CN103936436A - Yttrium-stabilized zirconia refractory product with gradient functions - Google Patents
Yttrium-stabilized zirconia refractory product with gradient functions Download PDFInfo
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- CN103936436A CN103936436A CN201410116753.9A CN201410116753A CN103936436A CN 103936436 A CN103936436 A CN 103936436A CN 201410116753 A CN201410116753 A CN 201410116753A CN 103936436 A CN103936436 A CN 103936436A
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- yttrium oxide
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Abstract
The invention belongs to the field of refractory materials, and provides a yttrium-stabilized zirconia refractory product with gradient functions. According to the provided yttrium-stabilized zirconia refractory product, raw materials comprise fused yttrium-oxide-stabilized zirconia particles, fused yttrium-oxide-stabilized zirconia fine powder, fused yttrium-oxide-stabilized zirconia micro powder, and an additional bonding agent. In fused yttrium-oxide-stabilized zirconia particles, fused yttrium-oxide-stabilized zirconia fine powder and fused yttrium-oxide-stabilized zirconia micro powder, yttrium oxide is taken as a stabilizing agent, and the stabilizing agent yttrium oxide accounts for 13%-20% by mass respectively of the fused zirconia particles, fine powder and micro powder. The raw materials of the yttrium oxide refractory product also comprise yttrium oxide powder, and yttrium oxide powder accounts for 3%-10% by mass of the zirconia refractory product raw materials. The service life of the zirconia product applied to sapphire crystal-growing furnaces is effectively prolonged and sapphire production quality is improved.
Description
Technical field
The invention belongs to fire resisting material field, relate generally to a kind of yttrium stable zirconium oxide refractory product of gradient function.
Background technology
Zirconium white is a kind of important refractory raw material, and fusing point is up to 2715 ℃, and physicochemical property is excellent.High-purity zirconia refractory product typically refers to zirconium white (comprising stablizer) content at more than 98% refractory product; it take zirconia particles or Bubble zirconia, powdered zirconium oxide, stablizer, bonding agent etc. is raw material, by founding, cast, machine press, etc. the moulding means such as static pressure, ramming prepare the refractory product of desired shape.High-purity zirconia refractory materials has difficult decomposition, good chemical stability under use temperature high (2300～2400 ℃ of maximum operation (service) temperatures), high temperature, is a kind of high-performance refractory goods.High-purity zirconia refractory product is divided into Bubble zirconia goods and heavy zirconia goods.Particulate material (the aggregate that Bubble zirconia goods are used, granularity is greater than 0.1mm) essential substance is Bubble zirconia, such Bubble zirconia is to make by the high-pressure air zirconium white liquation of jetting, Bubble zirconia goods are owing to having higher void content (>=50%), thereby there is lower thermal conductivity, be mainly used in 1800 ℃ of above heat insulatings.Particulate material (the aggregate that heavy zirconia goods are used, granularity is greater than 0.1mm) essential substance is zirconium white electric smelting particle (non-hollow ball), such zirconium white electric smelting particle is to make by the cooling rear fragmentation of electric-melting zirconia liquation, heavy zirconia goods have high, the resistance to erosion of structural strength, antiscour, use temperature higher (generally compared with high approximately 200 ℃ of Bubble zirconia goods safe handling temperature), be mainly used in 1800 ℃ of above pyroreaction linings and 2000 ℃ of above heat insulatings, as the growth of the sintering of tungsten goods, sapphire crystal etc.
Colourless sapphire (α-Al
2o
3) belonging to hexagonal system, maximum operating temperature can reach 1900 ℃.With its special physicochemical property, price advantage and crystalline size, become at present the crystalline inorganic oxide material of consumption maximum in photoelectron and microelectronic industry, especially in the solid light source revolution in this century, greatly developing of the GaN base blue green light LED industry that the sapphire of take is substrate, is constantly promoting the research to sapphire growth technology and crystal mass.In addition, because sapphire crystal is easy to obtain large size single crystal, and its thermal noise is only 1.9 times of silica glass, and pattern factor Q is than high two orders of magnitude of silica glass, therefore using sapphire crystal, as interferometer optics medium, will greatly improve optical sensitivity.High optical quality and large size sapphire crystal growing technology remain one of Hot Contents of industrial community exploration and research.
Kyropoulos is one of maturation method that can obtain at present high-quality sapphire macrocrystal.Principle and the technical characterstic of its crystal growth are: crystal raw material is put into resistant to elevated temperatures tungsten and molybdenum crucible heat fused, adjust temperature field in furnace, make the state of melt top in a little higher than fusing point; Make seed crystal on seed rod contact melting liquid level, after its surface is slightly molten, reduce surface temperature to fusing point, lift and rotate seed rod, make melt top in supercooled state and crystallization on seed crystal, in the process constantly lifting, grow cylinder crystal.Adopt kyropoulos can grow major diameter, high quality, colourless sapphire crystal.
The long brilliant stove of sapphire is the device of whole crystal growth, miramint crucible setting is in body of heater central authorities, crucible external application miramint carries out resistive heating as Heating element, the peripheral zirconia refractory that adopts of tungsten Heating element is as insulating lining, stop scattering and disappearing of heat, zirconia refractory is outside equipped with metal heat preservation screen and water cooling system.Whole said apparatus is placed in an outer cover, to be filled with rare gas element after vacuumizing, keeps the gas and the pressure that in growing environment, need.
Zirconia refractory is the insulating lining material that the long brilliant stove of sapphire generally adopts in recent years, its chemical purity is high, zirconium white and stablizer be greater than 99%(mass percent with amount), use temperature can reach more than 2400 ℃, in order to take into account its heat retaining property and intensity, general apparent porosity, 20% ~ 30%, is to be the heavy zircite product that raw material is prepared into by electric-melting zirconia particle and fine powder, has uniform heterogeneous microstructure.
The long brilliant stove heavy zircite product of sapphire, zirconium white raw material used (comprising particle, fine powder, micro mist) is electric smelting stable calcium oxide zirconium white, electrically molten magnesia stabilizing zirconia, electrically melt yttrium oxide stabilized zirconia etc., as the calcium oxide of stablizer, magnesium oxide, yttrium oxide etc. all solid solution in electric smelting stabilizing zirconia raw material, but not Individual existence.According to the difference of manufacture craft and service requirements, these electric-melting zirconia raw materials can be semistable can be also complete stable, as the mass percent of calcium oxide in electric smelting stable calcium oxide zirconium white raw material is generally 3% ~ 8%, in electrically molten magnesia stabilizing zirconia raw material, magnesian massfraction is generally 4% ~ 20%, and in electrically melt yttrium oxide stabilized zirconia raw material, the massfraction of yttrium oxide is generally 5% ~ 13%.Yttrium oxide (Y
2o
3) be a kind of common rare earth oxide, stable chemical nature, fusing point is up to 2410 ℃, and yttrium oxide is the best stablizer of zirconia refractory product, has advantages of not precipitation of long-time applied at elevated temperature, can be made into ZrO
2-Y
2o
3sosoloid, its fusing point reaches more than 2400 ℃; When the add-on of yttrium oxide be zirconia refractory product raw material total amount 8% time, zirconia refractory product can reach stable substantially; When the add-on of yttrium oxide be zirconia refractory product raw material total amount 13% time, zirconia refractory product reaches full steady state.
The long brilliant stove of sapphire with heavy zircite product be by the above-mentioned electric-melting zirconia particle that contains stablizer, fine powder, micro mist by interpolation bonding agent, be pressed into that base substrate forms through high-temperature firing.This class zircite product purity is high, and zirconium white (comprising stablizer) content is more than 98.5%, and stablizer is stable existence in the particle of zirconium white raw material and fine powder, is difficult for precipitation, precipitation hardly when particularly yttrium oxide is stablizer; And this class zirconium white chemical stability is good, even also do not react with the fugitive constituent (as aluminum oxide, tungsten, molybdenum etc.) in long brilliant stove under high temperature; This based article on the make, fired after and in applied at elevated temperature, there is comparatively weave construction uniformly, the performances such as the apparent porosity that macro manifestations is material, volume density, thermal expansivity are even, irrelevant with the variation of sampling point.
Generally, the long brilliant stove furnace lining zirconium white refractory brick of sapphire is that the zircite product by polylith arcuate structure surrounds cylindric, cylinder inner surface is near tungsten Heating element, brick surface temperature higher (approximately 2000 ~ 2200 ℃), cylinder outer surface is near water cooling system, brick surface temperature lower (approximately 1500 ~ 1800 ℃), that is: there is thermograde in using in zirconia refractory product, product surface is near a surface temperature high (hot side) at body of heater center, away from a surface temperature lower (huyashi-chuuka (cold chinese-style noodles)) at body of heater center.
As the long brilliant stove of jewel zirconium white product used, be uniform texture at present, there is consistent thermal conductivity and thermal expansivity.And this class zirconium white product purity is high, in the use procedure of sapphire production technique, temperature is insensitive on the impact of material microstructure.In use there is larger thermograde on same brick in this class zirconium white product, brick body heat face and huyashi-chuuka (cold chinese-style noodles) temperature differ hundreds of degree.The swell increment of material and temperature, thermal expansivity are directly proportional, when thermal expansivity one regularly, larger for the higher swell increment of zirconia material temperature, on the contrary shrinkage is also larger during cooling contraction.This phenomenon causes the long brilliant stove of sapphire very serious with zirconia brick damage, and the main situation of damage is that brick hot side position produces serious cracking, causes structure deteriorate, forms brick body and peels off, falls piece.Think, in use procedure, cold and hot surface thermograde is larger, and the inequality of temperature causes the inequality of swell increment, and causing whole brick volumetric expansion and shrinkage rates inequality is the major cause that causes whole brick structure to destroy.
In addition, in the long brilliant stove of sapphire, aluminum oxide becomes liquid state and gaseous state, and gaseous oxidation aluminium can be to concentration lower region diffusion in burner hearth.In order to reach good heat insulation effect, the long brilliant stove of sapphire is higher with the void content of zirconia refractory conventionally, and whole zirconia material structure is comparatively loose.The short texture of brick body heat face position very easily causes adhering to and infiltrating of aluminum oxide steam and tungsten metallic vapor.The own fusing point of aluminum oxide higher (2050 ℃), aluminum oxide steam infiltrates zircite product top layer, and depths can condensation, causes aluminum oxide at enrichment, the skinning on zircite product hot side top layer.The volatile matter of tungsten metallic vapor does not react with zirconium white yet, but its steam forces down, and is easy to infiltrate to zircite product is inner.Along with the growth of working time, aluminum oxide steam and tungsten steam, in the fouling of zircite product hot junction, due to the adaptation of dilation, cause brick surface layer to peel off.Peel off rear new top layer, hot junction and still there is comparatively loose structure, again cause fouling, then peel off.So, zircite product is corroded gradually, damage
Seriously.
Summary of the invention
The object of the invention is to propose a kind of yttrium stable zirconium oxide refractory product of gradient function, the phenomenon of can stop appearance be full of cracks in zirconia refractory product use, peeling off, meet hot face bit architecture relatively fine and close simultaneously, can effectively prevent a large amount of infiltrations of aluminum oxide steam and tungsten metallic vapor, huyashi-chuuka (cold chinese-style noodles) portion structure is relatively loose, can reach good heat-insulating property, effectively improve the work-ing life that the long brilliant stove of jewel is used zircite product.
The present invention adopts following technical scheme for completing above-mentioned purpose:
A yttrium stable zirconium oxide refractory product for gradient function, as the zirconia refractory product of the long brilliant furnace lining material of sapphire, ZrO in goods
2content>=98wt%, described ZrO
2content comprise stablizer; The raw material of described zirconia refractory product includes electrically melt yttrium oxide stabilized zirconia particle, electrically melt yttrium oxide stabilized zirconia fine powder, electrically melt yttrium oxide stabilized zirconia micro mist; In described electrically melt yttrium oxide stabilized zirconia particle, electrically melt yttrium oxide stabilized zirconia fine powder and electrically melt yttrium oxide stabilized zirconia micro mist, yttrium oxide is as stablizer, in described electrically melt yttrium oxide stabilized zirconia particle, electrically melt yttrium oxide stabilized zirconia fine powder and electrically melt yttrium oxide stabilized zirconia micro mist, as the massfraction of the yttrium oxide of stablizer, be 13% ~ 20%; The raw material of described zirconia refractory product also includes the yttrium oxide powder adding separately, and the mass percent of yttrium oxide powder in zirconia refractory product raw material is 3% ~ 10%; The raw material gross weight sum of described zirconia refractory product is 100%, and has bonding agent; Yttrium oxide powder and excessive stabilized with yttrium oxide agent and jewel are grown the raw material A l in brilliant stove
2o
3the resulting resultant melting degree under differing temps that reacts is different, makes zirconia refractory product have specific non-homogeneous interior microscopic weave construction, and from working face to non-working surface, the apparent porosity of these goods and volume density are linear gradient and change.
Prior art is using the only use of the stablizer in the raw material of making zircite product of yttrium oxide, the massfraction of yttrium oxide in zirconium white raw material is common can meet application below 13%, and uses in characteristics such as more than 2400 ℃ high thermal resistance, chemical stabilities outstanding.Yet for the long brilliant stove of jewel, it has life-time service temperature and maintains 2050 ℃ of left and right, has the features such as a large amount of aluminum oxide steam disperse in stove.The present invention utilizes zirconia refractory in the long brilliant stove of jewel to have thermograde and hot end surface aluminum oxide vapour concentration high in using, break traditions using yttrium oxide only as the fixedly thinking of zirconia material stablizer, the electric smelting of excessive oxidation yttrium stabiliser content of take in the production of zirconium white product is stablized raw material as main raw material, in feed composition, add again yttrium oxide simultaneously, cause in this zirconium white product yttrium oxide excessive, thereby make excessive yttrium oxide in the long brilliant process of jewel with make sapphire raw alumina steam reaction, in the zirconium white product different zones with thermograde, generate corresponding yttrium aluminum compound, form Functionally Graded Materials, improve the long brilliant stove of jewel and use the work-ing life of zirconia material.
Sapphire composition is aluminum oxide, and the long brilliant stove working temperature long term maintenance of jewel is 2050 ℃ of left and right.Zirconia refractory, as furnace lining, does not directly contact with aluminum oxide liquation, but at the aluminum oxide steam of the hot junction of zirconia refractory long-term existence higher concentration.In zirconia refractory, add excessive yttrium oxide, the Al in applied at elevated temperature in the long brilliant stove of yttrium oxide and sapphire
2o
3at high temperature can form multiple compounds, according to Y
2o
3and Al
2o
3the difference of mol ratio, can generate Y
3al
5o
12, YAlO
3, Y
4al
2o
9etc. multiple yttrium aluminum compound, the fusing point of these compounds is all at 1900 ℃ ~ 2000 ℃.The yttrium aluminum compound of melting forms a small amount of liquid phase, has greatly promoted the sintering of zirconia material, can make the density of material increase, the volumetric shrinkage of material; Zircite product is used the initial stage, aluminum oxide steam infiltrates from zircite product hot side, along with the progressively reduction of hot side to huyashi-chuuka (cold chinese-style noodles) temperature, aluminum oxide reacts the yttrium aluminum compound concentration of generation also along with reduction with yttrium oxide, near hot junction zircite product compact structure, and close cold junction zircite product structure is unchanged, still comparatively loose, from hot junction to cold junction, formed the new shape of the structure gradient with alumina concentration gradient and the formation of material density difference.This zirconia refractory with microtexture gradient, the bulk parameters such as its apparent porosity, volume density, thermal expansivity, thermal conductivity also can show because of the change of microtexture certain graded.
Add the zirconia refractory with gradient function of excessive oxidation yttrium, in the long brilliant stove of jewel, use, first, new impurity is not introduced in the interpolation of yttrium oxide, can not pollute sapphire goods; Secondly, the use temperature of this refractory materials does not significantly reduce, and can meet the service requirements of the long brilliant stove of jewel; Again, this zirconia refractory has gradient function, can offset the dilation mismatch that exists thermograde to cause due to same brick different sites in use procedure, reduces the generation that the damage situations such as piece were chapped, peeled off, fall on top layer; Finally, this zirconia material hot side is fine and close, is conducive to prevent the infiltration of tungsten metal gas, and huyashi-chuuka (cold chinese-style noodles) is loose, is conducive to heat-insulation and heat-preservation.
Following table has provided currently available products and in the long brilliant stove of jewel, has used the performance perameter after 3 months to contrast with product of the present invention:
As can be seen from the table, it is high that the present invention has use temperature, chemical purity is high, from working face (hot junction) to non-working surface (cold junction), the void content of material, volume density there is the features such as graded, furnace lining material as the long brilliant stove of jewel is used, reduced in zirconia refractory product use and occurred be full of cracks, surface scale, the phenomenon of peeling off, meet hot face bit architecture relatively fine and close simultaneously, a large amount of infiltrations of aluminum oxide steam and tungsten metallic vapor have been prevented, huyashi-chuuka (cold chinese-style noodles) portion structure is relatively loose, the heat-insulating property having reached better, in use, whole furnace lining heat distribution is even.
The apparent porosity of described yttrium stable zirconium oxide refractory product is 18% ~ 30%; Higher apparent porosity is conducive to aluminum oxide steam to the infiltration in zirconium white matrix; But void content is too high, affect the intensity of material, simultaneously too high void content causes the short texture of material own, and yttrium aluminum garnet shrinks excessive while causing the double sintering of material after generating.
Described yttrium oxide powder, its purity Y
2o
3>=99.0%, its granularity is less than or equal to 0.076mm for being more than or equal to 0.005mm; As high-purity zirconia goods, require the yttrium oxide adding to there is higher degree, in order to avoid cause the reduction of whole zircite product purity and the decline of performance; Simultaneously, to yttrium oxide Powder Particle Size, should be strict with, yttrium oxide Powder Particle Size is too slightly not easy to the sintering of zircite product, is more unfavorable for and the reacting of aluminum oxide steam, yttrium oxide Powder Particle Size too detailed rules and regulations is easily solidly soluted in zirconium white raw material, is difficult for reacting of precipitation and aluminum oxide steam.
In the present invention, yttrium oxide is usingd two kinds of kenels and is existed: 1. in the preparation process of electrically melt yttrium oxide stabilized zirconia particle, electrically melt yttrium oxide stabilized zirconia fine powder and electrically melt yttrium oxide stabilized zirconia micro mist, yttrium oxide adds as stablizer, its add-on when making preparation zirconium white raw materials quality 13% ~ 20%, in these raw materials, the mass concentration of yttrium oxide is 13% ~ 20%; 2. in zirconia refractory product preparation process, yttrium oxide powder adds as independent a kind of solid material, and the addition of yttrium oxide powder is 3% ~ 10% of zirconia refractory product raw material total amount.
The long brilliant stove of described sapphire is by melting Al
2o
3, control its melting-crystallization and realize monocrystalline Al
2o
3the device of producing, adopts tungsten resistive heating, and in stove, working temperature is 2050 ℃.
The yttrium stable zirconium oxide refractory product of described a kind of gradient function, by following technique, realize: first by electrically melt yttrium oxide stabilized zirconia particle, electrically melt yttrium oxide stabilized zirconia fine powder, electrically melt yttrium oxide stabilized zirconia micro mist, yttrium oxide powder, mixed with bonding agent, compression moulding is zirconium white base substrate; After body drying, under 1600 ℃ ~ 1850 ℃ atmospheric pressure oxidation atmosphere, burn till; Zircite product after burning till is piled up in heat treatment furnace along burner hearth center, make to be formed centrally in burner hearth cavity, in cavity, miramint is heating source heating, heat is to zirconia brick radiation, the interior heated oxide aluminium of while cavity makes it to form steam and infiltrates to zirconia brick, controlling zircite product internal surface temperature is 1950 ℃ ~ 2100 ℃, and continuous heating 10h ~ 20h obtains the zirconia refractory product of gradient function after Slow cooling; Or the zircite product after burning till under 1600 ℃ ~ 1850 ℃ atmospheric pressure oxidation atmosphere is built by laying bricks or stones in the long brilliant stove of sapphire and is used as furnace lining material, the long brilliant stove of heating sapphire is to 2100 ℃ ~ 2200 ℃ of technological temperatures, make aluminum oxide fusion and gasification in stove infiltrate zircite product, continue insulation 10h ~ 20h, after Slow cooling, also can form the zirconia refractory product with gradient function.
Described electrically melt yttrium oxide stabilized zirconia particle refers to that grain graininess scope is for being greater than 0.15 mm, be less than or equal to the particle of 3 mm, wherein granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the zirconia particles material that 0.15 mm is less than or equal to 0.5 mm and is respectively 20% ~ 40%, 20% ~ 30%, 10% ~ 20% of zirconia refractory product raw material total amount; The size range of described electrically melt yttrium oxide stabilized zirconia fine powder is less than or equal to 150 μ m for being greater than 30 μ m, is 10% ~ 20% of zirconia refractory product raw material total amount; Described electrically melt yttrium oxide stabilized zirconia micro mist, size range is that meso-position radius D50 is greater than 0.5 μ m and is less than or equal to 30 μ m, addition is 10% ~ 20% of zirconia refractory product raw material total amount.
The add-on of described bonding agent is 3% ~ 5% of zirconia refractory product raw material gross weight.
Described bonding agent is the combination of one or both any mass ratios in resol, polyvinyl alcohol water solution, epoxy resin, furane resin, water-base resin.
The yttrium stable zirconium oxide refractory product of a kind of gradient function that the present invention proposes, utilize high temperature and thermograde characteristic in long brilliant stove self use procedure of sapphire, utilize the diffusion property of aluminum oxide steam in sapphire growth process simultaneously, by adding in yttrium oxide powder and electric smelting yttrium stable zirconium oxide raw material, add excessive oxidation yttrium stablizer in yttrium stable zirconium oxide refractory product preparation process, reach the effect that zirconia refractory has gradient function, effectively improved the long brilliant stove of jewel with having improved sapphire production quality the work-ing life of zircite product.
Embodiment
Embodiment 1:
Zirconium white proportioning raw materials is as follows: granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the mass percent that stabilizing zirconia particle that 0.15 mm is less than or equal to 0.5 mm accounts for raw material and is respectively 20%, 20%, 20%; It is 20% that granularity is greater than the mass percent that stabilizing zirconia fine powder that 30 μ m are less than or equal to 150 μ m accounts for raw material; It is 10% that meso-position radius D50 is greater than the mass percent that yttria-stabilized zirconia micro mist that 0.5 μ m is less than or equal to 30 μ m accounts for raw material; Above stabilizing zirconia is stablizer Y
2o
3massfraction is 13% electrically melt yttrium oxide stabilized zirconia.Purity Y
2o
3>=99.0%, it is 10% that granularity is more than or equal to the mass percent that yttrium oxide powder that 0.005mm is less than or equal to 0.076mm accounts for raw material; Bonding agent is resol, and add-on is 3% of raw material total mass; Above-mentioned raw materials, bonding agent are mixed, and compression moulding is zirconium white base substrate; After body drying, under 1850 ℃ of atmospheric pressure oxidation atmosphere, burn till; Zircite product after burning till is built by laying bricks or stones in vacuum heat treatment furnace, in be formed centrally cavity, in cavity, miramint is heating source heating, heat is to zirconia brick radiation, the interior heated oxide aluminium of while cavity makes it to form steam and infiltrates to zirconia brick, controlling zirconia brick internal surface temperature is 2100 ℃, the cooling zirconia refractory product that obtains gradient function after insulation 10h.This zirconia refractory product is used as the long brilliant furnace lining material of sapphire; Through this zirconium white internal skin of XRD analysis, contain Y
2o
3and Al
2o
3the yttrium aluminum garnet forming; This zirconia refractory product ZrO
2+ Y
2o
3content=99.5wt%, there is Gradient distribution from hot side to huyashi-chuuka (cold chinese-style noodles) in internal microstructure, hot side place apparent porosity 18%, huyashi-chuuka (cold chinese-style noodles) place apparent porosity 24%.
Embodiment 2:
Zirconium white proportioning raw materials is as follows: granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the mass percent that stabilizing zirconia particle that 0.15 mm is less than or equal to 0.5 mm accounts for raw material and is respectively 20%, 20%, 20%; It is 20% that granularity is greater than the mass percent that stabilizing zirconia fine powder that 30 μ m are less than or equal to 150 μ m accounts for raw material; It is 15% that meso-position radius D50 is greater than the mass percent that yttria-stabilized zirconia micro mist that 0.5 μ m is less than or equal to 30 μ m accounts for raw material; Above stabilizing zirconia is stablizer Y
2o
3massfraction is 20% electrically melt yttrium oxide stabilized zirconia; Purity Y
2o
3>=99.0%, it is 5% that granularity is more than or equal to the mass percent that yttrium oxide powder that 0.005mm is less than or equal to 0.076mm accounts for raw material; Bonding agent is resol, and add-on is 3% of raw material total mass; Above-mentioned raw materials, bonding agent are mixed, and compression moulding is zirconium white base substrate; After body drying, under 1850 ℃ of atmospheric pressure oxidation atmosphere, burn till; Zirconia brick after burning till is directly built by laying bricks or stones in the long brilliant stove of sapphire and is used as furnace lining material, in the tungsten crucible of body of heater center, fill high purity aluminium oxide powder raw material, adopting miramint is heating source heating tungsten crucible, makes aluminum oxide fusion and gasification, and controlling technological temperature is 2100 ℃; Continue insulation 20h, after Slow cooling, obtain the zirconia refractory product of gradient function.This zirconia refractory product can be used as the long brilliant furnace lining material of sapphire and continues life-time service; Through this zirconium white internal skin of XRD analysis, contain Y
2o
3and Al
2o
3the yttrium aluminum garnet forming; This zirconia refractory product ZrO
2+ Y
2o
3content=99.5wt%, there is Gradient distribution from hot side to huyashi-chuuka (cold chinese-style noodles) in internal microstructure, hot side place apparent porosity 18%, huyashi-chuuka (cold chinese-style noodles) place apparent porosity 24%.
Embodiment 3:
Zirconium white proportioning raw materials is as follows: granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the mass percent that stabilizing zirconia particle that 0.15 mm is less than or equal to 0.5 mm accounts for raw material and is respectively 40%, 20%, 10%; It is 10% that granularity is greater than the mass percent that stabilizing zirconia fine powder that 30 μ m are less than or equal to 150 μ m accounts for raw material; It is 17% that meso-position radius D50 is greater than the mass percent that yttria-stabilized zirconia micro mist that 0.5 μ m is less than or equal to 30 μ m accounts for raw material; Above stabilizing zirconia is stablizer Y
2o
3massfraction is 20% electrically melt yttrium oxide stabilized zirconia; Purity Y
2o
3>=99.0%, it is 3% that granularity is more than or equal to the mass percent that yttrium oxide powder that 0.005mm is less than or equal to 0.076mm accounts for raw material; Bonding agent is water-base resin, and add-on is 5% of raw material total mass; Above-mentioned raw materials, bonding agent are mixed, and compression moulding is zirconium white base substrate; After body drying, under 1600 ℃ of atmospheric pressure oxidation atmosphere, burn till; Zircite product after burning till is built by laying bricks or stones in vacuum heat treatment furnace, in be formed centrally cavity, in cavity, miramint is heating source heating, heat is to zirconia brick radiation, the interior heated oxide aluminium of while cavity makes it to form steam and infiltrates to zirconia brick, controlling zirconia brick internal surface temperature is 1950 ℃, is incubated and after 20 hours, obtains the zirconia refractory product of gradient function.This zirconia refractory product is used as the long brilliant furnace lining material of sapphire; Through this zirconium white internal skin of XRD analysis, contain Y
2o
3and Al
2o
3the yttrium aluminum garnet forming; This zirconia refractory product ZrO
2+ Y
2o
3content=99.5wt%, there is Gradient distribution from hot side to huyashi-chuuka (cold chinese-style noodles) in internal microstructure, hot side place apparent porosity 20%, huyashi-chuuka (cold chinese-style noodles) place apparent porosity 25%.
Embodiment 4:
Zirconium white proportioning raw materials is as follows: granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the mass percent that stabilizing zirconia particle that 0.15 mm is less than or equal to 0.5 mm accounts for raw material and is respectively 30%, 30%, 10%; It is 10% that granularity is greater than the mass percent that stabilizing zirconia fine powder that 30 μ m are less than or equal to 150 μ m accounts for raw material; It is 10% that meso-position radius D50 is greater than the mass percent that yttria-stabilized zirconia micro mist that 0.5 μ m is less than or equal to 30 μ m accounts for raw material; Above stabilizing zirconia is stablizer Y
2o
3massfraction is 15% electrically melt yttrium oxide stabilized zirconia.Purity Y
2o
3>=99.0%, it is 10% that granularity is more than or equal to the mass percent that yttrium oxide powder that 0.005mm is less than or equal to 0.076mm accounts for raw material; Bonding agent is polyvinyl alcohol water solution, and add-on is 4% of raw material total mass; Above-mentioned raw materials, bonding agent are mixed, and compression moulding is zirconium white base substrate; After body drying, under 1750 ℃ of atmospheric pressure oxidation atmosphere, burn till; Zircite product after burning till is built by laying bricks or stones in vacuum heat treatment furnace, in be formed centrally cavity, in cavity, miramint is heating source heating, heat is to zirconia brick radiation, the interior heated oxide aluminium of while cavity makes it to form steam and infiltrates to zirconia brick, controlling zirconia brick internal surface temperature is 2050 ℃, is incubated 20 hours, obtains the zirconia refractory product of gradient function.This zirconia refractory product is used as the long brilliant furnace lining material of sapphire; Through this zirconium white internal skin of XRD analysis, contain Y
2o
3and Al
2o
3the Y forming
3al
5o
12, YAlO
3; This zirconia refractory product ZrO
2+ Y
2o
3content=99.5wt%, there is Gradient distribution from hot side to huyashi-chuuka (cold chinese-style noodles) in internal microstructure, hot side place apparent porosity 22%, huyashi-chuuka (cold chinese-style noodles) place apparent porosity 27%.
Embodiment 5:
Zirconium white proportioning raw materials is as follows: granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the mass percent that stabilizing zirconia particle that 0.15 mm is less than or equal to 0.5 mm accounts for raw material and is respectively 30%, 30%, 10%; It is 10% that granularity is greater than the mass percent that stabilizing zirconia fine powder that 30 μ m are less than or equal to 150 μ m accounts for raw material; It is 17% that meso-position radius D50 is greater than the mass percent that yttria-stabilized zirconia micro mist that 0.5 μ m is less than or equal to 30 μ m accounts for raw material; Above stabilizing zirconia is stablizer Y
2o
3massfraction is 18% electrically melt yttrium oxide stabilized zirconia.Purity Y
2o
3>=99.0%, it is 3% that granularity is more than or equal to the mass percent that yttrium oxide powder that 0.005mm is less than or equal to 0.076mm accounts for raw material; Bonding agent is epoxy resin, and add-on is 5% of raw material total mass; Above-mentioned raw materials, bonding agent are mixed, and compression moulding is zirconium white base substrate; After body drying, under 1750 ℃ of atmospheric pressure oxidation atmosphere, burn till; Zirconia brick after burning till is directly built by laying bricks or stones in the long crystalline substance of jewel and is used as furnace lining material, in the tungsten crucible of body of heater center, fill high purity aluminium oxide powder raw material, adopting miramint is heating source heating tungsten crucible, makes aluminum oxide fusion and gasification, and controlling technological temperature is 2100 ℃; Continue insulation 15h, after Slow cooling, obtain the zirconia refractory product of gradient function.This zirconia refractory product can be used as the long brilliant furnace lining material of sapphire and continues life-time service; Through this zirconium white internal skin of XRD analysis, contain Y
2o
3and Al
2o
3the YAlO forming
3, Y
4al
2o
9; This zirconia refractory product ZrO
2+ Y
2o
3content=99.0wt%, there is Gradient distribution from hot side to huyashi-chuuka (cold chinese-style noodles) in internal microstructure, hot side place apparent porosity 25%, huyashi-chuuka (cold chinese-style noodles) place apparent porosity 30%.
Embodiment 6:
Zirconium white proportioning raw materials is as follows: granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the mass percent that stabilizing zirconia particle that 0.15 mm is less than or equal to 0.5 mm accounts for raw material and is respectively 30%, 25%, 15%; It is 13% that granularity is greater than the mass percent that stabilizing zirconia fine powder that 30 μ m are less than or equal to 150 μ m accounts for raw material; It is 10% that meso-position radius D50 is greater than the mass percent that yttria-stabilized zirconia micro mist that 0.5 μ m is less than or equal to 30 μ m accounts for raw material; Above stabilizing zirconia is stablizer Y
2o
3massfraction is 18% electrically melt yttrium oxide stabilized zirconia.Purity Y
2o
3>=99.0%, it is 7% that granularity is more than or equal to the mass percent that yttrium oxide powder that 0.005mm is less than or equal to 0.076mm accounts for raw material; Bonding agent is furane resin, and add-on is 3.5% of raw material total mass; Above-mentioned raw materials, bonding agent are mixed, and compression moulding is zirconium white base substrate; After body drying, under 1600 ℃ of atmospheric pressure oxidation atmosphere, burn till; Zircite product after burning till is built by laying bricks or stones in vacuum heat treatment furnace, in be formed centrally cavity, in cavity, miramint is heating source heating, heat is to zirconia brick radiation, the interior heated oxide aluminium of while cavity makes it to form steam and infiltrates to zirconia brick, controlling zirconia brick internal surface temperature is 2050 ℃, is incubated 10 hours, obtains the zirconia refractory product of gradient function.This zirconia refractory product is used as the long brilliant furnace lining material of sapphire; Through this zirconium white internal skin of XRD analysis, contain Y
2o
3and Al
2o
3the Y forming
3al
5o
12, YAlO
3; This zirconia refractory product ZrO
2+ Y
2o
3content=99.5wt%, there is Gradient distribution from hot side to huyashi-chuuka (cold chinese-style noodles) in internal microstructure, hot side place apparent porosity 25%, huyashi-chuuka (cold chinese-style noodles) place apparent porosity 29%.
Embodiment 7:
Zirconium white proportioning raw materials is as follows: granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the mass percent that stabilizing zirconia particle that 0.15 mm is less than or equal to 0.5 mm accounts for raw material and is respectively 25%, 20%, 15%; It is 17% that granularity is greater than the mass percent that stabilizing zirconia fine powder that 30 μ m are less than or equal to 150 μ m accounts for raw material; It is 15% that meso-position radius D50 is greater than the mass percent that yttria-stabilized zirconia micro mist that 0.5 μ m is less than or equal to 30 μ m accounts for raw material; Above stabilizing zirconia is stablizer Y
2o
3massfraction is 15% electrically melt yttrium oxide stabilized zirconia.Purity Y
2o
3>=99.0%, it is 8% that granularity is more than or equal to the mass percent that yttrium oxide powder that 0.005mm is less than or equal to 0.076mm accounts for raw material; Bonding agent is water-base resin and polyvinyl alcohol mixing solution, and add-on is 4.5% of raw material total mass; Above-mentioned raw materials, bonding agent are mixed, and compression moulding is zirconium white base substrate; After body drying, under 1850 ℃ of atmospheric pressure oxidation atmosphere, burn till; Zircite product after burning till is built by laying bricks or stones in vacuum heat treatment furnace, in be formed centrally cavity, in cavity, miramint is heating source heating, heat is to zirconia brick radiation, the interior heated oxide aluminium of while cavity makes it to form steam and infiltrates to zirconia brick, controlling zirconia brick internal surface temperature is 2100 ℃, is incubated 15 hours, obtains the zirconia refractory product of gradient function.This zirconia refractory product is used as the long brilliant furnace lining material of sapphire; Through this zirconium white internal skin of XRD analysis, contain Y
2o
3and Al
2o
3the yttrium aluminum garnet forming; This zirconia refractory product ZrO
2+ Y
2o
3content=99.2wt%, there is Gradient distribution from hot side to huyashi-chuuka (cold chinese-style noodles) in internal microstructure, hot side place apparent porosity 25%, huyashi-chuuka (cold chinese-style noodles) place apparent porosity 30%.
Embodiment 8:
Zirconium white proportioning raw materials is as follows: granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the mass percent that stabilizing zirconia particle that 0.15 mm is less than or equal to 0.5 mm accounts for raw material and is respectively 25%, 20%, 20%; It is 20% that granularity is greater than the mass percent that stabilizing zirconia fine powder that 30 μ m are less than or equal to 150 μ m accounts for raw material; It is 10% that meso-position radius D50 is greater than the mass percent that yttria-stabilized zirconia micro mist that 0.5 μ m is less than or equal to 30 μ m accounts for raw material; Above stabilizing zirconia is stablizer Y
2o
3massfraction is 18% electrically melt yttrium oxide stabilized zirconia.Purity Y
2o
3>=99.0%, it is 5% that granularity is more than or equal to the mass percent that yttrium oxide powder that 0.005mm is less than or equal to 0.076mm accounts for raw material; Bonding agent is resol, and add-on is 5% of raw material total mass; Above-mentioned raw materials, bonding agent are mixed, and compression moulding is zirconium white base substrate; After body drying, under 1800 ℃ of atmospheric pressure oxidation atmosphere, burn till; Zirconia brick after burning till is directly built by laying bricks or stones in the long crystalline substance of jewel and is used as furnace lining material, in the tungsten crucible of body of heater center, fill high purity aluminium oxide powder raw material, adopting miramint is heating source heating tungsten crucible, makes aluminum oxide fusion and gasification, and controlling technological temperature is 2200 ℃; Continue insulation 10h, after Slow cooling, obtain the zirconia refractory product of gradient function.This zirconia refractory product can be used as the long brilliant furnace lining material of sapphire and continues life-time service; Through this zirconium white internal skin of XRD analysis, contain Y
2o
3and Al
2o
3the yttrium aluminum garnet forming; This zirconia refractory product ZrO
2+ Y
2o
3content=99.0wt%, there is Gradient distribution from hot side to huyashi-chuuka (cold chinese-style noodles) in internal microstructure, hot side place apparent porosity 25%, huyashi-chuuka (cold chinese-style noodles) place apparent porosity 28%.
Embodiment 9:
Zirconium white proportioning raw materials is as follows: granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the mass percent that stabilizing zirconia particle that 0.15 mm is less than or equal to 0.5 mm accounts for raw material and is respectively 30%, 20%, 20%; It is 15% that granularity is greater than the mass percent that stabilizing zirconia fine powder that 30 μ m are less than or equal to 150 μ m accounts for raw material; It is 10% that meso-position radius D50 is greater than the mass percent that yttria-stabilized zirconia micro mist that 0.5 μ m is less than or equal to 30 μ m accounts for raw material; Above stabilizing zirconia is stablizer Y
2o
3massfraction is 17% electrically melt yttrium oxide stabilized zirconia.Purity Y
2o
3>=99.5%, it is 5% that granularity is more than or equal to the mass percent that yttrium oxide powder that 0.015mm is less than or equal to 0.043mm accounts for total solids raw material; Bonding agent is resol, and add-on is 3.5% of raw material total mass; Above-mentioned raw materials, bonding agent are mixed, and compression moulding is zirconium white base substrate; After body drying, under 1850 ℃ of atmospheric pressure oxidation atmosphere, burn till; Zircite product after burning till is built by laying bricks or stones in vacuum heat treatment furnace, in be formed centrally cavity, in cavity, miramint is heating source heating, heat is to zirconia brick radiation, the interior heated oxide aluminium of while cavity makes it to form steam and infiltrates to zirconia brick, controlling zirconia brick internal surface temperature is 2100 ℃, is incubated 15 hours, obtains the zirconia refractory product of gradient function.This zirconia refractory product is used as the long brilliant furnace lining material of sapphire; Through this zirconium white internal skin of XRD analysis, contain Y
2o
3and Al
2o
3the yttrium aluminum garnet forming; This zirconia refractory product ZrO
2+ Y
2o
3content=99.5wt%, there is Gradient distribution from hot side to huyashi-chuuka (cold chinese-style noodles) in internal microstructure, hot side place apparent porosity 23%, huyashi-chuuka (cold chinese-style noodles) place apparent porosity 30%.
Claims (7)
1. a yttrium stable zirconium oxide refractory product for gradient function, as the zirconia refractory product of the long brilliant furnace lining material of sapphire, ZrO in goods
2content>=98wt%, described ZrO
2content comprise stablizer; The raw material of described zirconia refractory product includes electrically melt yttrium oxide stabilized zirconia particle, electrically melt yttrium oxide stabilized zirconia fine powder, electrically melt yttrium oxide stabilized zirconia micro mist; In described electrically melt yttrium oxide stabilized zirconia particle, electrically melt yttrium oxide stabilized zirconia fine powder and electrically melt yttrium oxide stabilized zirconia micro mist, yttrium oxide is as stablizer, in described electrically melt yttrium oxide stabilized zirconia particle, electrically melt yttrium oxide stabilized zirconia fine powder and electrically melt yttrium oxide stabilized zirconia micro mist, as the massfraction of the yttrium oxide of stablizer, be 13% ~ 20%; The raw material of described zirconia refractory product also includes the yttrium oxide powder adding separately, and the mass percent of yttrium oxide powder in zirconia refractory product raw material is 3% ~ 10%; The raw material gross weight sum of described zirconia refractory product is 100%, and has bonding agent; Yttrium oxide powder and excessive stabilized with yttrium oxide agent and jewel are grown the raw material A l in brilliant stove
2o
3the resulting resultant melting degree under differing temps that reacts is different, makes zirconia refractory product have specific non-homogeneous interior microscopic weave construction, and from working face to non-working surface, the apparent porosity of these goods and volume density are linear gradient and change.
2. the yttrium stable zirconium oxide refractory product of a kind of gradient function according to claim 1, is characterized in that: the apparent porosity of described yttrium stable zirconium oxide refractory product is 18% ~ 30%.
3. the yttrium stable zirconium oxide refractory product of a kind of gradient function according to claim 1, is characterized in that: described yttrium oxide powder, its purity Y
2o
3>=99.0%, its granularity is less than or equal to 0.076mm for being more than or equal to 0.005mm.
4. the yttrium stable zirconium oxide refractory product of a kind of gradient function according to claim 1, it is characterized in that: described electrically melt yttrium oxide stabilized zirconia particle refers to that grain graininess scope is for being greater than 0.15 mm, be less than or equal to the particle of 3 mm, wherein granularity is greater than 1 mm and is less than or equal to 3 mm, granularity and is greater than 0.5 mm and is less than or equal to 1 mm, granularity and is greater than the zirconia particles material that 0.15 mm is less than or equal to 0.5 mm and is respectively 20% ~ 40%, 20% ~ 30%, 10% ~ 20% of zirconia refractory product raw material gross weight; The size range of described electrically melt yttrium oxide stabilized zirconia fine powder is less than or equal to 150 μ m for being greater than 30 μ m, is 10% ~ 20% of zirconia refractory product raw material gross weight; Described electrically melt yttrium oxide stabilized zirconia micro mist, size range is that meso-position radius D50 is greater than 0.5 μ m and is less than or equal to 30 μ m, addition is 10% ~ 20% of zirconia refractory product raw material gross weight.
5. the yttrium stable zirconium oxide refractory product of a kind of gradient function according to claim 1, is characterized in that: the add-on of described bonding agent is 3% ~ 5% of zirconia refractory product solid material total amount.
6. a kind of yttrium stable zirconium oxide refractory product of gradient function according to claim 1 or 5, is characterized in that: described bonding agent is the combination of one or both any mass ratios in resol, polyvinyl alcohol water solution, epoxy resin, furane resin, water-base resin.
7. the yttrium stable zirconium oxide refractory product of a kind of gradient function according to claim 1, it is characterized in that: the yttrium stable zirconium oxide refractory product of described gradient function, by following technique, realize: first by electrically melt yttrium oxide stabilized zirconia particle, electrically melt yttrium oxide stabilized zirconia fine powder, electrically melt yttrium oxide stabilized zirconia micro mist, yttrium oxide powder, mixed with bonding agent, compression moulding is zirconium white base substrate; After body drying, under 1600 ℃ ~ 1850 ℃ atmospheric pressure oxidation atmosphere, burn till; Zircite product after burning till is piled up in heat treatment furnace along burner hearth center, make to be formed centrally in burner hearth cavity, in cavity, miramint is heating source heating, heat is to zirconia brick radiation, the interior heated oxide aluminium of while cavity makes it to form steam and infiltrates to zirconia brick, controlling zircite product internal surface temperature is 1950 ℃ ~ 2100 ℃, and continuous heating 10h ~ 20h obtains the zirconia refractory product of gradient function after Slow cooling; Or the zircite product after burning till under 1600 ℃ ~ 1850 ℃ atmospheric pressure oxidation atmosphere is built by laying bricks or stones in the long brilliant stove of sapphire and is used as furnace lining material, the long brilliant stove of heating sapphire is to 2100 ℃ ~ 2200 ℃ of technological temperatures, make aluminum oxide fusion and gasification in stove infiltrate zircite product, continue insulation 10h ~ 20h, after Slow cooling, also can form the zirconia refractory product with gradient function.
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| CN114315379A (en) * | 2022-02-23 | 2022-04-12 | 中钢集团洛阳耐火材料研究院有限公司 | Glass phase coated zirconia spherical powder and preparation method thereof |
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