CN116969771A - 一种高抗侵蚀熔铸高锆砖及其制备方法 - Google Patents
一种高抗侵蚀熔铸高锆砖及其制备方法 Download PDFInfo
- Publication number
- CN116969771A CN116969771A CN202310785054.2A CN202310785054A CN116969771A CN 116969771 A CN116969771 A CN 116969771A CN 202310785054 A CN202310785054 A CN 202310785054A CN 116969771 A CN116969771 A CN 116969771A
- Authority
- CN
- China
- Prior art keywords
- percent
- zirconium
- casting
- melting
- sand
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 39
- 239000011449 brick Substances 0.000 title claims abstract description 33
- 230000003628 erosive effect Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000005266 casting Methods 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002844 melting Methods 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000000137 annealing Methods 0.000 claims abstract description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004576 sand Substances 0.000 claims abstract description 15
- 239000006004 Quartz sand Substances 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010431 corundum Substances 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 238000005482 strain hardening Methods 0.000 claims abstract description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000009413 insulation Methods 0.000 claims abstract 2
- 239000012774 insulation material Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 12
- 238000010891 electric arc Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 6
- 239000003110 molding sand Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 abstract description 16
- 238000010309 melting process Methods 0.000 abstract description 5
- 239000004615 ingredient Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 9
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 8
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011819 refractory material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/653—Processes involving a melting step
- C04B35/657—Processes involving a melting step for manufacturing refractories
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6565—Cooling rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
本发明公开了一种高抗侵蚀熔铸高锆砖及其制备方法，所述耐火砖配方为脱硅锆89.5～93.9%、工业氧化铝粉0.2～1.2%、氧化钇2.5～5.3%、精石英砂3.5～9.0%和碳酸钠0.05～1.0%；其中脱硅锆重量百分比ZrO2含量≥98.5%，精石英砂重量百分比SiO2含量≥99.5%。其生产方法为先配料；再用高功率三相电弧炉和高压强电流的熔化工艺熔融配料，熔化电压300～390V，电流6000～12000A；然后浇铸成型，铸型用石墨或刚玉整体砂型，重量比为型砂∶水玻璃＝90～100∶6～12，水玻璃模数3.1～3.3，浇铸温度2050～2400℃，浇铸速度180～1000kg/min；浇铸后退火，用优质散状隔热材料作保温介质，退火速度0.03～0.14℃/(kg·h)；最后冷加工制成耐火砖。本发明的熔铸高锆砖气孔率低，体积密度高，且抗玻璃液侵蚀性强。
Description
技术领域
本发明属于耐火材料范畴，涉及高抗侵蚀熔铸高锆砖及制备方法，产品主要用于砌筑太阳能光伏玻璃和信息显示玻璃熔窑。
背景技术
近些年，随着新能源技术和信息显示技术的快速发展，带动了太阳能玻璃和信息显示玻璃的不断发展。然而，由于缺乏抗侵蚀能力强的耐火材料，耐火材料易损耗、窑炉寿命短是上述玻璃生产面临的主要难题。在这类玻璃熔窑上应用的普通熔铸高锆砖的服役寿命与预期寿命的差距很大，对使用前后的熔铸高锆砖的检测分析表明：未使用前的熔铸高锆砖主要由单斜相（m-ZrO2）的斜锆石和少量以SiO2为主成分的非晶态玻璃相组成；使用后，与玻璃液接触的熔铸高锆砖的内侧的单斜相ZrO2转变为四方相的氧化锆（t-ZrO2），朝向窑外的熔铸高锆砖的外侧的ZrO2仍保持单斜相的结构。这是因为在没有晶型稳定剂的作用下，高锆砖中ZrO2以单斜相的形式存在，而且，ZrO2在高温下会发生以下相变：c-ZrO 2 ↔ t-ZrO2↔ m-ZrO2，c-ZrO2（立方相）与t-ZrO2相互转变温度约为1740℃，t-ZrO2 与m-ZrO2相互转变的温度为1170℃。由于高锆砖内侧的ZrO2相变，伴随5%左右的体积收缩，产生微裂纹，导致高锆砖内侧与玻璃液接触的部分致密度降低，为玻璃液的侵蚀渗透提供了通道，使得高锆砖的侵蚀加快。
此外，在正常玻璃生产过程中，熔窑的温度基本稳定，熔铸高锆砖内外侧可以稳定地保持这种内侧ZrO2为四方相，外侧ZrO2为单斜相的结构。但是，一旦停窑降温，在低于ZrO2四方-单斜相变的1170℃，内侧的四方相ZrO2会迅速发生马氏体相变，转变为单斜相，产生5%左右的体积膨胀，导致高锆砖在内外侧1170℃的温度界面处发生开裂，因而在停窑取样时发现，高锆砖沿内外侧温度的界面处均发生开裂现象。
为提高熔铸高锆砖的耐侵蚀性，进而延长窑炉寿命，满足太阳能玻璃和信息显示玻璃日益增长的发展需求，急需开发抗侵蚀性能优异的熔铸高锆耐火砖。
发明内容
本发明所要解决的技术问题是提供一种主要由大部分稳定的ZrO2组成、物相致密结合、气孔率低，不易开裂，具有良好抗侵蚀性能的熔铸高锆砖及制备方法，以满足太阳能玻璃和信息显示玻璃生产的需要。
为解决上述技术问题，本发明所采用的技术方案如下：
熔铸高锆砖是由脱硅锆、工业氧化铝粉、氧化钇、精石英砂和碳酸钠组成的配合料制成，其配料比按重量百分比是：脱硅锆89.5～93.9%、工业氧化铝粉0.2～1.2%、氧化钇2.5～5.3%、精石英砂3.5～9.0%和碳酸钠0.05～1.0%；所述脱硅锆重量百分比ZrO2含量≥98.5%，所述精石英砂重量百分比SiO2含量≥99.5%。
制备上述高抗侵蚀熔铸高锆砖的方法，它包括熔融、浇铸成型、退火和冷加工工序，其特征在于熔融工艺应用高功率的三相电弧炉，采取高压强电流的熔化技术在三相电弧炉中熔融配合料，浇铸成型时的浇铸温度为2050～2400℃，浇铸速度180～1000kg/min，冷却退火的降温速度0.03～0.14℃/(kg·h)，铸型采用石墨或刚玉制作的整体砂型。
本发明产品主要由大部分稳定的ZrO2及少量无定形的硅酸盐相组成，其中ZrO2的稳定化率为70～85%（稳定化率(%)=[(w 立方相 + w 四方相)/(w 立方相 + w 四方相 + w 单斜相)] ×100%）。其配合料通过高温熔融后，在材料的凝固结晶退火过程中，ZrO2在氧化钇的作用下主要以立方相和四方相的氧化锆结晶析出，单斜相（m-ZrO2）的斜锆石较少。本发明产品形成的结晶结构致密度高，气孔率极低。由于立方相、四方相和单斜相的氧化锆都是抗侵蚀性强的物相，它们分布均匀，致密结合，而且，材料ZrO2的稳定化率高，因而在其服役使用过程中ZrO2的相变程度低，不会导致微裂纹的产生及材料致密程度的降低，因此，极大地提高材料的抗侵蚀性能。本发明产品具有杂质含量少，气孔率低，不易开裂，体积密度和耐压强度高，抗侵蚀性能强的显著特点。
上述的熔融工序中应用高功率的三相电弧炉，采取高压强电流的熔化工艺在三相电弧炉中对配合料进行熔融，电弧炉的熔化电压300～390V，熔化电流6000～12000A。
本工艺优于现有普通熔铸耐火产品的熔化工艺。通过采用高压强电流的熔化技术，合理地提高电弧电压，促使电弧功率大幅度增加，显著提高了难熔物料的熔化效率和产品的质量。从而，达到对炉内配合料的强制快熔效果。该熔化技术有利于减少电弧炉的冗余功率设计，同时减轻对电网电压的冲击，从而使电弧炉熔化过程中，不产生电压闪变，电弧连续稳定，有功功率高，提高了生产效率。
上述的浇铸成型工序中熔液的浇铸温度为2050～2400℃，浇铸速度180～1000kg/min。
上述的石墨或刚玉整体砂型中，其重量比例为：
型砂∶水玻璃＝90～100∶6～12，其中水玻璃的模数3.1～3.3 。
型砂指石墨砂或白刚玉段砂，整体砂型优于现有的砂模板拼装模工艺。
上述的退火工序中采用优质散状隔热材料作保温介质，上述的熔铸高锆砖耐火制品在退火工序中的降温速度0.03～0.14℃/（kg·h）。
本工艺优于硅藻土、氧化铝粉、膨胀蛭石、石英砂等作为保温材料的退火方式，极大降低熔铸高锆砖耐火制品的内应力，提高产品退火合格率，消除退火工序粉尘污染，改善工作环境。
上述的冷加工工序中采用金刚石研磨、切割机床加工制品。
采用本发明工艺制造的新型熔铸高锆砖耐火制品，其主晶相为稳定态的立方相和四方相的氧化锆晶体，非稳定态的单斜相的斜锆石较少。在玻璃熔窑长期使用时，该新型制品由于ZrO2的稳定化率高，不会因使用环境内外温度的高低差异，导致制品的内外侧ZrO2处于截然不同的晶型状态，进而有利于使制品在使用时保持内外结构基本一致。因此，该制品可避免因斜锆石大量相变伴随的体积膨胀或收缩所导致的裂纹形成或制品开裂的弊端，显著提高了该材料制品服役的可靠性和使用寿命。
具体实施方式
实施例1
配料：配合料由脱硅锆、工业氧化铝粉、氧化钇、精石英砂和碳酸钠组成，其配料比按重量百分比是：脱硅锆89.5%、工业氧化铝粉0.6～0.8%、氧化钇3.01%、精石英砂6.5～7.0%和碳酸钠0.06～0.15%。
制备工艺包括配料、电炉熔融、浇铸成型、冷却退火和冷加工。
型砂用自控高速混合机混合均匀，装入木模型内，经振动成型后钻取排气孔，涂刷市售高温离型剂后用高强度粘结剂制成完整的模型。
电炉熔融：混匀的配合料在高功率三相电弧炉中熔融，电弧炉熔化电压340～370V，熔化电流6800～10000A。
浇铸成型：浇铸温度为2285℃，浇铸速度485kg/min。
铸型采用石墨砂整体铸型。其重量比例为石墨砂∶水玻璃＝90∶6.8，水玻璃模数3.22。
退火工序：制品退火降温速度0.08℃/（kg·h）。
冷加工：采用金刚石研磨、切割机床加工制品。
本发明产品质量好，其理化性能数据如下：
1.化学成分(wt%):ZrO2 SiO2 Al2O3 Na2O Y2O3
≥88% ≤7.0% ≤1.0% ≤0.05% 3.0%
2.物理性能： 熔铸砖 烧结砖
ZrO2稳定化率（％） 75 38
显气孔率（％） 1.0 19.0
体积密度（g/cm3） 4.9 4.1
常温耐压强度（MPa） 365 62
抗玻璃侵蚀性（mm/24h，1500℃） 0.18 5.92
实施例2
配料：配合料由脱硅锆、工业氧化铝粉、氧化钇、精石英砂和碳酸钠组成，其配料比按重量百分比是：脱硅锆93.4%、工业氧化铝粉0.2～0.4%、氧化钇2.66%、精石英砂3.5～3.8%和碳酸钠0.08～0.15%。
电炉熔融：混匀的配料在高功率三相电弧炉中熔融，电弧炉熔化电压340～390V，熔化电流6500～11000A。
浇铸成型：浇铸温度为2300℃，浇铸速度495kg/min。
铸型用白刚玉整体砂型。其重量比例为白刚玉砂∶水玻璃＝100∶9，水玻璃模数3.29。
退火工序：制品退火降温速度0.09℃/（kg·h）。
采用金刚石研磨机床对制品冷加工后，产品的理化性能数据如下：
1.化学成分(wt%):ZrO2 SiO2 Al2O3 Na2O Y2O3
≥92% ≤4.0% ≤0.6% ≤0.05% 2.65%
2.物理性能： 熔铸砖 烧结砖
ZrO2稳定化率（％） 70 32
显气孔率（％） 0.9 18.5
体积密度（g/cm3） 5.3 4.2
常温耐压强度（MPa） 390 65
抗玻璃侵蚀性（mm/24h，1500℃） 0.15 5.84。
Claims (1)
1.一种高抗侵蚀熔铸高锆耐火砖，其特征在于：配合料由脱硅锆、工业氧化铝粉、氧化钇、精石英砂和碳酸钠组成，所述配合料的配方按重量百分比是：脱硅锆89.5～93.9%、工业氧化铝粉0.2～1.2%、氧化钇2.5～5.3%、精石英砂3.5～9.0%和碳酸钠0.05～1.0%；所述脱硅锆重量百分比ZrO2含量≥98.5%，所述精石英砂重量百分比SiO2含量≥99.5%。所述熔铸高锆耐火砖的生产方法包括配料、熔融、浇铸成型、退火和冷加工工序，其特征在于：利用高功率的三相电弧炉，采取高压强电流的熔化技术在三相电弧炉中熔融配合料，再浇铸成型，最后冷加工制成产品，所述熔化电压300～390V，熔化电流6000～12000A，浇铸温度为2050～2400℃，浇铸速度180～1000kg/min，所述的退火工序中采用优质散状隔热材料作保温介质，退火工序的降温速度0.03～0.14℃/(kg·h)，所述浇铸成型的铸型采用石墨或刚玉砂整体砂型，其重量比例为型砂∶水玻璃＝90～100∶6～12，其中水玻璃的模数3.1～3.3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310785054.2A CN116969771A (zh) | 2023-06-29 | 2023-06-29 | 一种高抗侵蚀熔铸高锆砖及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310785054.2A CN116969771A (zh) | 2023-06-29 | 2023-06-29 | 一种高抗侵蚀熔铸高锆砖及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116969771A true CN116969771A (zh) | 2023-10-31 |
Family
ID=88482320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310785054.2A Pending CN116969771A (zh) | 2023-06-29 | 2023-06-29 | 一种高抗侵蚀熔铸高锆砖及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116969771A (zh) |
-
2023
- 2023-06-29 CN CN202310785054.2A patent/CN116969771A/zh active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114507077B (zh) | 熔铸锆铬刚玉耐火砖及其制备方法 | |
| CN112608138B (zh) | 高抗氧化性非水泥结合Al2O3-SiC-C耐火浇注料及其制备方法 | |
| CN112979292B (zh) | 一种加入氧化钇的低渗出电熔锆刚玉砖的制备方法 | |
| US9481594B2 (en) | Refractory product having a high content of zirconia | |
| CN112225558A (zh) | 用于玻璃窑炉领域的梯度渐变复合技术陶瓷砖及其制备方法 | |
| CN101830701B (zh) | 高电阻高氧化锆浇铸耐火材料 | |
| CN101891369B (zh) | 熔铸α-β氧化铝筒形砖及其生产方法 | |
| JP3904264B2 (ja) | アルミナ・ジルコニア・シリカ質溶融耐火物 | |
| CN102285803A (zh) | 一种电熔锆刚玉耐火砖的生产方法 | |
| CN102538468B (zh) | 低导热熔铸锆刚玉复合砖及其生产方法 | |
| CN111484347A (zh) | 一种高强Al2O3-SiC-C耐火浇注料及其制备方法 | |
| CN111348903A (zh) | 一种铝碳质整体塞棒及其制备方法 | |
| CN112225543A (zh) | 一种应用于玻璃窑炉蓄热室的熔铸成型筒型陶瓷砖及其制备方法 | |
| CN116969771A (zh) | 一种高抗侵蚀熔铸高锆砖及其制备方法 | |
| JPH092870A (ja) | 高ジルコニア電鋳煉瓦 | |
| CN109231972B (zh) | 轻质电熔刚玉砖 | |
| CN108218192B (zh) | 耐低铁玻璃侵蚀的电熔azs砖 | |
| CN112321281B (zh) | 一种复合座砖及其制备工艺 | |
| CN114394842A (zh) | 一种烧结的致密高锆砖的制备方法 | |
| JP3928818B2 (ja) | 誘導炉 | |
| CN113045182B (zh) | 一种复合砖及其制备工艺 | |
| JPH0818880B2 (ja) | 高ジルコニア質熱溶融耐火物 | |
| CN107759237A (zh) | 一种电熔锆刚玉的热加工方法 | |
| CN117923886B (zh) | 耐侵蚀的α-β氧化铝熔铸砖及其制备方法 | |
| CN116143529B (zh) | 一种环保型铁沟浇注料及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |