CN101244842A - Electric melting production process for steady zirconium dioxide raw material and technique for producing steady zirconium dioxide product - Google Patents

Electric melting production process for steady zirconium dioxide raw material and technique for producing steady zirconium dioxide product Download PDF

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CN101244842A
CN101244842A CNA2008100151769A CN200810015176A CN101244842A CN 101244842 A CN101244842 A CN 101244842A CN A2008100151769 A CNA2008100151769 A CN A2008100151769A CN 200810015176 A CN200810015176 A CN 200810015176A CN 101244842 A CN101244842 A CN 101244842A
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zirconium dioxide
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steady
steady zirconium
dioxide raw
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CN101244842B (en
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王光强
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Shandong Leibao Zirconium Sci&tech Co ltd
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ZIBOCITY ZHOUCUN LEIBAO REFRACTRIES CO Ltd
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Abstract

The invention relates to an electric melting production method for stable zirconium dioxide, which comprises the following steps: adopting ZrO2 with the mass content of more than or equal to 99.95%, high-purity zirconia with the impurity microelements of no more than 10ppm, and high-purity yttria or calcium oxide as stabilizing agent to form furnace charge; melting using an electric arc with high temperature; controlling the electrodes to be not contacted with the liquid surface with the distance of no more than 2cm; naturally cooling after high temperature electric arc melting to form low-carbon white transparent crystal frit; grinding the frit into granular sand; acid washing the granular sand using hydrochloric acid to form the finished sand; evenly mixing the stable zirconium dioxide material and organic bonding agent and forming through high pressure; calcining in a kiln with high temperature to form stable zirconium dioxide products. The zirconium dioxide produced using the method has the advantages of high purity with the ZrO2 plus (CaO) Y2O3 of more than or equal to 99.8%, high melting point of more than or equal to 2700 DEG C, increased normal service temperature of more than or equal to 2400 DEG C, and high cubic phase content of zirconium dioxide of 65 to 95%.

Description

The electric melting production method of steady zirconium dioxide raw material and the production technique of steady zirconium dioxide product
Technical field
The invention belongs to the production method of refractory materials, particularly the production technique of a kind of electric melting production method of steady zirconium dioxide raw material and steady zirconium dioxide product.
Background technology
Along with the develop rapidly of laser technology, the laser particularly application of high power laser light aspect civilian and military more and more is subject to people's attention.The core component of solid statelaser is its operation material, just laser crystals.The critical material of solid statelaser is exactly a laser host material, as ND:YAG and ND:GGG crystal, all is very outstanding laser host material.Usually, laser crystals all is at high temperature to use Czochralski grown, therefore, obtain high-quality laser crystals, and a suitable temperature field must be arranged.So the selection of a temperature material is just very important, a temperature material is directly determining the quality quality of laser crystals.These material require high temperature of growing, high purity, therefore high temperature high purity lagging material is that this crystal of growth is necessary, wherein the zirconium white lagging material is first-selected, and temperature is generally at the 1800-2200 degree, and requires zirconia material purity height, minimizing is to the pollution of crystalline material, need make various heat insulation systems, and have good physical strength, these all are the necessary supporting lagging materials of growing crystal.
Opto-electronic device is the core and the key of information photoelectron technology, and photodiode then is the photoelectric device that is widely used, and under the drive of electronics and information industry, high-brightness LED market was keeping the developing state of steady-state growth in recent years always.
In addition zirconium white and goods thereof have superior physical and chemical performance, are continuous casting of iron and steel water nozzle, laser crystals, found pure quartz glass, refractory metal smelting, high-temperature coatings, far infrared coating, electronics filler.One of Modern High-Tech's structural ceramics, conductivity ceramics, function ceramics, biological ceramics, modern metallurgical main raw of using high-performance refractory material, high-performance high temperature insulating material are one of pillars that supports hi-tech new material industry such as modern high-temperature electric heat equipment, aerospacecraft member, sensor, metallurgical refractory materials, glass refractory materials.And the state of the art of the Materials science in these fields also is one of symbol of national overall technology strength and level.
Therefore, it is significant to the development of China's photoelectric technology and hi tech and new material industry to develop and produce high temperature resistant high-quality zirconium white series refractory materials.
Zirconium white has three kinds of crystal habits: stable low temperature is monocline crystalline phase (M-ZrO mutually 2), cubic crystalline phase (t-ZrO 2), cube crystalline phase (c-ZrO 2).Because ZrO 2Polycrystallinity (monocrystalline, four directions, cubic), zirconium white only occurs mutually with monocline under the normal temperature, is heated to and changes cubic phase about 1100 ℃ into, is heated to higher temperature and can be converted into a cube phase.Owing in the cubic in opposite directions phase phase of monocline co-conversion, can produce bigger volume change, cause the cracking of product easily, limited the application of pure zirconia in the high temperature field.But after the interpolation stablizer, the four directions can be stablized mutually at normal temperatures, has expanded zirconic range of application greatly.Zirconium dioxide (ZrO 2) have a high fire performance (2710 ℃ of high-melting-points), antioxidant property is strong, and thermal conductivity is low, except that overbased materials, majority of gas, acid-basicity material and metal are had good erosion-resisting characteristics, are very ideal high-temperature refractory, abrasive substance and a high temperature insulating material.Add an amount of stablizer and after the electric smelting stabilizing treatment, make stabilized zirconia.Be widely used in continuous casting of iron and steel water nozzle, laser crystals, found pure quartz glass, refractory metal smelting, high-temperature coatings, far infrared coating, electronics filler etc.
Present domestic major technique present situation: 1, low-temperature sintering stable form zirconium white, equilibrium temperature (900-1700 ℃), crystalline phase mainly are that monocline is mutually with mutually cubic; 2, electric smelting stabilizing zirconia; Mainly decompose the desiliconization method and stablize crystalline phase skewness, foreign matter content height, decarburization posterior spiracle rate height (〉=12%) with the zirconium silicate electric smelting.More than two kinds the stabilizing zirconia use temperature is low, foreign matter content is high.Can not satisfy the high temperature non-ferrous metal metallurgy, fused quartz particularly high temperature artificial crystal growth needs.Pollute crystal easily, can not influence the artificial lens development by the growing high quality artificial lens.
Summary of the invention
Technical problem to be solved by this invention provides a kind of production technique of electric melting production method and steady zirconium dioxide product of steady zirconium dioxide raw material, improves the purity of zirconium dioxide, satisfies pyrotic smelting and artificial crystal growth needs.
A kind of electric melting production method of steady zirconium dioxide raw material is formed through the high-temperature electric arc fusing by high-purity zirconia and stablizer, it is characterized in that with ZrO 2Mass content 〉=99.95%, the high-purity zirconia of foreign matter content≤10ppm, Y 2O 3〉=99.99% high purity yttria or calcium oxide are that stablizer forms furnace charge, the high-temperature electric arc melting, control electrode does not contact and leaves liquid level≤2cm with liquation, high-temperature electric arc fusing back naturally cooling forms low-carbon (LC) white transparent crystals shape frit, form granularity sand through fragmentation, form finished sand (being steady zirconium dioxide raw material) through cleanup acid treatment.
Preferably enter according to known technology mode furnace charge in batches and to carry out melting in the three-phawse arc furnace, smelting temperature is 2700~3500 ℃, and electrode voltage is 100~130 volts, and electric current is 200~2000 peaces.
By weight percentage, high-purity zirconia is 92%-86%, and stablizer is 14%-4%.
Low-carbon (LC) white transparent crystals shape frit is by the fragmentation of closed Mechanical Crushing method, to avoid introducing other impurity.Broken granularity determines according to service requirements, general particle diameter can be 5-3mm, 3-2mm, 2-1mm ,≤1mm and≤320 orders.
, in 1900~2400 ℃ high temperature kiln, burn till and to prepare steady zirconium dioxide product after high-pressure molding with the above-mentioned steady zirconium dioxide raw material that obtains and organic bond mixed grind batching.
Organic bond adopts the raw material that the industry such as dextrin, Mierocrystalline cellulose, raw spirit, starch are habitual and be fit to, and these raw materials do not burn till and can remain in the goods through high temperature.
Steady zirconium dioxide raw material and organic bond and water mix, and wherein in mass percent, adding organic bond is 4~9% of steady zirconium dioxide raw material amount, and water is 4~8% of steady zirconium dioxide raw material amount.
In mould, apply pressure high-pressure molding according to required shape of products greater than 200T.
Advantage of the present invention:
1, because the raw material that the production steady zirconium dioxide raw material uses is highly purified zirconium white and stablizer, lays a good foundation for obtaining the high stabilized zirconia of purity.When high melt, electrode does not insert in the melt, has avoided electrode fouling, has avoided the introducing of carbon, so frit need not to heat carbonization treatment among the preparation method, has simplified production technique especially.Be beneficial to the high ZrO of stabilized zirconia purity that the inventive method is produced 2+ (CaO) Y 2O 3〉=99.8%, fusing point height 〉=2700 ℃, normal use temperature improves 〉=2400 ℃.Cube phase content of zirconium dioxide is 65~95%.
2, because the zirconium dioxide purity height that the present invention produces uses, help obtaining pollution-free transparent artificial lens in semiconducter substrate and high power laser light crystal growth single crystal growing furnace, reduce production costs, promote industry development to lay a good foundation.
3, utilize the highly purified steady zirconium dioxide raw material that obtains to produce highly purified steady zirconium dioxide product, satisfy the use of different purposes.
Embodiment
Below in conjunction with embodiment the present invention is described, but does not limit the present invention.
Embodiment 1:
High-purity zirconia (the ZrO that adopts the yellow soda ash chemical reaction method to produce 2〉=99.95% is raw material, foreign matter content≤10ppm), select high purity rare earth oxides Y for use 2O 3(Y 2O 3〉=99.99%) is stablizer, high-purity zirconia 94.8% weight part and high purity yttria 5.2% weight part are respectively charged into homogenizing in the mixing machine, make furnace charge.Furnace charge dropped in batches carry out melting in the three-phawse arc furnace, control electrode promotes the maintenance long arc, and (electrode and liquation spacing distance are in 2cm, but do not contact), melt is progressively reinforced at 2700 ℃, secondary voltage (electrode voltage) is 100 volts, electric current is 1200 peaces, and liquation is incubated 1 hour (insulation electric current 200 peaces) again.And then feed in raw material, heat again, insulation again, repeatedly repeat said process, until obtaining the about 500mm frit of diameter, or can determine size as required.Frit is broken for different granularity sands or powder after conventional method (tramp iron separator) deironing, handles and washing forms stand-by finished sand or powder (being the high purity steady zirconium dioxide raw material) through chlorohydric acid pickling again.With granularity closestpacking principle, with steady zirconium dioxide raw material 100%, add dextrin 6%, water 5% (mass percent) mixed 30 minutes in mixing roll, through 〉=100 tons of high-pressure moldings.Work in-process pass through drying treatment again, burn till in 6 hours with ultrahigh-temperature kiln (1900 ℃) insulation.Check finally obtains qualified product after tested.
High purity zirconium dioxide raw material: ZrO 2+ Y 2O 3=99.9%, cube phase mass content 76%.
High purity zirconium dioxide product: show the empty rate 22% of gas, volume density 4.53g/cm 3, compressive strength 22mp.
Embodiment 2:
According to the method for embodiment 1, wherein high-purity zirconia 92% weight part and high purity yttria 8% weight part are respectively charged into homogenizing in the mixing machine, make furnace charge.In three-phawse arc furnace, melt progressively feeds in raw material at 3000 ℃, and 130 volts of secondary voltages (electrode voltage), electric current are 1400 peaces, are incubated 1 hour, form stand-by finished sand or powder (being the high purity steady zirconium dioxide raw material).
With varigrained steady zirconium dioxide raw material (wherein granularity be 5-1mm the steady zirconium dioxide raw material amount that accounts for 32% ,≤1mm account for 28% ,≤320 purposes account for 40%) 100%, add starch 5%, water 6% and in mixing roll, mixed 30 minutes, through 〉=100 tons of high-pressure moldings.Work in-process pass through drying treatment again, burn till in 6 hours with ultrahigh-temperature kiln (2200 ℃) insulation.Check finally obtains qualified product after tested.
High purity zirconium dioxide raw material: ZrO 2+ Y 2O 3=99.8%, cube phase mass content 80%.
High purity zirconium dioxide product: show the empty rate 23% of gas, volume density 4.4g/cm 3, compressive strength 19mp.
Embodiment 3:
According to the method for embodiment 1, wherein high-purity zirconia 96% weight part and light calcium carbonate 8% (being equivalent to calcium oxide 4%) weight part is respectively charged into homogenizing in the mixing machine, makes furnace charge.In three-phawse arc furnace, melt is progressively feeding in raw material greater than 2700 ℃, and 120 volts of secondary voltages (electrode voltage), electric current are 1000 peaces, are incubated 1 hour, form stand-by finished sand or powder (being the high purity steady zirconium dioxide raw material).
With varigrained steady zirconium dioxide raw material (wherein granularity be 3-1mm the steady zirconium dioxide raw material amount that accounts for 32% ,≤1mm account for 28% ,≤320 purposes account for 40%) 100%, add raw spirit 4%, water 4% and in mixing roll, mixed 30 minutes, through 〉=100 tons of high-pressure moldings.Work in-process pass through drying treatment again, burn till in 6 hours with ultrahigh-temperature kiln (2000 ℃) insulation.Check finally obtains qualified product after tested.
High purity zirconium dioxide raw material: ZrO 2+ CaO=99.85%, cube phase mass content 82%.
High purity zirconium dioxide product: show the empty rate 22% of gas, volume density 4.5g/cm 3, compressive strength 20mp.
Embodiment 4:
According to the method for embodiment 1, wherein high-purity zirconia 95% weight part and light calcium carbonate 8% weight part are respectively charged into homogenizing in the mixing machine, make furnace charge.In three-phawse arc furnace, melt progressively feeds in raw material at 2800 ℃, and 110 volts of secondary voltages (electrode voltage), electric current are 1200 peaces, are incubated 1 hour.
With varigrained steady zirconium dioxide raw material (wherein granularity be 2-1mm the steady zirconium dioxide raw material amount that accounts for 30% ,≤1mm account for 28% ,≤320 purposes account for 42%) 100%, plus fiber element 6%, water 6% mixed 30 minutes in mixing roll, through 〉=100 tons of high-pressure moldings.Work in-process pass through drying treatment again, burn till in 6 hours with ultrahigh-temperature kiln (2100 ℃) insulation.Check finally obtains qualified product after tested.
High purity zirconium dioxide raw material: ZrO 2+ CaO=99.8%, cube phase mass content 80%.
High purity zirconium dioxide product: show the empty rate 21% of gas, volume density 4.5g/cm 3, compressive strength 28mp.
Embodiment 5:
According to the method for embodiment 1, wherein high-purity zirconia 87% weight part and high purity yttria 13% weight part are respectively charged into homogenizing in the mixing machine, make furnace charge.In three-phawse arc furnace, melt progressively feeds in raw material at 2900 ℃, and 120 volts of secondary voltages (electrode voltage), electric current are 1800 peaces, are incubated 1 hour, form stand-by finished sand or powder (being the high purity steady zirconium dioxide raw material).
With varigrained steady zirconium dioxide raw material (wherein granularity be 2-1mm the steady zirconium dioxide raw material amount that accounts for 35% ,≤1mm account for 25% ,≤320 purposes account for 40%) 100%, add starch 6%, water 4% and in mixing roll, mixed 30 minutes, through 〉=100 tons of high-pressure moldings.Work in-process pass through drying treatment again, burn till in 6 hours with ultrahigh-temperature kiln (1900 ℃) insulation.Check finally obtains qualified product after tested.
High purity zirconium dioxide raw material: ZrO 2+ Y 2O 3=99.86%, cube phase mass content 90%.
High purity zirconium dioxide product: show the empty rate 20% of gas, volume density 4.6g/cm 3, compressive strength 27mp.

Claims (6)

1, a kind of electric melting production method of steady zirconium dioxide raw material is formed through the high-temperature electric arc fusing by high-purity zirconia and stablizer, it is characterized in that with ZrO 2Mass content 〉=99.95%, the high-purity zirconia of foreign matter content≤10ppm, Y 2O 3〉=99.99% high purity yttria or calcium oxide are that stablizer forms furnace charge, the high-temperature electric arc melting, control electrode does not contact and leaves liquid level≤2cm with liquation, high-temperature electric arc fusing back naturally cooling forms low-carbon (LC) white transparent crystals shape frit, form granularity sand through fragmentation, obtain steady zirconium dioxide raw material through cleanup acid treatment.
2, the electric melting production method of steady zirconium dioxide raw material according to claim 1, it is characterized in that furnace charge adds in batches carries out melting in the three-phawse arc furnace, and smelting temperature is 2700~3500 ℃, and electrode voltage is 100~130 volts, and electric current is 200~2000 peaces.
3, the electric melting production method of steady zirconium dioxide raw material according to claim 1 is characterized in that by weight percentage, and high-purity zirconia is 86%-96%, and stablizer is 14%-4%.
4, a kind of steady zirconium dioxide raw material that obtains according to the electric melting production method of the described steady zirconium dioxide raw material of claim 1 production technique of producing steady zirconium dioxide product, it is characterized in that steady zirconium dioxide raw material and organic bond mixed grind batching is after high-pressure molding burns till the preparation steady zirconium dioxide product in 1900~2400 ℃ high temperature kiln.
5, the production technique of steady zirconium dioxide product according to claim 4 is characterized in that described organic bond adopts dextrin, Mierocrystalline cellulose, raw spirit or starch.
6, the production technique of steady zirconium dioxide product according to claim 4, it is characterized in that steady zirconium dioxide raw material and organic bond and water mix, wherein in mass percent, adding organic bond is 4~9% of steady zirconium dioxide raw material amount, and adding water is 4~8% of steady zirconium dioxide raw material amount.
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CN102241510A (en) * 2010-05-13 2011-11-16 郑州振中电熔锆业有限公司 Electric melting method for manufacturing yttria stabilized zirconia
CN102653417A (en) * 2012-03-26 2012-09-05 三祥新材股份有限公司 Method for preparing stable-type zirconium dioxide by electric smelting method
CN103936436A (en) * 2014-03-27 2014-07-23 中钢集团洛阳耐火材料研究院有限公司 Yttrium-stabilized zirconia refractory product with gradient functions
CN105905942A (en) * 2014-12-05 2016-08-31 三祥新材股份有限公司 High-purity electric smelting zirconium oxide
CN105948739A (en) * 2016-04-28 2016-09-21 郑州方铭高温陶瓷新材料有限公司 Yttria-zirconia sosoloid ceramics for temperature field of ultrahigh-temperature crystal growing furnace and preparation method for yttria-zirconia sosoloid ceramics
CN106904963A (en) * 2017-03-02 2017-06-30 山东磊宝锆业科技股份有限公司 The production method of continuous casting quartz stove zircite product
CN108046772A (en) * 2017-12-20 2018-05-18 山东磊宝锆业科技股份有限公司 The production method of fused alumina/titanium oxide composite material
CN111635228A (en) * 2017-05-08 2020-09-08 三祥新材股份有限公司 Preparation method of zirconia composite biological ceramic material with high volume density
CN113174636A (en) * 2021-04-27 2021-07-27 三祥新材股份有限公司 Method for producing single crystal electric melting zirconium dioxide

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CN1068860C (en) * 1996-12-04 2001-07-25 金玉琢 Method for prodn. of fused ZrO2 with stable calcium oxide
CN1181011C (en) * 2002-09-28 2004-12-22 郑州振中电熔锆业有限公司 Calcium stabilizing zircon alba and electric melting producing method thereof
US7125536B2 (en) * 2004-02-06 2006-10-24 Millennium Inorganic Chemicals, Inc. Nano-structured particles with high thermal stability
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CN102241510A (en) * 2010-05-13 2011-11-16 郑州振中电熔锆业有限公司 Electric melting method for manufacturing yttria stabilized zirconia
CN102653417A (en) * 2012-03-26 2012-09-05 三祥新材股份有限公司 Method for preparing stable-type zirconium dioxide by electric smelting method
CN103936436A (en) * 2014-03-27 2014-07-23 中钢集团洛阳耐火材料研究院有限公司 Yttrium-stabilized zirconia refractory product with gradient functions
CN103936436B (en) * 2014-03-27 2016-01-20 中钢集团洛阳耐火材料研究院有限公司 A kind of yttrium stable zirconium oxide refractory product of gradient function
CN105905942A (en) * 2014-12-05 2016-08-31 三祥新材股份有限公司 High-purity electric smelting zirconium oxide
CN105948739A (en) * 2016-04-28 2016-09-21 郑州方铭高温陶瓷新材料有限公司 Yttria-zirconia sosoloid ceramics for temperature field of ultrahigh-temperature crystal growing furnace and preparation method for yttria-zirconia sosoloid ceramics
CN105948739B (en) * 2016-04-28 2019-06-21 郑州方铭高温陶瓷新材料有限公司 High-purity yttrium zirconium solid solution ceramics and preparation method thereof for superhigh temperature crystal growing furnace thermal field
CN106904963A (en) * 2017-03-02 2017-06-30 山东磊宝锆业科技股份有限公司 The production method of continuous casting quartz stove zircite product
CN111635228A (en) * 2017-05-08 2020-09-08 三祥新材股份有限公司 Preparation method of zirconia composite biological ceramic material with high volume density
CN108046772A (en) * 2017-12-20 2018-05-18 山东磊宝锆业科技股份有限公司 The production method of fused alumina/titanium oxide composite material
CN113174636A (en) * 2021-04-27 2021-07-27 三祥新材股份有限公司 Method for producing single crystal electric melting zirconium dioxide
CN113174636B (en) * 2021-04-27 2023-11-10 三祥新材股份有限公司 Method for producing monocrystal electric smelting zirconium dioxide

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