CN1456532A - Calcium stabilizing zircon alba and electric melting producing method thereof - Google Patents
Calcium stabilizing zircon alba and electric melting producing method thereof Download PDFInfo
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- CN1456532A CN1456532A CN 02139126 CN02139126A CN1456532A CN 1456532 A CN1456532 A CN 1456532A CN 02139126 CN02139126 CN 02139126 CN 02139126 A CN02139126 A CN 02139126A CN 1456532 A CN1456532 A CN 1456532A
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Abstract
A Ca stabilized ZrO2 contains ZrO2 (more than 94%) and CaO (3.5-4.5%). Its electrosmelting preparing process includes such steps as proportionally mixing the monoclinic ZrO2 and calcite or light calcium carbonate, segmental smelting in arc furnace, holding temp for a certain time, cooling in air to 800 deg.C, sudden cooling, crushing, removing iron and ageing. It can be used as the refractory sprue material with high resistance to heat shock and molten steel flushing.
Description
(1) technical field the present invention relates to a kind of refractory materials and production method thereof, particularly relates to a kind of calcium stable zirconium dioxide and electric melting production method thereof.
(2) background technology:, generally contain monoclinic crystal, tetragonal crystal and cubic system because monoclinic zirconium dioxide is the oxide compound that a kind of polycrystalline symbiosis also can transform mutually.Under certain condition, zirconium dioxide is a kind of material that can produce volume change, if contain the zirconium dioxide material, must use stabilized zirconia in the vicissitudinous product of use temperature possibility.CaO is a kind of low-cost stablizer, when CaO at ZrO
2Middle content reaches at 3.5～4.5% o'clock, then ZrO
2Index of stability can reach more than 70%.The production method of current production stabilized zirconia has sintering process and electric smelting method, and its product is at electronics, pottery, chemical industry, be used widely in the industries such as building materials, but if when being used for functional refractory that metallurgical continuous casting uses, its thermostability and resistance to fouling do not reach service requirements.The defective that the stabilized zirconia that former electric smelting method is produced exists is that production method causes.Former electric smelting method is produced stabilized zirconia probably three kinds of methods: first kind is used the pouring-type three-phawse arc furnace, and compound is dropped into melting in the electric arc furnace, and refining is poured in the water cooled mo(u)ld and cools off, and carries out fragmentation then; Second kind of production method is: the molten materials after the refining, blow ball with high-pressure air, and cooling, broken then; The third method is to use fixed three-phawse arc furnace, add partially mixed material after, fusing, shelling cooling is broken after the refining.The common defective that exists of the stabilized zirconia of these three kinds original electric smelting method productions is: the material surface pore is many, and is not fine and close, and the fluctuation of stabilization rate is big, can not satisfy the requirement of metallurgy industry functional refractory.
(3) summary of the invention: the objective of the invention is: the electric melting production method of reforming former stabilized zirconia, improve the stabilized zirconia product quality, make it to reach the requirement of metallurgy industry functional refractory, succeed in developing calcium stable zirconium dioxide and electric melting production method thereof.
Technical scheme of the present invention is: a kind of calcium stable zirconium dioxide, ZrO
2Content 〉=94%, 3.5%≤CaO content≤4.5%, the compactness of this material structure are that in the ken under 2000 times of Electronic Speculum, total void content≤0.03%, its crystalline size can reach the millimeter level, are the transparent xln of yellow or lilac.
A kind of electric melting production method of calcium stable zirconium dioxide,
A, with ZrO
2Content is 〉=98.5% monoclinic zirconium dioxide 91.7～93.5 weight parts, and calcite or light calcium carbonate 6.5～8.3 weight parts mix in the mixing machine of packing into, make furnace charge,
B, furnace charge dropped in the fixed settling process three-phawse arc furnace in batches carry out melting, and progressively promote electrode in the electric arc furnace, the segmentation melting, segmentation insulation homogenizing repeatedly repeats said process, up to meet the demands or full stove till, every section smelting time L, every section soaking time B, both ratios are B/L=0.9～2.2
After c, the last melting of every stove, be incubated 1.6～2.2 hours, furnace shell is sloughed in blowing out, allows the melt air cooling, when temperature is reduced to below 800 ℃, melt supercooled is lowered the temperature rapidly, and again with the melt fragmentation, pick,
D, will be after pick be crossed Material deironing, aging time surpasses 8 hours in the heat treatment furnace of packing into, aging temp is 800～1300 ℃.
Mixing machine can adopt ball mill, put into the zirconium ball made from zirconium dioxide in the machine, zirconium white melt diameter is 1: 0.5～1 with the ratio of height, the height of every section melting adding furnace charge is 240～260mm, aging time was equal to or greater than more than 10 hours, aging temp is 1000～1100 ℃, and chilling is to melt water spray rapid cooling, or with 4～10kg/cm
2The powerful blowing of pressure rapid cooling.
The voltage of melting of heating is 100～180 volts, and electric current is 1500～5000 peaces, and the last insulation of every stove is 2 hours, and melting section electric current is 4000～4500 peaces, and the holding-zone electric current is 2000～2500 peaces.Be crushed to below 8 orders with twin rollers, or press the customer requirements fragmentation, carry out pick, remove material skin and loose material piece, collect the compact block material.
It is as follows that the present invention has useful positively effect:
1, the calcium stable zirconium dioxide refractory that uses production method of the present invention to produce, material structure compactness is good, under 2000 times of Electronic Speculum, in a ken, can't see or only can see a spilehole, all the other all are densest crystals, total void content is no more than 0.03%, because the material pore seldom, density is big, thermal shock resistance improves, so prolong refractory life.
2, the calcium stable zirconium dioxide refractory melt crystallization size of using the present invention to produce reaches the millimeter level, maximum can reach 1.5mm, crystal is big, shown good resistance to fouling, the calcium stable zirconium dioxide refractory that uses the present invention to produce, the metering nozzle that is used for metallurgy industry can make extend to 16 hours by original 10 hours its work-ing life.
3, calcium oxide stablizing in zirconia crystal lattice, show the time effect of heating, in 1000～1200 ℃ cube phases or four directions and temperature range that monocline changes mutually, make the zirconium dioxide lattice perfection of its calcium stable, reduce defective, make the position stability of CaO, be difficult for migration, when meeting temperature variation, CaO can show maximum stability, difficult drop-off, and this time that the present invention explores should be more than 10 hours, after the making sample was with 1100 ℃ of air coolings, its thermostability can be brought up to more than 3 times by original 1 time.
(4) concrete embodiment:
Embodiment one, selects electric smelting monocline ZrO for use
2, its SiO
2Content is equal to or less than 0.5%, and with zirconium dioxide 93.5 weight parts of content 〉=98.5%, calcite 6.5 weight parts are respectively charged in the ball mill, do blending agent with zirconia balls, mix about 60 minutes, obtain furnace charge.
Adopt fixed settling process three-phawse arc furnace, furnace bottom is paved high alumina brick, spread the 400mm furnace charge, suit cylinder furnace shell, pile the starting the arc of a little charcoal piece, 120 volts of voltages, electric current 3500～4000 peaces, reinforced melting progressively promotes electrode, make and generate a cylindric melt of Φ 1000 * h900mm in the stove gradually, after beginning to melt about 50 minutes, be incubated about 75 minutes, electric current is reduced to 2000～2500 peaces, and then reinforced melting, insulation so repeatedly repeats this process, till meeting the demands again, after the last melting, outage natural thermal insulation 2 hours is sloughed furnace shell, cools off in air, when melt temperature drops to below 800 ℃, the water spray chilling, fragmentation, pick, remove melt outermost layered material skin and loose many pores material piece, to be less than or equal 0.3% by void content under 2000 times of Electronic Speculum, crystallization be the good material piece of millimeter level compactness, deironing, be crushed to its requirement granularity by customer requirement, the mullite corundum casket Bowls that packs into goes into the electric kiln timeliness, and temperature is controlled at 1000～1100 ℃, aging time is more than 10 hours, and the kiln discharge cooling packing becomes product.Can obtain calcium oxide content is 3.5%, and zirconia content is 95.5% calcium stable zirconium dioxide.
Embodiment two, select for use zirconium dioxide content that chemical method produces more than or equal to 98.5%, 91.7 weight part, calcite 8.3 weight parts, mix and make furnace charge with embodiment one, make at the bottom of the electric arc furnace, put a round shape furnace shell, the melting of feeding in raw material, 160 volts of voltages, electric current 1500～2000 peaces progressively promote electrode, melting 1 hour, insulation homogenizing 1.5 hours, this process repeatedly, other production process does not repeat with embodiment one, obtain fine and close big crystallization frit, when the electrical kiln timeliness, 1000～1100 ℃ of temperature controls, aging time is more than 15 hours, the kiln discharge cooling, be packaged into product, can obtain calcium oxide content is 4.5%, the calcium stable zirconium dioxide of zirconia content 94.5%.
Embodiment three, select natural monocline zirconium (SiO for use
2Contain 0.7%) 92.6 weight parts, calcite 7.4 weight parts, its production process does not repeat with embodiment one or two.Can obtain calcium oxide content is 4%, and zirconia content is 95% calcium stable zirconium dioxide.
So because the CaO content of light calcium carbonate does not repeat near the relevant embodiment of calcite very much.
Claims (4)
1. a calcium stable zirconium dioxide is characterized in that: ZrO
2Content 〉=94%, 3.5%≤CaO content≤4.5%, the compactness of this material structure are that in the ken under 2000 times of Electronic Speculum, total void content≤0.03%, its crystalline size can reach the millimeter level, are the transparent xln of yellow or lilac.
2. the electric melting production method of a calcium stable zirconium dioxide is characterized in that:
A, with ZrO
2Content is 〉=98.5% monoclinic zirconium dioxide 91.7～93.5 weight parts, and calcite or light calcium carbonate 6.5～8.3 weight parts mix in the mixing machine of packing into, make furnace charge,
B, furnace charge dropped in the fixed settling process three-phawse arc furnace in batches carry out melting, and progressively promote electrode in the electric arc furnace, the segmentation melting, segmentation insulation homogenizing repeatedly repeats said process, up to meet the demands or full stove till, every section smelting time L, every section soaking time B, both ratios are B/L=0.9～2.2
After c, the last melting of every stove, be incubated 1.6～2.2 hours, furnace shell is sloughed in blowing out, allows the melt air cooling, when temperature is reduced to below 800 ℃, melt supercooled is lowered the temperature rapidly, and again with the melt fragmentation, pick,
D, will be after pick be crossed Material deironing, aging time surpasses 8 hours in the heat treatment furnace of packing into, aging temp is 800～1300 ℃.
3. production method according to claim 2, it is characterized in that: mixing machine can adopt ball mill, put into the zirconium ball made from zirconium dioxide in the machine, zirconium white melt diameter is 1: 0.5～1 with the ratio of height, the height of every section melting adding furnace charge is 240～260mm, and aging time was equal to or greater than more than 10 hours, and aging temp is 1000～1100 ℃, chilling is to melt water spray rapid cooling, or with 4～10kg/cm
2The powerful blowing of pressure rapid cooling.
4. according to claim 2 or 3 described production methods, it is characterized in that: the voltage of the melting of heating is 100～180 volts, and electric current is 1500～5000 peaces, and the last insulation of every stove is 2 hours, melting section electric current is 4000～4500 peaces, and the holding-zone electric current is 2000～2500 peaces.Be crushed to below 8 orders with twin rollers, or press the customer requirements fragmentation, carry out pick, remove material skin and loose material piece, collect the compact block material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021391262A CN1181011C (en) | 2002-09-28 | 2002-09-28 | Calcium stabilizing zircon alba and electric melting producing method thereof |
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| CNB021391262A CN1181011C (en) | 2002-09-28 | 2002-09-28 | Calcium stabilizing zircon alba and electric melting producing method thereof |
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| CN1181011C CN1181011C (en) | 2004-12-22 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244842B (en) * | 2008-03-18 | 2010-06-02 | 淄博市周村磊宝耐火材料有限公司 | Electric melting production process for steady zirconium dioxide raw material and technique for producing steady zirconium dioxide product |
| CN101939272B (en) * | 2008-02-07 | 2013-03-20 | 京瓷株式会社 | Zirconia sintered body and manufacturing method thereof |
| CN106242565A (en) * | 2016-07-14 | 2016-12-21 | 广东省材料与加工研究所 | A kind of wear-resisting ZrO2al2o3complex phase ceramic granule and its preparation method and application |
| CN107162590A (en) * | 2017-05-25 | 2017-09-15 | 三祥新材股份有限公司 | A kind of method that electric smelting method produces magnesium stabilised zirconia |
| 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 |
| CN114524673A (en) * | 2021-12-23 | 2022-05-24 | 太仓宏达俊盟新材料有限公司 | Preparation process of high-volume-density zirconia refractory material |
| CN115010484A (en) * | 2022-07-07 | 2022-09-06 | 郑州振中电熔新材料有限公司 | Method for manufacturing fused calcium stabilized zirconia by using waste zirconia nozzle and sliding plate |
-
2002
- 2002-09-28 CN CNB021391262A patent/CN1181011C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101939272B (en) * | 2008-02-07 | 2013-03-20 | 京瓷株式会社 | Zirconia sintered body and manufacturing method thereof |
| CN101244842B (en) * | 2008-03-18 | 2010-06-02 | 淄博市周村磊宝耐火材料有限公司 | Electric melting production process for steady zirconium dioxide raw material and technique for producing steady zirconium dioxide product |
| CN106242565A (en) * | 2016-07-14 | 2016-12-21 | 广东省材料与加工研究所 | A kind of wear-resisting ZrO2al2o3complex phase ceramic granule and its preparation method and application |
| CN106242565B (en) * | 2016-07-14 | 2018-12-21 | 广东省材料与加工研究所 | A kind of wear-resisting ZrO2-Al2O3Complex phase ceramic particle and its preparation method and application |
| CN107162590A (en) * | 2017-05-25 | 2017-09-15 | 三祥新材股份有限公司 | A kind of method that electric smelting method produces magnesium stabilised zirconia |
| 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 |
| CN114524673A (en) * | 2021-12-23 | 2022-05-24 | 太仓宏达俊盟新材料有限公司 | Preparation process of high-volume-density zirconia refractory material |
| CN115010484A (en) * | 2022-07-07 | 2022-09-06 | 郑州振中电熔新材料有限公司 | Method for manufacturing fused calcium stabilized zirconia by using waste zirconia nozzle and sliding plate |
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| Publication number | Publication date |
|---|---|
| CN1181011C (en) | 2004-12-22 |
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Owner name: ZHENGZHOU ZHENZHONG FUSED NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: ZHENGZHOU ZHENZHONG ELECTRIC ZIRCONIUM MELTING INDUSTRY CO., LTD. Effective date: 20140504 |
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Effective date of registration: 20140504 Address after: Xinmi City, Henan province 452384 small Liu Zhaicun Gou Town Hall Patentee after: ZHENGZHOU ZHENZHONG FUSED ZIRCONIA CO.,LTD. Address before: 888 mailbox 452384, Henan City, Xinmi Province Patentee before: Zhengzhou Zhenzhong Fused Zirconia Co.,Ltd. |
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Granted publication date: 20041222 |