CN109400191A - A kind of high-purity zirconia heat insulation refractory product - Google Patents

A kind of high-purity zirconia heat insulation refractory product Download PDF

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CN109400191A
CN109400191A CN201811500407.5A CN201811500407A CN109400191A CN 109400191 A CN109400191 A CN 109400191A CN 201811500407 A CN201811500407 A CN 201811500407A CN 109400191 A CN109400191 A CN 109400191A
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refractory product
zirconia
zirconium oxide
heat insulation
purity
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孙红刚
谭清华
闫双志
杜昊
杜一昊
耿可明
尚心莲
黄振武
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Sinosteel Luoyang Institute of Refractories Research Co Ltd
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Sinosteel Luoyang Institute of Refractories Research Co Ltd
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Abstract

The invention belongs to fire resisting material fields, relate generally to a kind of high-purity zirconia heat insulation refractory product.A kind of high-purity zirconia heat insulation refractory product proposed is made of aggregate and matrix；Aggregate is a kind of to use that sintering process preparation, bulk density is 3.0 ~ 5.0 g/cm3Zirconium oxide porous particle；Aggregate accounts for the 55%~80% of entire refractory product gross mass, and the granularity of aggregate is 0.2~3 mm；Matrix includes the mixture that powdered zirconium oxide and zirconium oxide micro mist are constituted；High-purity zirconia heat insulation refractory product is that have effigurate refractory material under a kind of room temperature, have passed through the heat treatment under the high temperature oxidative atmosphere that maximum sintering temperature is 1600 ~ 1800 DEG C.The present invention has the characteristics that have heat preservation and structural support function under high temperature concurrently using temperature is high, thermal conductivity is moderate, mechanical strength is high.

Description

A kind of high-purity zirconia heat insulation refractory product
Technical field
The invention belongs to fire resisting material fields, relate generally to a kind of high-purity zirconia heat insulation refractory product.
Background technique
Zirconium dioxide fusing point is up to 2715 DEG C, has using it as the zirconia refractory of primary raw material preparation and changes under high temperature Many advantages, such as property is stable, using can be used under thermo-field thoery (up to 2400 DEG C or more), oxidation or reducing atmosphere is learned, being At present can industrialized production and application superhigh temperature field refractory material the most mature.
Except the reaction vessels as superhigh temperature field, zirconia refractory is mainly used in the another of superhigh temperature field Insulation.Compared with the superhigh temperature metal material such as tungsten, the thermal conductivity of zirconia refractory not and its 1/10th, does not exist such as It is insulating inner lining that zirconia refractory is commonly used in sapphire crystal growing furnace, infusibility tungsten-molybdenum alloy sintering furnace.Heat-insulated oxidation Zr refractory material is usually the aggregate that is constituted using the particle of the zirconium oxide containing stabilizer and using zirconium oxide as the thin of primary raw material The compositions such as powder, micro mist it is substrate composed, combined through the thick provisional bonding agent of liquid, after compression moulding, through high temperature firing Refractory product.
Crystal of zirconium oxide has monocline, four directions, cube 3 kinds of crystal structures, this 3 kinds of crystal structures vary with temperature generation can Inverse transformation, and the transformation of crystal structure is along with biggish volume change.Pure zirconia is monoclinic phase in a natural environment, when It is heated to 1100 ~ 1200 DEG C and is then converted to tetragonal phase, generate volume contraction, and when temperature reduces by 950-100 DEG C four of process again Side mutually can be transformed into monoclinic phase again, generate great volume expansion (volume expansion amount about 4.7%).This phase transition process causes The fragmentation or even dusting of pure zirconia product.Thus, pure zirconia refractory material almost can not be produced and be used.In zirconium oxide Add stabilizer, the metal ion in high temperatures agent enters zirconia crystal lattice, be still able to maintain under period low temperature cubic phase or Tetragonal phase (stable phase), common stabilizer are calcium oxide, magnesia, yttrium oxide, cerium oxide etc..In addition, industrial oxidation zirconium is former Material is by being often associated with hafnium oxide in mineral preparation process.Thus, zirconia refractory main chemical compositions are ZrO2、HfO2、 And stabilizer CaO, MgO, Y2O3、CeO2Deng.
Zirconia material is predominantly artificial synthesized in addition to natural baddeleyite.Higher (the > of purity can be produced using chemical method 99.5%) monoclinic zirconia raw material, and the desiliconization zirconium oxide for using zircon mineral and carbon to generate through the desiliconization method of high temperature electric smelting Purity lower (> 98.5%) but cost is relatively low.Above-mentioned zirconia material is monocline phase zircite, is only capable of in zirconia refractory In add on a small quantity.And the main material as zirconia refractory is then that partially stabilized zirconia or fully stabilized zirconia (are stablized The content of agent is different).Partially stabilized zirconia or fully stabilized zirconia are mainly prepared using electric smelting method at present --- by monocline oxygen High temperature after change zirconium powder material and the mixing of stabilizer powder in three-phawse arc furnace through 3000 DEG C or so, fills zirconium oxide and stabilizer Divide and melt and dissolve, is passed through after melt is cooling and the processes such as be crushed, sieve, clean to get electric smelting stabilizing zirconia particle or fine powder.? During electrically smelting is for stabilizing zirconia, compact zirconia particle (also known as oxidation zircon sand) is obtained if directly cooling down melt；If Before melt is cooling, by compressed air spraying, then there must be the Bubble zirconia particle of hollow structure.
Compact zirconia particle and Bubble zirconia particle are all the main aggregates of zirconia refractory.With fine and close oxygen Changing zirconium particle (Quan Wending or partially stabilized) is aggregate, and powdered zirconium oxide/micro mist (Quan Wending or partially stabilized or monocline) is base Matter can prepare heavy zircite product (also known as zirconium oxide sanded brick).It is with Bubble zirconia particle (Quan Wending or partially stabilized) Aggregate, powdered zirconium oxide/micro mist (Quan Wending or partially stabilized or monocline) are that matrix can prepare Bubble zirconia product (also known as Bubble zirconia brick).
Zirconia refractory is basically divided into 3 major class: 1) Zirconium oxide fibre product according to heat-proof quality at present, with oxygen Changing zirconium crystal fibre is that raw material is mixed with high-temperature agglomerant, and high temperature is heat-treated after forming, thermal conductivity extremely low (about 0.2 1000 DEG C of W/ (mK)@), mechanical strength is low (about 1 MPa of cold crushing strength), uses at 1700 DEG C ~ 2000 DEG C, has fabulous Thermal and insulating performance；2) high-purity zirconia hollow sphere insulating product, with 3mm or less electric-melting zirconia hollow sphere and zirconium oxide Fine powder mixing after form, fired through high temperature, have thermal conductivity low (about 0.6 1100 DEG C of W/ (mK)@), mechanical strength compared with The characteristics of high (about 5 MPa of cold crushing strength), be 1800 DEG C ~ 2100 DEG C preferable heat preserving and insulating materials；3) heavy zirconium oxide Product is fired after molding through high temperature using electric smelting stabilizing zirconia particle and fine powder as raw material, and there is superhigh temperature lower volume to stablize Property good, high mechanical strength (cold crushing strength be greater than 30MPa), thermal conductivity high (about 2.0 1200 DEG C of W/ (mK)@) the characteristics of, It is presently available for the reaction lining and insulating lining of 2200 DEG C ~ 2500 DEG C hyperthermal environments.
Zirconium oxide fibre product thermal conductivity is low, with high purity, chemical stability is good, has special make in high temperature insulating field With.Current industrialized Zirconium oxide fibre generallys use sol-gal process, and the colloidal sol containing zirconium added with stabilizer is solidified into silk Heat treatment is carried out after shape gel forms the zirconia crystal fiber containing stabilizer.And Zirconium oxide fibre product is then containing oxidation The slurry of the compositions such as the crystal fibre and zirconia sol, bonding agent of zirconium adds after high temperature heat treatment after filtering technological forming Work is at about 0.8 ~ 1.5 g/cm of the density of certain shapes and size3Shape product.Zirconium oxide fibre in Zirconium oxide fibre product And powder etc. all has higher sintering activity, and further physicochemical change can be generated in applied at elevated temperature, reheating line becomes Rate is big, and being used for a long time in the case where being higher than 2000 DEG C of hot environments will appear apparent dusting and contraction, seriously affects furnace lining structure Safety and furnace lining be used for a long time heat insulation.
Bubble zirconia refractory product thermal conductivity is lower, raw materials used predominantly superhigh temperature electric smelting technique preparation, high Stability is good in warm use, and shrinking percentage is low, thus has compared with Zirconium oxide fibre product higher using temperature.Bubble zirconia is resistance to Fiery product is usually raw material by electric smelting stabilizing zirconia hollow sphere, electric smelting stabilizing zirconia fine powder and micro mist, through liquid binder After being mixed evenly, it is packed into the adobe that the internal vibration of shape mould is press-formed into specific shape and size, through drying, high temperature is fired into About 2.0 ~ 3.0 g/cm of density3Bubble zirconia product.Function of heat insulation is played in Bubble zirconia refractory product Main matter is Bubble zirconia, and the ratio of Bubble zirconia is higher, and the thermal conductivity of product is lower, and heat insulation is better. But Bubble zirconia is the preparation of electric smelting blowing process, and hollow sphere crystallite dimension is big, any surface finish, sintering activity are poor, thus oxygen The being tightly combined property for changing zirconium hollow sphere and powdered zirconium oxide is poor, even if Bubble zirconia and zirconium oxide under very high firing temperature The bond strength of matrix is lower, causes Bubble zirconia content ratio higher, and the mechanical strength under room temperature and high temperature is lower.Oxygen Change in the use of zirconium hollow sphere refractory product and finds that it just will appear more serious open after a period of use at 2200 DEG C It splits, mechanical strength sharply declines, and constitutes furnace lining structure security risk.
Heavy zircite product is electric smelting stabilizing zirconia fine powder, zirconium oxide using electric smelting stabilizing zirconia particle as aggregate Micro mist etc. is matrix, after mixing with bonding agent, using machine pressure, etc. the moulding process such as static pressure, ramming prepare certain shapes base Body is fired after dry through high temperature, and about 4.0 ~ 5.0 g/cm of density is prepared3Zircite product.Due to raw materials used master in the product It to be the fine and close raw material of high temperature electric smelting method production, so its thermal conductivity is high, mechanical strength height, contraction distortion are small under high temperature, resist molten Body good penetrability, frequently as the reactor in superhigh temperature and the insulating lining under 2200 ~ 2500 DEG C of hyperthermal environments.But Heat insulation effect is poor when heavy zircite product is as furnace lining, heat loss is serious.
As it can be seen that heavy zircite product chemical purity is high, mechanical strength is high, volume stability is good, be current 2200 DEG C with On the thermal insulation material that generallys use, but its material structure is excessively fine and close, and heat-proof quality is poor, and thermal losses is excessively high, to superhigh temperature equipment Energy conservation and lighting it is totally unfavorable.And Bubble zirconia insulating product and Zirconium oxide fibre product although all have it is lower Thermal conductivity, but they will appear serious firing when used for a long time at 2100 DEG C or more and shrink, and collapse there are furnace lining deformation Hidden danger, the long-time service of Zirconium oxide fibre product there is also dusting, this not only causes increased dramatically for insulating layer thermal conductivity, even more The overall structure of furnace lining material is caused to seriously affect.Thus, make in superhigh temperature is heat-insulated to improve zirconia refractory With performance, the collaboration control of the performances such as chemical purity, density, intensity, thermal conductivity and the volume stability of zirconia material is solved System is its key.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to propose to a kind of high-purity zirconia heat insulation refractory products.
The present invention adopts the following technical solutions to accomplish the above objectives:
A kind of high-purity zirconia heat insulation refractory product, chemical componentw(ZrO2+HfO2+CaO+MgO+Y2O3) >=98.5%, volume Density is 2.8 ~ 4.0 g/cm3, high-purity zirconia heat insulation refractory product is made of aggregate and matrix；The aggregate is a kind of Use sintering process preparation, bulk density for 3.0 ~ 5.0 g/cm3Zirconium oxide porous particle；The aggregate accounts for entire fire resisting The 55%~80% of product gross mass, the granularity of aggregate are 0.2~3 mm；The matrix includes powdered zirconium oxide and zirconium oxide The mixture that micro mist is constituted；The matrix accounts for the 20%~45% of entire refractory product gross mass, and the granularity of powdered zirconium oxide is 0.043~0.1 mm, the granularity of zirconium oxide micro mist are D50≤10μm；The high-purity zirconia heat insulation refractory product is a kind of normal The effigurate refractory material of the lower tool of temperature, have passed through under the high temperature oxidative atmosphere that maximum sintering temperature is 1600 ~ 1800 DEG C Heat treatment.
Combination in the matrix also containing stabilizer, pore creating material or both.
The powdered zirconium oxide is electric smelting stabilizing zirconia fine powder or electric smelting stabilizing zirconia fine powder and sintered zirconia The mixture of fine powder.
The powdered zirconium oxide quality accounts for the 8%~35% of entire refractory product gross mass.
The zirconium oxide porous particle is a kind of stabilizing zirconia raw material, and purity isw(ZrO2+HfO2+CaO+MgO+ Y2O3) >=98.0%.
The powdered zirconium oxide or sintered zirconia fine powder purity bew(ZrO2+HfO2+CaO+MgO+Y2O3) >= 99.0%。
The stabilizer is CaO, MgO, Y2O3Fine powder or high temperature under react produce CaO, MgO, Y2O3Fine powder, Such as one of yttrium oxide, calcium carbonate, magnesium carbonate, calcium hydroxide, additional amount is to account for entire refractory product gross mass 0.3% ~ 1% (with CaO, MgO, Y2O3Meter).
The pore creating material is the carbonaceous material that stomata is left after being burnt mistake under a type high temp.
The pore creating material is flour or carbon dust or plastic beads, and granularity is not more than 0.1 mm, and additional amount is to account for entirely Refractory product gross mass 1% ~ 3%.
A kind of high-purity zirconia heat insulation refractory product proposed by the present invention, the zirconia particles with the preparation of sintering process technique are Aggregate, with it is traditional using the particle of electric smelting method technique compared with, sintering process preparation grain crystalline is small, particle surface layer roughness Height, more, the sintering activity height of crystal defect etc., these are all conducive to the high temperature bond of particle and matrix, greatly improve heat-insulated The mechanical strength of refractory material；Zirconium oxide sintering aggregate in the present invention is a kind of particle of porous structure, and bulk density is 3.0~5.0 g/cm3, the theoretical density of zirconium oxide is 6.0 g/cm3, the relative density of particle is only 50% ~ 83% in the present invention, On the one hand the zirconium oxide of porous structure advantageously reduces the thermal conductivity of refractory product entirety, play the effect of heat-insulation and heat-preservation, another Aspect, this porous structure have pore opening different, and air hole structure is irregular, perforation and non-through the characteristics of interlocking, improve The thermal shock resistance of refractory product；There is electric smelting stabilizing zirconia fine powder and zirconium oxide micro mist, electric smelting in matrix in the present invention Stabilizing zirconia fine powder volume stability in firing is good, and zirconium oxide micro mist then active height, is easy to the characteristics of being sintered, and two Person is used in mixed way, that is, product sintering strength, which can be improved, again can prevent product volume change rate product caused greatly when firing from cracking； Aggregate and the Proportionality design of matrix have comprehensively considered intensity and thermal conductivity after the burning of product；The present invention claims the zircite products to need By 1600 DEG C ~ 1800 DEG C high-temperature heat treatments, this is because the based article is mainly used in hot environment, the high warm before use Processing is conducive to the volatile matter being discharged in refractory product, release stress, improves intensity and keep the knot of furnace lining masonry in use Structure stability；The study found that working as firing temperature >=1600 DEG C, zirconia material sintering degree is obvious, as firing temperature > 1800 DEG C, sintering is no longer obvious by the raised variation of temperature, and excessively high firing temperature will cause the significant wastage of the energy；High-purity zirconia Thermal coefficient at 1100 DEG C of heat insulation refractory product is 0.4 ~ 1.0 W/ (mK),.
To sum up, a kind of high-purity zirconia heat insulation refractory product proposed by the present invention, it is porous using having for sintering process preparation The stabilizing zirconia particle of structure is aggregate, utilizes the porous particle rough surface of this sintering process preparation, large specific surface area, burning The high feature of knot activity；So that the matrix being made of powdered zirconium oxide and zirconium oxide micro mist at high temperature can well with aggregate knot It closes, improves the bond strength of aggregate and matrix, while leading for material can be effectively reduced in the porous structure in aggregate and matrix Hot coefficient, compared with prior art, the present invention have the characteristics that using temperature is high, thermal conductivity is moderate, mechanical strength is high, under high temperature It has heat preservation and structural support function concurrently, is a kind of high-performance refractory material that super high-temp. energy-saving field uses.
Specific embodiment
In conjunction with the embodiment provided, the present invention is illustrated, but does not constitute any limitation of the invention.
Embodiment 1:
Weighing chemical composition of the granularity greater than 43 μm less than or equal to 100 μm respectively is that purity isw(ZrO2+HfO2+ CaO) >= 99.0% electric smelting stable calcium oxide powdered zirconium oxide 35 kg, granularity D50≤ 10 μm of chemical composition isw(ZrO2+HfO2)≥ 99.5% 8 kg of monoclinic zirconia micro mist, granularity are greater than 43 μm of calcium carbonate fine powder 1kg for being less than or equal to 100 μm, and granularity is greater than 43 μm it is less than or equal to 100 μm of 1 kg of edible wheat flour, is sufficiently premixed through ball mill, be prepared into matrix fine powder；It is big to weigh granularity It is less than or equal to 3mm in 0.2 mm,w(ZrO2+HfO2+ CaO) >=98.3%, 2.8 g/cm of bulk density3Sintering process preparation oxygen Change calcia-stabilised zirconia porous particle 55kg, is added in forced stirrer and mixes；Bonding agent mass fraction is added into particulate material For about 4 kg of 5% polyvinyl alcohol water solution, the matrix fine powder after premix, after being sufficiently mixed, ageing mixture are added after stirring；Friction pressure brick Machine molding blank, it is resistance to get zirconia barrier in 1600 DEG C of firings in the unsealed conventional, electric-resistance furnace of normal pressure after 110 DEG C of dryings Fiery product.The performance parameter of the product is as shown in the table, which has purity is high, high mechanical strength, heat-proof quality excellent, and 2300 It is good using volume stability under DEG C superhigh temperature, the advantages that not collapsing, be indeformable.
Embodiment 2:
Weighing chemical composition of the granularity greater than 43 μm less than or equal to 100 μm respectively is that purity isw(ZrO2+HfO2 +Y2O3) >= 99.0% electrically melt yttrium oxide stabilized zirconia fine powder 30 kg, granularity D50≤ 5 μm of chemical composition isw(ZrO2+HfO2)≥ 99.5% 7 kg of monoclinic zirconia micro mist, granularity are greater than 43 μm of industrial oxidation yttrium fine powder 1kg for being less than or equal to 74 μm, and granularity is big It is less than or equal to 74 μm of powdered carbon 2kg in 43 μm, is sufficiently premixed through ball mill, be prepared into matrix fine powder；Granularity is weighed greater than 0.2 Mm is less than or equal to 3mm,w(ZrO2+HfO2+CaO+MgO+Y2O3) >=98.0%, 3.6 g/cm of bulk density3Sintering process preparation Calcium and magnesium yttrium stable composition zirconium oxide porous particle 60kg is added in forced stirrer and mixes；Bonding agent phenol is added into particulate material Urea formaldehyde alcoholic solution 5kg, the matrix fine powder after premix is poured into after stirring, after being sufficiently mixed, ageing mixture；Friction press is at parison Body, in 1650 DEG C of firings in the unsealed conventional, electric-resistance furnace of normal pressure to get zirconia barrier refractory product after 110 DEG C of dryings.It should The performance parameter of product is as shown in the table, which has purity is high, high mechanical strength, heat-proof quality excellent, 2300 DEG C of superhigh temperature It is lower good using volume stability, the advantages that not collapsing, be indeformable.
Embodiment 3:
Weighing chemical composition of the granularity greater than 43 μm less than or equal to 74 μm respectively is that purity isw(ZrO2+HfO2 +Y2O3) >= 99.3% electrically melt yttrium oxide stabilized zirconia fine powder 28 kg, granularity D50≤ 2 μm of chemical composition isw(ZrO2+HfO2)≥ 99.5% 5 kg of monoclinic zirconia micro mist, granularity is greater than 74 μm of vinyon bead 2kg for being less than or equal to 100 μm, through ball milling Machine sufficiently premixes, and is prepared into matrix fine powder；It weighs granularity and is less than or equal to 3mm greater than 0.2 mm,w(ZrO2+HfO2 +Y2O3) >= 99.5%, 3.6 g/cm of bulk density3Sintering process preparation yttria-stabilized zirconia porous particle 65kg, be added force stir It mixes in machine and mixes；Bonding agent phenolic resin alcoholic solution 5kg is added into particulate material, the matrix after premix is poured into after stirring is thin Powder, after being sufficiently mixed, ageing mixture；Pressuring machine molding blank is vibrated, in 1700 DEG C in the shuttle kiln of gas heating after 110 DEG C of dryings Firing is to get zirconia barrier refractory product.The performance parameter of the product is as shown in the table, which has purity is high, machinery Intensity is high, heat-proof quality is excellent, good using volume stability under 2500 DEG C of superhigh temperature, the advantages that not collapsing, is indeformable.
Embodiment 4:
Weighing chemical composition of the granularity greater than 43 μm less than or equal to 100 μm respectively is that purity isw(ZrO2+HfO2 +Y2O3) >= 99.0% electrically melt yttrium oxide stabilized zirconia fine powder 15 kg, granularity D50≤ 2 μm of chemical composition isw(ZrO2+HfO2+Y2O3) >=99.5% 12 kg of partially stabilized zirconia micro mist, granularity are less than or equal to 43 μm of powdered carbon 3kg, sufficiently premix through ball mill, It is prepared into matrix fine powder；It weighs granularity and is less than or equal to 2mm greater than 0.2 mm,w(ZrO2+HfO2 +Y2O3) >=99.0%, volume are close Spend 3.0 g/cm3Sintering process preparation 70 kg of yttria-stabilized zirconia porous particle, be added forced stirrer in mix； 4 kg of bonding agent phenolic resin alcoholic solution is added into particulate material, the matrix fine powder after premix is poured into after stirring is sufficiently mixed Afterwards, ageing mixture；Pressuring machine molding blank is vibrated, in 1750 DEG C of firings in the shuttle kiln of gas heating to get oxygen after 110 DEG C of dryings Change zirconium heat insulation refractory product.The performance parameter of the product is as shown in the table, which has purity is high, high mechanical strength, heat-insulated Performance is excellent, good using volume stability under 2300 DEG C of superhigh temperature, the advantages that not collapsing, is indeformable.
Embodiment 5:
Weighing chemical composition of the granularity greater than 43 μm less than or equal to 100 μm respectively is that purity isw(ZrO2+HfO2+ MgO) >= 98.7% electrically molten magnesia stabilizing zirconia fine powder 12 kg, granularity D50≤ 8 μm of chemical composition isw(ZrO2+HfO2)≥ 99.5% 10 kg of monoclinic zirconia micro mist, granularity are greater than 43 μm of 0.65 kg of carbonic acid magnesium powder for being less than or equal to 100 μm, and granularity is big It is less than or equal to 100 μm of 2.2 kg of edible wheat flour in 43 μm, is sufficiently premixed through ball mill, be prepared into matrix fine powder；It weighs Granularity is greater than 0.2 mm and is less than or equal to 1mm,w(ZrO2+HfO2+ MgO) >=98.9%, 3.9 g/cm of bulk density3Sintering process The stabilized magnesium hydroxide zirconium oxide porous particle 75kg of preparation is added in forced stirrer and mixes；Bonding agent is added into particulate material Water-soluble resin 5kg, the matrix fine powder after premix is poured into after stirring, after being sufficiently mixed, ageing mixture；Pressuring machine molding blank is vibrated, In 1800 DEG C of firings in the shuttle kiln of gas heating to get zirconia barrier refractory product after 110 DEG C of dryings.The property of the product Energy parameter is as shown in the table, which has purity is high, high mechanical strength, heat-proof quality excellent, and body is used under 2300 DEG C of superhigh temperature Product stability is good, the advantages that not collapsing, is indeformable.
Embodiment 6:
Weighing chemical composition of the granularity greater than 43 μm less than or equal to 74 μm respectively is that purity isw(ZrO2+HfO2 +CaO+MgO+ Y2O3Electrically melt yttrium oxide stabilized zirconia fine powder 8 kg, granularity D of) >=99.0%50≤ 4 μm of chemical composition isw(ZrO2+HfO2+ Y2O312 kg of yttria-stabilized zirconia micro mist of) >=99.5%, sufficiently premixes through ball mill, is prepared into matrix fine powder；Weigh grain Degree is greater than 0.5 mm and is less than or equal to 3mm,w(ZrO2+HfO2+CaO+MgO+Y2O3) >=99.0%, 4.0 g/cm of bulk density3Burning The calcium and magnesium yttrium stable composition zirconium oxide porous particle 80kg of connection preparation, is added in forced stirrer and mixes；Add into particulate material Enter bonding agent phenolic resin alcoholic solution 3.5kg, the matrix fine powder after premix is poured into after stirring, after being sufficiently mixed, ageing mixture；Friction Brick machine molding blank, in 1800 DEG C of firings in combustion gas shuttle kiln to get zirconia barrier refractory product after 110 DEG C of dryings.It should The performance parameter of product is as shown in the table, which has purity is high, high mechanical strength, heat-proof quality excellent, 2300 DEG C of superhigh temperature It is lower good using volume stability, the advantages that not collapsing, be indeformable.
Embodiment 7:
Weighing chemical composition of the granularity greater than 43 μm less than or equal to 100 μm respectively is that purity isw(ZrO2+HfO2 +Y2O3) >= 99.5% 10 kg of electrically melt yttrium oxide stabilized zirconia fine powder weighs the chemistry that granularity is less than or equal to 100 μm greater than 43 μm respectively Group is as purityw(ZrO2+HfO2+CaO+MgO+Y2O3Sintering yttrium stable zirconium oxide fine powder 10 kg, granularity D of) >=99.5%50 ≤ 2 μm of chemical composition isw(ZrO2+HfO2+Y2O3Yttrium stable zirconium oxide micro mist 15 kg of) >=99.5%, it is abundant through ball mill Premix, is prepared into matrix fine powder；It weighs granularity and is less than or equal to 3mm greater than 0.2 mm,w(ZrO2+HfO2 +Y2O3) >=98.8%, 3.6 g/cm of bulk density3Sintering process preparation yttria-stabilized zirconia porous particle 65kg, be added forced stirrer in It mixes；Bonding agent water-soluble resin 5kg is added into particulate material, the matrix fine powder after premix is poured into after stirring, after being sufficiently mixed, Ageing mixture；Pressuring machine molding blank is vibrated, in 1750 DEG C of firings in the shuttle kiln of gas heating to get zirconium oxide after 110 DEG C of dryings Heat insulation refractory product.The performance parameter of the product is as shown in the table, which has purity is high, high mechanical strength, heat-proof quality It is excellent, it is good using volume stability under 2500 DEG C of superhigh temperature, the advantages that not collapsing, be indeformable.
Embodiment 8:
Weighing chemical composition of the granularity greater than 74 μm less than or equal to 100 μm respectively is that purity isw(ZrO2+HfO2+ CaO) >= 99.0% 15 kg of electric smelting stable calcium oxide powdered zirconium oxide, weighing chemical composition of the granularity greater than 43 μm less than or equal to 74 μm is Purity isw(ZrO2+HfO2+ CaO) >=99.0% sintering oxidation calcia-stabilised zirconia fine powder 5 kg, granularity D50≤ 1 μm of change Group becomesw(ZrO2+HfO2The monoclinic zirconia micro mist 9kg of) >=99.5%, granularity are greater than 43 μm of hydrogen-oxygens for being less than or equal to 74 μm Change calcium powder 1kg, is sufficiently premixed through ball mill, be prepared into matrix fine powder；It weighs granularity and is less than or equal to 3 mm greater than 0.2 mm,w (ZrO2+HfO2+ CaO) >=98.5%, 3.2 g/cm of bulk density3Sintering process preparation yttria-stabilized zirconia porous 70 kg of grain, are added in forced stirrer and mix；4 kg of bonding agent phenolic resin alcoholic solution is added into particulate material, after stirring Matrix fine powder after pouring into premix, after being sufficiently mixed, ageing mixture；Pressuring machine molding blank is vibrated, it is non-in normal pressure after 110 DEG C of dryings 1600 DEG C of firings are in closed resistance furnace to get zirconia barrier refractory product.The performance parameter of the product is as shown in the table, the material Material has purity is high, high mechanical strength, heat-proof quality excellent, good using volume stability under 2300 DEG C of superhigh temperature, does not collapse, is constant The advantages that shape.
The performance of 1-8 each product of gained of embodiment is as shown in the table.

Claims (9)

1. a kind of high-purity zirconia heat insulation refractory product, it is characterised in that: its chemical componentw(ZrO2+HfO2+CaO+MgO+Y2O3) >=98.5%, bulk density is 2.8 ~ 4.0 g/cm3, high-purity zirconia heat insulation refractory product is made of aggregate and matrix；It is described Aggregate be a kind of to use that sintering process preparation, bulk density is 3.0 ~ 5.0 g/cm3Zirconium oxide porous particle；The bone Material accounts for the 55%~80% of entire refractory product gross mass, and the granularity of aggregate is 0.2~3 mm；The matrix includes zirconium oxide The mixture that fine powder and zirconium oxide micro mist are constituted；The matrix accounts for the 20%~45% of entire refractory product gross mass, zirconium oxide The granularity of fine powder is 0.043~0.1 mm, and the granularity of zirconium oxide micro mist is D50≤10μm；The high-purity zirconia insulating refractory Product is that have effigurate refractory material under a kind of room temperature, have passed through the height that maximum sintering temperature is 1600 ~ 1800 DEG C Heat treatment under warm oxidizing atmosphere.
2. a kind of high-purity zirconia heat insulation refractory product as described in claim 1, it is characterised in that: also contain in the matrix There is the combination of stabilizer, pore creating material or both.
3. a kind of high-purity zirconia heat insulation refractory product as described in claim 1, it is characterised in that: the powdered zirconium oxide For electric smelting stabilizing zirconia fine powder or the mixture of electric smelting stabilizing zirconia fine powder and sintered zirconia fine powder.
4. a kind of high-purity zirconia heat insulation refractory product as described in claim 1, it is characterised in that: the powdered zirconium oxide Quality accounts for the 8%~35% of entire refractory product gross mass.
5. a kind of high-purity zirconia heat insulation refractory product as described in claim 1, it is characterised in that: the zirconium oxide is porous Particle is a kind of stabilizing zirconia raw material, and purity isw(ZrO2+HfO2+CaO+MgO+Y2O3) >=98.0%.
6. a kind of high-purity zirconia heat insulation refractory product as described in claim 1, it is characterised in that: the powdered zirconium oxide Or sintered zirconia fine powder purity isw(ZrO2+HfO2+CaO+MgO+Y2O3) >=99.0%.
7. a kind of high-purity zirconia heat insulation refractory product as claimed in claim 2, it is characterised in that: the stabilizer is CaO、MgO、Y2O3Fine powder or high temperature under react produce CaO, MgO, Y2O3Fine powder, as yttrium oxide, calcium carbonate, magnesium carbonate, One of calcium hydroxide, additional amount are to account for entire refractory product gross mass 0.3% ~ 1%.
8. a kind of high-purity zirconia heat insulation refractory product as claimed in claim 2, it is characterised in that: the pore creating material is one The carbonaceous material of stomata is left after being lost by burning under type high temp.
9. a kind of high-purity zirconia heat insulation refractory product as claimed in claim 8, it is characterised in that: the pore creating material is face Powder or carbon dust or plastic beads, granularity are not more than 0.1 mm, and additional amount is to account for entire refractory product gross mass 1% ~ 3%.
CN201811500407.5A 2018-12-10 2018-12-10 A kind of high-purity zirconia heat insulation refractory product Pending CN109400191A (en)

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