CN100467423C - Al-AlN-ZrO2 thermal shock resistant ceramic material - Google Patents
Al-AlN-ZrO2 thermal shock resistant ceramic material Download PDFInfo
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- CN100467423C CN100467423C CNB2007100845239A CN200710084523A CN100467423C CN 100467423 C CN100467423 C CN 100467423C CN B2007100845239 A CNB2007100845239 A CN B2007100845239A CN 200710084523 A CN200710084523 A CN 200710084523A CN 100467423 C CN100467423 C CN 100467423C
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- zro
- aln
- metal
- sintering
- zro2
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Abstract
The invention discloses an Al-AlN-ZrO2 thermal shock resistance ceramic material in the ceramic based multiple-phase metal ceramic structure material domain, which comprises the following parts: 4-10% metal Al with grain size less than 0. 074mm, 85-92% partial stable ZrO2 with grain size less than 0. 074mm, 3-6% AIN with grain size less than 0. 074mm, 0. 5-2% sintering-assisting agent with grain size less than 0. 01mm, wherein the partial stable ZrO2 is composed of 10-40% monocline ZrO2 and 60-90% cubic ZrO2; the sintering-assisting agent contains SrCO3, TiO2 or La2O3; the blank after allocating and moulding can produce the Al-AIN connected ZrO2 multiple-phase material through nitrifying and sintering under 1500deg. c for 3h. The invention improves the thermal shock resistance property more than the partial stable ZrO2 material, which is a hopefully updated material of steel smelting casting material with sizing nozzle.
Description
[technical field]
The invention belongs to the stupalith field, be specifically related to highly heatproof and shockproof Zirconia ceramic matrix multiphase metal ceramics structured material.
[background technology]
To such an extent as at present the molten steel tundish metering nozzle material in the metallurgical industry billet continuous casting system exists and is subjected to that the transient heat shock action takes place very easily that the thermal shock cracking peels off, aperture, the mouth of a river enlarges and cause watering the practical problems that badly bleeding damage continuous casting key equipment crystallizer is interrupted even causes in the steel operation, and never solved well, be badly in need of studying more novel material.
Continuous casting of iron and steel water the steel system 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, substitute existing metering nozzle zirconia material, the thermal shock resistance that improves metering nozzle is to promote continuous casting of iron and steel art progressive to guarantee, and can reduce the production cost of continuous casting of iron and steel system, improve the smelting iron and steel economic benefit of enterprises.The material science that also can be simultaneously China increases the functional novel material of high temperature.
Since the seventies in last century, countries in the world pottery, fire resisting material field have been carried out zirconium white (ZrO in succession
2) stress induced self malleableize, the fundamental research and the applied research of astable Zirconium oxide plasticizing body material aspect of stablizer selection, stable crystal form phase transformation control, PSZ.
Domestic at raising ZrO
2The research of material heat-shock resistance aspect is to realize that by controlled oxidation zirconium degree of transformation malleableize improves its intensity, toughness, reaches thermal shock resistance.Study and used PSZ (P-ZrO in succession
2) material, except as ferrous metallurgy continuous casting system tundish metering nozzle high-temperature structural material, important use is also arranged at aspects such as metal cutting tool, high-abrasive material, engine piston and cylinder block material, shellproof armor materials.
The nineties in last century, the Lanxide company of the U.S. once developed the AlN-Al-MgO composite diphase material, and its thermal shock resistance and erosion-resisting characteristics are good, more traditional Al
2O
3-ZrO
2-C material lifetime improves 2-3 doubly, and its technical thought is ZrO
2The improvement of metering nozzle material provides the researchdevelopment direction.Metallic aluminium-aluminium nitride combined corundum (Al-AlN-Al has been studied in Institutes Of Technology Of Hebei's Materials Academy and the cooperative development of Tang Gang refractory materials company limited
2O
3) composite diphase material, the Al-AlN-Al that is developed
2O
3It is existing Al work-ing life that slide plate waters steel
2O
32 times of-C matter slide plate.But Al
2O
3Compare ZrO
2High temperature resistant and anti-molten steel erosion performance low, Al-AlN-Al
2O
3Composite diphase material is difficult to the use properties requirement of competent tundish metering nozzle.
AlN is applied to the rare at present report of research of refractory materials aspect, but it is a kind of high temperature resistant, thermal shock resistance is excellent high temperature resistant structure ceramics that the example table of above-mentioned domestic and international two successful Application is understood AlN, the working conditions that can be competent at ferrous metallurgy continuous casting system tundish metering nozzle.With metal A l or metal A l and AlN and ZrO
2Mixing, moulding, reaction is burnt till preparation metal A l-AlN in conjunction with ZrO under condition of nitrogen gas
2Composite diphase material, the utmost point are expected to obtain the more novel material of metallurgical continuous casting metering nozzle.To the research of this composite diphase material, still belong to blank at home at present.
[summary of the invention]
A kind of metal A l-AlN is in conjunction with ZrO
2Composite diphase material is characterized in that this composite diphase material weight percent raw materials used and raw material is: metal A l 4-10%; Partially stabilized ZrO
285-92%; AlN 3-6%; Sintering aid 0.5-2%.
Raw materials used particle diameter is: particle diameter＜0.074mm of metal A l; Particle diameter＜0.074mm of partially stabilized ZrO2; Particle diameter＜0.074mm of AlN; Particle diameter＜the 0.01mm of sintering aid.
Partially stabilized ZrO in raw materials used
2By monocline ZrO
2With a cube ZrO
2Constitute, the weight percent of the two is: monocline ZrO
210-40%; Cube ZrO
260-90%.
Described sintering aid is SrCO
3, TiO
2Or La
2O
3
The forming method of this composite diphase material comprises: pressure forming; Isostatic pressing; Hot die-casting molding; Injection forming; Roll forming or extrusion under vacuum.
The sintering method of this composite diphase material comprises: the high-temperature pressure air calcination; Hot pressed sintering; High-temperature vacuum sintering or high-temperature ammonolysis sintering.The sintering temperature of different sintering processes all 〉=1500 ℃.
The present invention is according to ZrO
2, AlN and metal A l high-temp plastic good characteristic mutually, intend to adopt at ZrO
2Introduce metal A l, AlN in the material as in conjunction with phase, prepare metal A l-AlN in conjunction with ZrO
2Composite diphase material obtains to have high-heat resistance shock resistant, is expected to substitute existing fixed more novel material through mouth of a river 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 at the mouth of a river was risen sharply to 1650 ℃ of liquid steel temperatures by 800 ℃ of preheating temperatures when zirconia metering nozzle watered steel work, so harsh thermal shock condition very easily causes zirconia metering nozzle to produce the thermal shock cracking, and deterioration metering nozzle molten steel washed away the erosion resistivity, reduce the work-ing life of zirconia metering nozzle greatly, even strengthen because of the aperture and to make the excessive casting process that interrupts of molten steel flow, if control improper bleed-out, the continuous casting key equipment crystallizer that the damage valency is high of also can taking place.
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 knot body 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.
AlN is the new type functional stupalith of a kind of high temperature resistant, high heat conduction and relatively low thermel expansion.Its theoretical density is 3.26g/cm
3, under normal pressure, do not have fusing point, and decompose 2450 ℃ of distillations, can tolerate 1650 ℃ high temperature action; Thermalexpansioncoefficient is lower by (4.6 * 10
-6/ ℃, be about ZrO
2Thermal expansivity 1/2), thermal conductivity is very high, and (theoretical value is 320Wm
-1K
-1, be about ZrO
2888 times), have the good thermal shock resistance of the withstand temp sudden turn of events and high temperature difference; This material is difficult for by non-ferrous metal such as metal A l and melt thereof wetting, a kind of good anti-erosion high temperature resistant structure ceramics that is difficult for for the molten steel infiltration.
The theoretical density of metal A l is 2.7g/cm
3, fusing point is 660 ℃ only, thermal conductivity is up to 203Wm
-1K
-1Usually the use temperature of refractory materials or high temperature resistant structure ceramics〉1000 ℃, so metal A l seldom is used for high-temperature structural ceramics or refractory materials.
Al-AlN-ZrO of the present invention
2The composition of thermal shock resistant ceramic material and structure Design thinking are:
(1) with high-melting-point, anti-molten steel erosive ZrO
2Be the principal constituent of composite diphase material, cooperate a spot of metal A l and AlN to constitute Al-AlN-ZrO
2Composite diphase material.The content of metal A l in composite diphase material should be controlled in the certain limit, and metal A l should exist only in the gap of zirconia particles in composite diphase material.Even metal A l is at high temperature for the fusion plastic state, its content is little and be in the gap of zirconia particles, to Al-AlN-ZrO
2The also unlikely generation damaging effect of the high-temperature behavior of composite diphase material.Work as Al-AlN-ZrO
2During the thermal shock process of the big and thermal shocking of the composite diphase material experience temperature difference, plastic state under the metal A l high temperature has reduced the elastic strain energy of composite diphase material, and can have good passivation and relexation, thereby improve Al-AlN-ZrO to thermal shock crack tip stress in the composite diphase material
2The thermal shock resistance of composite diphase material.
(2) metal A l and AlN compare ZrO
2Etc. high many of the thermal conductivity of conventional stupalith, the high thermal conductivity of metal A l and AlN has strong samming ability to composite diphase material, the material surface and the inner temperature difference in the time of can reducing composite diphase material experience thermal shock process, reduce the thermal stresses that produces in the composite diphase material, thereby improved the thermal shock resistance of composite diphase material.
(3) metal A l and the AlN that is in the composite diphase material upper layer is resistant to elevated temperatures Al at high temperature oxidation
2O
3, the upper layer that its volumetric expansion effect of following can closely knit composite diphase material helps the raising of the anti-molten steel erosional competency of composite diphase material.High temperature oxidation product A l
2O
3Also can react the better γ-AlON of generation chemical resistance of concrete under 1600 ℃ high temperature working conditions with AlN, this process helps the raising of composite diphase material density and corrosion resistance also with the volumetric expansion effect.
AlN and ZrO
2Be than the hard-to-sinter material, in batching, introduce a spot of sintering aid (SrCO
3, TiO
2Or La
2O
3Deng) can promote the sintering and the densification of composite diphase material.
In sum, the present invention is at ZrO
2Introduce out-phase materials such as a spot of metal A l and AlN in the material, utilize high heat conductance, the metal A l plasticity thermal stresses buffering mutually of AlN and metal A l, the highly heatproof and shockproof ZrO of exploitation
2Ceramic base multiphase metal ceramics structured material, the working conditions that can be competent at ferrous metallurgy continuous casting system tundish metering nozzle, be expected to become the continuous casting metering nozzle more novel material, but and application to other industrial circle.At present to the Al-AlN of high thermal shock stability in conjunction with ZrO
2The research of composite diphase material still belongs to blank at home.
The raw materials used technical requirements of the embodiment of the invention is as shown in table 1.Embodiment prepares Al-AlN in conjunction with ZrO
2Composite diphase material adopts nitriding atmosphere to burn till, and firing temperature is 1500 ℃ of insulation 3h, burns each sample thermal shock resistance of back and is shown in table 2.The SEM microstructure of ANZ-1 sample and ANZ-4 sample is shown in accompanying drawing 1, accompanying drawing 2.By the thermal shock performance of each sample of table 2 as can be known, metal A l-AlN is in conjunction with ZrO
2The thermal shock resistance of composite diphase material is good, compares ZrO
2The thermal shock performance of material sample has tangible raising.
The technical requirements of table 1 raw material
Folding strength after the thermal shock of each sample of table 2
[description of drawings]
Fig. 1 is the SEM microstructure of ANZ-1 sample of the present invention
Fig. 2 is the SEM microstructure of ANZ-4 sample of the present invention
[embodiment]
Embodiment 1
Batching is formed: the zirconium white 87.5% of particle diameter≤0.06mm, the metal A l 8% of particle diameter≤0.06mm, the AlN 3% of particle diameter≤0.06mm, the SrCO of particle diameter≤0.01mm
31.5%.
Earlier with metal A l, partially stabilized ZrO
2, synthetic AlN and SrCO in advance
3Prepare burden and dried mixing 1 minute; Add dehydrated alcohol then and make it to form the slurry with flowability, wet method stirred 30 minutes; Slurries filtration after wet method stirred removed behind the ethanol seasoning 2 hours; Adopt pressing machine to carry out the sample moulding, moulding pressure is 100MPa; Sample material adopts nitriding atmosphere to burn till, and firing temperature is 1500 ℃, and soaking time is 3h.
The intensity of burning the back sample is 65.2MPa, the intensity 15.2MPa after the thermal shock, the intensity 10.6MPa after three thermal shocks, the intensity 6.4MPa after five thermal shocks.Contrast experiment's zirconia material sample only experiences 2 thermal shocks fracture damage just takes place.
The thermal shock test condition is that sample is heated to 1100 ℃ of insulations 30 minutes, takes out and carries out 20 ℃ of water-cooleds of room temperature, repeats repeatedly to carry out.
Embodiment 2
Batching is formed: the zirconium white 86.5% of particle diameter≤0.06mm, the metal A l 9% of particle diameter≤0.06mm, the AlN 3% of particle diameter≤0.06mm, the TiO of particle diameter≤0.01mm
21.5%.
Earlier with metal A l, partially stabilized ZrO
2, synthetic AlN and TiO in advance
2Prepare burden and dried mixing 1 minute; Add dehydrated alcohol then and make it to form the slurry with flowability, wet method stirred 30 minutes; Slurries filtration after wet method stirred removed behind the ethanol seasoning 2 hours; Adopt pressing machine to carry out the sample moulding, moulding pressure is 100MPa; Sample material adopts nitriding atmosphere to burn till, and firing temperature is 1500 ℃, and soaking time is 3h.
The intensity of burning the back sample is 51.6MPa, the intensity 10.7MPa after the thermal shock, the intensity 7.1MPa after three thermal shocks, the intensity 4.3MPa after five thermal shocks.Contrast experiment's zirconia material sample only experiences 2 thermal shocks fracture damage just takes place.
The thermal shock test condition is with embodiment 1.
Embodiment 3
Batching is formed: the zirconium white 87.5% of particle diameter≤0.06mm, the metal A l 7% of particle diameter≤0.06mm, the AlN 4% of particle diameter≤0.06mm, the La of particle diameter≤0.01mm
2O
31.5%.
Earlier with metal A l, partially stabilized ZrO
2, synthetic AlN and La in advance
2O
3Prepare burden and dried mixing 1 minute; Add dehydrated alcohol then and make it to form the slurry with flowability, wet method stirred 30 minutes; Slurries filtration after wet method stirred removed behind the ethanol seasoning 2 hours; Adopt pressing machine to carry out the sample moulding, moulding pressure is 100MPa; Sample material adopts nitriding atmosphere to burn till, and firing temperature is 1500 ℃, and soaking time is 3h.
The intensity of burning the back sample is 40.3MPa, the intensity 9.5MPa after the thermal shock, the intensity 6.4MPa after three thermal shocks, the intensity 3.9MPa after five thermal shocks.Contrast experiment's zirconia material sample only experiences 2 thermal shocks fracture damage just takes place.
The thermal shock test condition is with embodiment 1.
Claims (5)
1, a kind of metal A l-AlN is in conjunction with ZrO
2Composite diphase material is characterized in that this composite diphase material weight percent raw materials used and raw material is: metal A l 4-10%; Partially stabilized ZrO
285-92%; AlN 3-6%; Sintering aid SrCO
3, TiO
2Or La
2O
30.5-2%.
2, metal A l-AlN as claimed in claim 1 is in conjunction with ZrO
2Composite diphase material is characterized in that raw materials used particle diameter is: particle diameter＜0.074mm of metal A l; Partially stabilized ZrO
2Particle diameter＜0.074mm; Particle diameter＜0.074mm of AlN; Particle diameter＜the 0.01mm of sintering aid.
3, metal A l-AlN as claimed in claim 1 is in conjunction with ZrO
2Composite diphase material is characterized in that the partially stabilized ZrO in raw materials used
2By monocline ZrO
2With a cube ZrO
2Constitute, the weight percent of the two is: monocline ZrO
210-40%; Cube ZrO
260-90%.
4, metal A l-AlN as claimed in claim 1 is in conjunction with ZrO
2Composite diphase material is characterized in that the forming method of this composite diphase material comprises: hot die-casting molding, injection forming, roll forming or extrusion under vacuum.
5, metal A l-AlN as claimed in claim 1 is in conjunction with ZrO
2Composite diphase material is characterized in that the sintering method of this composite diphase material comprises: hot pressed sintering, high-temperature vacuum sintering or high-temperature ammonolysis sintering; The sintering temperature of different sintering processes all 〉=1500 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100845239A CN100467423C (en) | 2007-02-12 | 2007-02-12 | Al-AlN-ZrO2 thermal shock resistant ceramic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100845239A CN100467423C (en) | 2007-02-12 | 2007-02-12 | Al-AlN-ZrO2 thermal shock resistant ceramic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101058506A CN101058506A (en) | 2007-10-24 |
| CN100467423C true CN100467423C (en) | 2009-03-11 |
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ID=38864831
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|---|---|---|---|
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Families Citing this family (5)
| 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 |
| CN102815957B (en) * | 2012-08-03 | 2014-05-07 | 西安特种设备检验检测院 | Nonferrous metal alloy-toughened aluminum nitride ceramic-based composite material and preparation method thereof |
| CN104193361B (en) * | 2014-08-15 | 2015-08-12 | 郑州大学 | A kind of ZrO 2the preparation technology of-AlN-C embedded ring |
| CN106946567B (en) * | 2017-03-10 | 2019-10-11 | 南通通州湾新材料科技有限公司 | A kind of intermetallic Fe-Al compound and ZrO2The preparation method of composite diphase material mobile phone pottery backboard |
| CN108101535B (en) * | 2018-01-05 | 2020-09-08 | 济南麦哈勃冶金技术开发有限公司 | Zirconia ceramic material for steelmaking continuous casting crystallizer and preparation method thereof |
-
2007
- 2007-02-12 CN CNB2007100845239A patent/CN100467423C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Al2TiO5-ZrO2复相材料中ZrO2的相变特性. 王志发等.耐火材料，第38卷第6期. 2004 |
| Al2TiO5-ZrO2复相材料中ZrO2的相变特性. 王志发等.耐火材料，第38卷第6期. 2004 * |
| 铝－氮化铝结合刚玉质滑板的抗氧化性能. 于之东等.耐火材料，第39卷第2期. 2005 |
| 铝－氮化铝结合刚玉质滑板的抗氧化性能. 于之东等.耐火材料，第39卷第2期. 2005 * |
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Inventor after: Wang Zhifa Inventor after: Wang Ronglin Inventor after: Bo Jinglong Inventor after: Jia Cui Inventor after: Hu Chunfang Inventor after: Zhang Jian Inventor after: Wang Xibei Inventor before: Wang Zhifa Inventor before: Wang Ronglin Inventor before: Bo Jinglong Inventor before: Jia Cui Inventor before: Hu Chunfang Inventor before: Zhang Jian |
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Free format text: CORRECT: INVENTOR; FROM: WANG ZHIFA WANG RONGLIN BU JINGLONG JIA CUI HU CHUNFANG ZHANG JIAN TO: WANG ZHIFA WANG RONGLIN BU JINGLONG JIA CUI HU CHUNFANG ZHANG JIAN WANG XIBEI |
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Granted publication date: 20090311 Termination date: 20120212 |