesia is feedstock production ZrO both at home and abroad
2-Al
2TiO
5The research of matrix material aspect and application report.This matrix material has good high temperature resistant, intensity, thermal shock resistance, is expected to the more novel material as ferrous metallurgy continuous casting metering nozzle.
Summary of the invention
The goal of the invention of wood invention is above-mentioned deficiency of the prior art, and the ZrO of a kind of high temperature resistant, Strong degree height, highly heatproof and shockproof is provided
2-Al
2TiO
5The preparation method of matrix material.
The present invention is a kind of ZrO
2-Al
2TiO
5The preparation method of matrix material is characterized in that this matrix material weight percent raw materials used and raw material is: nano zircite 92-96%; Nano barium titanate aluminium 2-5%; Nano magnesia 2-3%.This preparation method may further comprise the steps: blank preparation, blank forming, body drying, matrix material high temperature burn till.
The raw materials used particle diameter of this matrix material is: the particle diameter＜100nm of nano zircite＜100nm, nano barium titanate aluminium＜100nm, nano magnesia.
The weight percent content of the raw materials used purity of this matrix material is: the ZrO in the nano zircite
2〉=99%; Al in the nano barium titanate aluminium
2TiO
5〉=94%; MgO in the nano magnesia 〉=99%.
The blank preparation method of this matrix material is: the adding mass concentration is 0.5% polyvinyl alcohol solution 6% (weight percent) in the composite granule of nano zircite, nano barium titanate aluminium, nano magnesia, leave standstill 4h after stirring 10min, with 100MPa pressure moulding test block, crushing and screening, the material particular diameter＜0.03mm behind the crushing and screening are carried out in test block behind 110 ℃ of dry 4h; It is 0.5% polyvinyl alcohol solution 6% (weight percent) that material behind the crushing and screening is added mass concentration once more, leaves standstill 4h after stirring 10min, obtains the blank of using for composite material forming.
The blank forming method of this matrix material is: adopting hydraulic press is base substrate with blank compression moulding, the pressure 〉=100MPa of blank forming.
The body drying method of this matrix material is: base substrate is at 110 ℃ of dry 2h after the moulding.
This matrix material high temperature process for calcining is: dry back base substrate adopts electric furnace to burn till, 1350-1400 ℃ of firing temperatures, and insulation 2-3h, obtaining with zirconium white after burning till is the ZrO of main composition
2-Al
2TiO
5Matrix material.
ZrO of the present invention
2-Al
2TiO
5The matrix material batching is formed the technical thought of determining:
Utilizing the reactive sintering effect of nano particle high-ratio surface energy, is that raw material can burn till ZrO for 1350 ℃-1400 ℃ at lesser temps with nano zircite, nano barium titanate aluminium, nano magnesia
2-Al
2TiO
5Matrix material.The effect of nano barium titanate aluminium is the thermal expansivity that can reduce matrix material, in the matrix material sintering process, can prevent the inhomogeneous growth of zirconium white crystal grain, obtain aluminium titanates in conjunction with zirconic even fine crystalline structure, make matrix material have high intensity and thermal shock resistance.The effect of nano magnesia is the stablizer as zirconium white and aluminium titanates in the batching, and magnesium oxide can enter the lattice of zirconium white and aluminium titanates when high temperature sintering, forms PSZ and stablizes aluminium titanates.
The thermal dilation difference of each crystallographic axis of aluminium titanates crystal is bigger, causes aluminium titanates to produce tiny crack when high temperature cooling, and tiny crack makes the physics thermal expansion that aluminium titanates takes place up when being warming up to 950 ℃.And the m-ZrO in the PSZ
2When 950 ℃ of high temperature, take place to t-ZrO
2Reversible crystal conversion, and be attended by volume effect.At ZrO
2-Al
2TiO
5When matrix material is warming up to 950 ℃ from low temperature, m-ZrO
2Change t-ZrO into
2Volumetric shrinkage can partly be offset so ZrO by volumetric expansion behind the aluminium titanates tiny crack
2-Al
2TiO
5Matrix material has high intensity and thermal shock resistance.
In sum, the present invention is with the ZrO of nano zircite, nano barium titanate aluminium, nano magnesia preparation
2-Al
2TiO
5Matrix material has high temperature resistant, high intensity and high thermal shock stability, be expected to be applied to ferrous metallurgy and water the steel system, become ferrous metallurgy continuous casting metering nozzle more novel material, but and field such as application nonferrous metallurgy, glass, automobile exhaust purifier, space flight, military project.
Embodiment
Embodiment 1
The weight percent of matrix material blank is: the nano zircite 92% of＜100nm, the nano magnesia 3% of＜100nm, the nano barium titanate aluminium 5% of＜100nm.With adding mass concentration in the composite granule of nano zircite, nano barium titanate aluminium, nano magnesia is 0.5% polyvinyl alcohol solution 6% (weight percent), leave standstill 4h after stirring 10min, with 100MPa pressure moulding test block, crushing and screening, the material particular diameter＜0.03mm behind the crushing and screening are carried out in test block behind 110 ℃ of dry 4h; With adding mass concentration in the material behind the crushing and screening once more is 0.5% polyvinyl alcohol solution 6% (weight percent), leaves standstill 4h after stirring 10min, obtains the blank of using for composite material forming.Adopting hydraulic press is base substrate with blank compression moulding, and the pressure of blank forming is 100MPa.Molding blank is behind 110 ℃ of dry 2h, and burning till acquisition through 1350 ℃ of insulation 2h in electric furnace is the ZrO of main composition with zirconium white
2-Al
2TiO
5Matrix material.
Burn back ZrO
2-Al
2TiO
5The folding strength of matrix material is 25.3MPa, and residual strength is 22.2MPa (1100 a ℃～room temperature water-cooled) after 3 thermal shocks.
Embodiment 2
The weight percent of matrix material blank is: the nano zircite 95% of＜100nm, the nano magnesia 3% of＜100nm, the nano barium titanate aluminium 2% of＜100nm.With adding mass concentration in the composite granule of nano zircite, nano barium titanate aluminium, nano magnesia is 0.5% polyvinyl alcohol solution 6% (weight percent), leave standstill 4h after stirring 10min, with 100MPa pressure moulding test block, crushing and screening, the material particular diameter＜0.03mm behind the crushing and screening are carried out in test block behind 110 ℃ of dry 4h; With adding mass concentration in the material behind the crushing and screening once more is 0.5% polyvinyl alcohol solution 6% (weight percent), leaves standstill 4h after stirring 10min, obtains the blank of using for composite material forming.Adopting hydraulic press is base substrate with blank compression moulding, and the pressure of blank forming is 100MPa.Molding blank is behind 110 ℃ of dry 2h, and burning till acquisition through 1350 ℃ of insulation 2h in electric furnace is the ZrO of main composition with zirconium white
2-Al
2TiO
5Matrix material.
Burn back ZrO
2-Al
2TiO
5The folding strength of matrix material is 28.5MPa, and residual strength is 11.4MPa (1100 a ℃～room temperature water-cooled) after 3 thermal shocks.
Claims (7)
1, a kind of ZrO
2-Al
2TiO
5The preparation method of matrix material is characterized in that may further comprise the steps: blank preparation, blank forming, body drying, matrix material high temperature burn till, and the raw material of described matrix material and the weight percent of each raw material are: nano zircite 92-96%; Nano barium titanate aluminium 2-5%; Nano magnesia 2-3%.
2, ZrO as claimed in claim 1
2-Al
2TiO
5The preparation method of matrix material is characterized in that the weight percent content of raw materials used purity is: the ZrO in the nano zircite
2〉=99%; Al in the nano barium titanate aluminium
2TiO
5〉=94%; MgO in the nano magnesia 〉=99%.
3, ZrO as claimed in claim 1
2-Al
2TiO
5The preparation method of matrix material is characterized in that raw materials used particle diameter is: the particle diameter＜100nm of nano zircite＜100nm, nano barium titanate aluminium＜100nm, nano magnesia.
4, ZrO as claimed in claim 1
2-Al
2TiO
5The preparation method of matrix material, it is characterized in that the blank preparation method is at nano zircite, nano barium titanate aluminium, the adding mass concentration is 0.5% polyvinyl alcohol solution 6% (weight percent) in the composite granule of nano magnesia, leave standstill 4h after stirring 10min, with 100MPa pressure moulding test block, crushing and screening is carried out in test block behind 110 ℃ of dry 4h, material particular diameter＜0.03mm behind the crushing and screening, with adding mass concentration in the material behind the crushing and screening once more is 0.5% polyvinyl alcohol solution 6% (weight percent), leave standstill 4h after stirring 10min, obtain the blank of using for composite material forming.
5, ZrO as claimed in claim 1
2-Al
2TiO
5The preparation method of matrix material is characterized in that the blank forming method is that the employing hydraulic press is a base substrate with blank compression moulding, the pressure 〉=100MPa of blank forming.
6, ZrO as claimed in claim 1
2-Al
2TiO
5The preparation method of matrix material, it is characterized in that the body drying method be after the moulding base substrate at 110 ℃ of dry 2h.
7, ZrO as claimed in claim 1
2-Al
2TiO
5The preparation method of matrix material is characterized in that matrix material high temperature process for calcining is that dry back base substrate adopts electric furnace to burn till, 1350-1400 ℃ of firing temperatures, and insulation 2-3h, obtaining with zirconium white after burning till is the ZrO of main composition
2-Al
2TiO
5Matrix material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100068499A CN101486572A (en) | 2009-02-24 | 2009-02-24 | Process for preparing ZrO2-Al2TiO5 composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100068499A CN101486572A (en) | 2009-02-24 | 2009-02-24 | Process for preparing ZrO2-Al2TiO5 composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101486572A true CN101486572A (en) | 2009-07-22 |
Family
ID=40889658
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100068499A Pending CN101486572A (en) | 2009-02-24 | 2009-02-24 | Process for preparing ZrO2-Al2TiO5 composite material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350236A (en) * | 2011-07-11 | 2012-02-15 | 北京纳辰科技发展有限责任公司 | Nano zirconia alcohol slurry and preparation method thereof |
| CN112010659A (en) * | 2020-08-05 | 2020-12-01 | 武汉重远炉窑工程技术服务有限公司 | Magnesia-alumina spinel refractory material and preparation method thereof |
| CN114477999A (en) * | 2022-03-28 | 2022-05-13 | 泰州市宏华冶金机械有限公司 | Preparation method of thermal shock resistant Al2TiO5-Ti3AlC2 ceramic |
| CN116496074A (en) * | 2023-03-20 | 2023-07-28 | 河南瑞泰耐火材料科技有限公司 | Magnesia-alumina-titanium-zirconium brick and preparation method thereof |
-
2009
- 2009-02-24 CN CNA2009100068499A patent/CN101486572A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350236A (en) * | 2011-07-11 | 2012-02-15 | 北京纳辰科技发展有限责任公司 | Nano zirconia alcohol slurry and preparation method thereof |
| CN112010659A (en) * | 2020-08-05 | 2020-12-01 | 武汉重远炉窑工程技术服务有限公司 | Magnesia-alumina spinel refractory material and preparation method thereof |
| CN114477999A (en) * | 2022-03-28 | 2022-05-13 | 泰州市宏华冶金机械有限公司 | Preparation method of thermal shock resistant Al2TiO5-Ti3AlC2 ceramic |
| CN114477999B (en) * | 2022-03-28 | 2022-09-20 | 泰州市宏华冶金机械有限公司 | Preparation method of thermal shock resistant Al2TiO5-Ti3AlC2 ceramic |
| CN116496074A (en) * | 2023-03-20 | 2023-07-28 | 河南瑞泰耐火材料科技有限公司 | Magnesia-alumina-titanium-zirconium brick and preparation method thereof |
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Open date: 20090722 |