CN1950313A - 陶瓷配料及适于耐火应用的相关产品 - Google Patents
陶瓷配料及适于耐火应用的相关产品 Download PDFInfo
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- CN1950313A CN1950313A CNA2005800144882A CN200580014488A CN1950313A CN 1950313 A CN1950313 A CN 1950313A CN A2005800144882 A CNA2005800144882 A CN A2005800144882A CN 200580014488 A CN200580014488 A CN 200580014488A CN 1950313 A CN1950313 A CN 1950313A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 17
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 77
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 70
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 42
- 239000000395 magnesium oxide Substances 0.000 claims description 42
- 230000009970 fire resistant effect Effects 0.000 claims description 39
- 239000011029 spinel Substances 0.000 claims description 19
- 229910052596 spinel Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims 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 description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 11
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052863 mullite Inorganic materials 0.000 claims description 9
- 239000004927 clay Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 7
- 239000010431 corundum Substances 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011044 quartzite Substances 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 4
- 229910003023 Mg-Al Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
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- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
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- 229910052851 sillimanite Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
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- 229910052845 zircon Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- 239000000470 constituent Substances 0.000 abstract description 3
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- 238000004079 fireproofing Methods 0.000 abstract 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
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- 241000294743 Gamochaeta Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910020068 MgAl Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
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- 229910000500 β-quartz Inorganic materials 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical class COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- 101100129500 Caenorhabditis elegans max-2 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
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- 208000034189 Sclerosis Diseases 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- 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
- C04B35/16—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 silicates other than clay
- C04B35/18—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 silicates other than clay rich in aluminium oxide
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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Abstract
本发明涉及一种适于耐火应用的陶瓷配料,其含83-99.5重量%的至少一种粒级<8mm的耐火基材,0.5-12重量%的至少一种单独的粒状SiO2载体,以及可能的其余物料。本发明还涉及应用该配料的产品。
Description
本发明涉及一种陶瓷配料及适于耐火应用的相关产品。
含耐火基材的陶瓷配料用于制备耐火陶瓷产品,并可用于许多技术领域,特别是用于衬砌和修理冶金熔炉或工业用炉的衬里。另外,这类基材还用于制备所谓的功能性产品,例如用于嘴嘴、浸入管、盲管、闸板等,其在所述的熔融装置和熔炉中是所需的。
耐火基材是碱性类也可是非碱性类。MgO,特别是MgO烧结物是所有MgO产品和MgO-尖晶石产品的主要成分。MgO烧结物的主成分方镁石。制备MgO烧结物的主要基本原料是菱镁矿即碳酸镁或合成氧化镁源。
为调节某些材料特性,特剂是为改进对渣的化学耐受性,改进延展性以及抗温度交变性能和耐热性,已知与各种添加剂相组合的各种耐火陶瓷配料,由这些配料可生产相应的非成形的或成形的产品。
其中包括例如用于制备所谓镁铬铁砖(Magnesiachromitsteine)的铬矿石。其优点在于,与纯的氧化镁砖相比有更低的脆性(或更高的延展性)。但越来越需不含Cr2O3的耐火建筑材料,以避免形成毒性Cr6+的可能性。
为此提出了不含氧化铬的各种配料。DE 4403869 C2中公开的这种配料是由50-97重量%的MgO烧结物和3-50重量%的Herzynit型的尖晶石组成。与纯的MgO产品相比,由该配料烧制成的产品具有减小的脆性。
非成形的产品如浇铸物料由配料形成,该配料通过水或其它液体以及任选地通过添加剂(如粘结剂、液化剂、分散剂)形成具有一定粘度的所需加工稠度。接着将该物料以整块物料形式进行直接加工,如加工成冶金熔炉的衬里,或应用该物料制备所谓的成品构件。在此情况下,该配料也可本身或与某些添加剂相组合进行加工,如浇铸入模。
在上述浇铸物料也包括耐火混凝土物料在内的情况下,在随后的烧结过程中接着进行干燥和/或收缩时会产生裂纹,该裂纹降低了炉衬或成品构件的使用寿命。
该裂纹在用非碱性浇铸物料衬砌钢铁工业用的浇铸铁水包的情况下经常出现。为对抗该裂纹,在现有技术中建议使用形成尖晶石的物料。在形成尖晶石时引起体积增大,从而阻碍干缩。但裂纹的形成常在低于尖晶石形成的温度下就发生。不可能达到所需的较长使用寿命。
基于MgO和各种尖晶石相组合的上述产品基本上是适用的。但通过引入尖晶石在该配料中引入了附加的氧化物,这导致焙烧产品的耐热性下降。例如在含添加物MgAl2O4的氧化镁砖的情况下,不变点即第一熔体相形成的温度仅为1325℃。特别是富钙渗入物如碱性渣或混凝土熔渣会降低耐热性和使用寿命。
在焙烧的成形产品情况下,上述的影响(如渣的侵蚀、温度变化等)也常会导致耐火产品不足的使用寿命。这特别适用于例如预计有机械应力或热机械应力的应用。其包括出现周期***替变形的装置如用于制备水泥的管式转炉的耐火衬里。但在钢金属工业和非铁金属工业的炉装置中也需要具有减小的脆性(或具有提高的“挠性”)的耐火产品。
这些问题在碱性材料下比非碱性材料更严重。这主要是由于非碱性产品通常有较低的热膨胀和一定的玻璃相含量。
最后,为减少脆性己知可在配料中混入粒状的经稳定化的氧化锆(二氧化锆;ZrO2)。其缺点在于仅达到较小的脆性降低,且ZrO2的价格高。
本发明的目的在于提供一种陶瓷配料和其相关产品,该产品兼有上述所需的特性。特别是由该配料制成的产品在应用时应具有减小的脆性(即改进的延展性)、优良的热冲击性、有利的耐热性和最可能的耐腐蚀性,并且同时制造成本低。本文中术语“产品”特别是包括不成形的产品和成形产品(在应用前经热处理和不经热处理)、烧结产品和在使用时经热处理(加热)的产品。
本发明基于如下发现,即如果避免形成宏观可见(大的)裂纹且为此调节该体系使其仅在结构中形成微裂纹,则可明显降低耐火产品的脆性或预定用于耐火应用的产品的脆性。这可在配料中通过加入单独的SiO2载体达到。该方法虽然增加了裂纹密度(例如以单每平方米表面的裂纹数表示),但该裂纹具有小得多的裂纹宽度(特别是<20μm),因此比现有技术产品的宏观可见裂纹明显小。这些微裂纹对产品的使用寿命并没有同样产生不利影响。这些产品也更耐受在应用时的热机械应力,如通过热冲击产生的热机械应力。由于SiO2载体在热处理后还保持为基本上单独的组分并不形成熔体相,所以在热处理后仍保留了微裂纹形成的效果。
按本发明,结构的物理改变可通过加入一定量比的单独的粒状SiO2载体达到。本文中术语“SiO2载体”包括所有的在室温下具有足够稳定性的晶状SiO2变体。主要包括方晶石(β-形)和鳞石英(γ-鳞石英)。另一可能的SiO2变体是柯石英。石英(β-形)或石英制品也可用作SiO2载体。也可应用由所述SiO2基材通过物理和/或化学工艺(预加工)处理过的物质。例如可将石英研磨、密实、烧结和接着加工成合适的粒度。可对SiO2载体进行预处理或加工,使粗密度减小到<2.65g/cm3,例如减小到2.2-2.5g/cm3。通过混入如CaO可进一步改变该SiO2载体的化学组成。
微裂纹形成由晶状SiO2载体在相转变时的非线性热膨胀引起。这种相转变是例如在573℃时β-石英向α-石英的相转变以及在超过1050℃,经常在1250℃下的β-石英向α-方晶石的相转变,β-方晶石在270℃时即已转变成α-方晶石,这时也伴有体积膨胀。因此在下面的实施例5的产品中经380℃下的干燥后就看到所需的效果。
在最通常的实施方式中,本发明涉及包含下列组分的适于耐火应用的陶瓷配料:
A:83-99.5重量%的至少一种粒级<8mm的耐火基材,
B:0.5-12重量%的至少一种单独的粒状SiO2载体,和
C:可能的其余物料;其它组分。
该配料可仅由组分A和B组成。
所述耐火基材可以是碱性物质如煅烧白云石(即焙烧后的白云石)或氧化镁(即MgO),或是非碱性物质如基于Al2O3或ZrO2的物质。
按一种实施方式,耐火基材的含量为90-99重量%。粒状SiO2载体的含量按总配料计例如为≥1和/或≤7重量%,其上限也可为<5重量%或<4重量%。
按现有研究结果,由耐火基材如MgO基材和晶状SiO2载体组成的混合物在配料成形后的热处理(特别是焙烧)期间在SiO2载体的相应变体转换时会导致膨胀,由此产生结构中的微裂纹。该微裂纹是脆性降低的原因。
与含尖晶石添加剂如Herzynit的氧化镁产品不同,在添加晶状SiO2载体时的微裂纹形成是在烧制过程的加热期间发生的,而在现有技术中,微裂纹形成是在冷却期间发现的。
在应用玻璃状SiO2载体(石英制品)时,裂纹形成是基于烧制后冷却时耐火基本组分的较大干缩。
通过单独的粒状SiO2载体引发微裂纹的原理基本上与原料(耐火基本组分)无关,所以该原理可应用于以陶瓷粘合的、化学粘合的、碳粘合的、水粘合的、成形的和不成形的、退火的、焙烧的和未焙烧的耐火配料和产品。
温度可以是选择SiO2载体的准则。
因此,例如在述的成品构件、浇铸物料或碳粘合的耐火产品情况下,使用方晶石作为SiO2载体是合适的。以此方法,在非常低的温度水平例如在加热浇铸物料时即己可形成所需的微裂纹。由此可避免有害的干缩裂纹。
这例如也适用于整块物料的干燥或合成树脂粘合的或沥青粘合的耐火产品的硬化(退火)。
适于本发明应用的重要类型是非成形产品,例如用于制备耐火衬里或成品构件的混凝土物料或浇铸物料。这些物料可经水硬化或半水硬化,即例如是基于水泥,特别是高铝水泥的物料。本发明也可应用于贫水泥或无水泥的浇铸物料,如基于铝矾土作为非碱性耐火基材的物料。
为达到所需的加工稠度,可将干配料(如由矾土和方晶石组成的配料)与所需的水量混合。需要时加入添加剂如流动剂。干燥期间即已从270℃开始发生所述的从β-方晶石向α-方晶石的转变。
所述的作用方式与耐火基本组分的粒级基本无关。但小的最大粒度(如2mm)或粗粒级(如2-4mm)的低含量可能对降低脆性不利。尽管如此,如果SiO2载体的粒度d50或d05大于该耐火基材的细粒份的最大颗粒(或大于至少95重量%),则证明是有利的。其相应于50或95重量%的SiO2载体大于95或100重量%的该耐火基材的细颗粒。
该耐火基材通常以较宽的颗粒谱应用。除粗颗粒份(<8mm)如1-6mm外,该组分还可含中等颗粒份如0.25-<1mm和<0.25mm的细颗粒份(粉末成分)。
粗颗粒和中等颗粒之间的粒度限值也可以是1.5或2mm。粉末粒份也可例如规定为<0.125mm(125μm)的粒度级。
按各种实施方案,耐火基材的前述细粒含量按总配料计为10-30重量%、15-25重量%或25-30重量%。如前所述的中等颗粒含量的数量级按总配料计可例如为5-30重量%、10-25重量%或10-20重量%。由上述的细颗粒或中等颗粒的含量可相应计算粗颗粒含量。
按另一实施方案,耐火的、特别是氧化性基材的颗粒分布建议如下:
50-60重量%为1-6mm,
10-25重量%为0.25-<1mm,
25-30重量%为<0.25mm,
总量均为100重量%。
按一种实施方案,粒状SiO2载体的粒度不超过6mm,该颗粒的上限值也可选为3.0或1.5mm,颗粒下限也可选为0.25、0.50、1或2mm。SiO2载体的粒级通常为0.5-3mm。与小于1mm的颗粒相比,在相同量情况下粒度的增加(>1mm)可导致本发明中的更高有效性。因此1-2mm的颗粒比0.5-1mm的颗粒更有效。
作为非碱性耐火基材可选用下列组分中的至少一种:耐火粘土、硅线石、红柱石、蓝晶石、富铝红柱石、铝矾土、刚玉原材料如白刚玉或褐刚玉、片状氧化铝、煅烧氧化铝、含氧化锆的基材如锆富铝红柱石、锆刚玉、硅酸锆或氧化锆、氧化钛(TiO2)、Mg-Al尖晶石、碳化硅。
也可使用石英岩作为耐火基材,这时使用方英石、鳞石英、柯石英和/或上述经预处理的SiO2载体作为添加剂。
作为碱性耐火基材特别建议使用含83-99.5重量%的MgO含量的MgO基材。按各种实施方案,MgO含量的下限为85、88、93、94、95、96或97重量%,上限为97、98或99重量%。
按一种实施方案,MgO含量为94-99重量%,或96-99重量%。
MgO基材可由烧结氧化镁、熔融氧化镁或其混合物组成。
按一种实施方案,配料的MgO含量按总混合物计可由3-20重量%(或3-10重量%)的Herzynit型尖晶石、锰尖晶石型尖晶石或其混合物提供。在此情况下,由粒状SiO2载体在加热期中引发的微裂纹会由在高温过程的冷却期中尖晶石组分产生的其它微裂纹所补充。
此外,所述配料可含较少量的其它成分,例如至少一种如下组分:(元素)碳、石墨、树脂、沥青、炭黑、焦炭、焦油。
因此,该配料可用于制备碳粘合的产品。特别是可将该配料用于碳粘合的产品或焦油浸渍的产品。
所谓ASC产品属此列,其命名是源自主成分A(表示Al2O3载体)、S(表示SiC和/或Si金属)和C(表示碳载体)。氧化镁载体(用于尖晶石形成)以及Mg-Al尖晶石也可以是该配方的成分。这种配料用合成树脂如酚醛树脂作为粘合剂粘合。其例如用于生铁铁水包,但也可用于盲管、浸入管等。
对合成树脂粘合的产品,其硬化过程可如下进行,即例如可达到或超过从β-方英石转变成α-方英石的转变温度,从而使得在提供预成型的模制件时在产品中己存在微裂纹。或者,也可在较低温度(如160-220℃)下硬化(退火),并将微裂纹形成的过程推移到较后的使用中。该微裂绞的形成在产品安装后加热该产品时发生。
己提及,所述配料也特别可用于制备焙烧的耐火产品,特别是焙烧的耐火模制件。这时如通常一样可将粘合剂,特别是暂时的粘合剂如木质素磺酸盐溶液混入配料中,然后例如将该混合物压制成砖,并进行干燥和焙烧。典型的焙烧温度为1300-1700℃。适于含96重量%的MgO和4重量%的粒状SiO2载体的配料的典型焙烧温度为1400℃(±50℃)。在选择焙烧温度时,下面的经验是适用的:太高的焙烧温度或使用温度会由于太强的烧结(通常伴随有熔融相)导致SiO2载体的作用降低,并由此使脆性增加。这样要考虑在SiO2载体和耐火基材之间的反应特性,特别是熔融相的形成,同时又不能阻碍足够的烧结。由此,准确的焙烧温度与具体选定的配料组分有关,并由经验来确定。
下列将以各种实施方案详述本发明。下面总共描述5种含非碱性基本成分的配料(Nr.1-5)、一种基于MgO的配料(Nr.7)和每一情况下的按现有技术的对比例(Nr.6、8),其中原料组成和化学组成以氧化物分析形式给出。
实施例1-3的配料用于制备基于非碱性基材的焙烧的成形产品。
当然必需在该配料成分中混入暂时的粘合剂。这些可包括例如亚硫酸盐废液、磷酸或单铝磷酸盐。也可在配方中加入粘合剂粘土。由该配料在通常的压机压力(如65-130MPa)下制成砖或其它模制件,并接着进行焙烧。焙烧温度的选择应使烧结充分,但温度不能高到产生太强的烧结而有碍于脆性的降低作用。为此在给定的成分组成下,非碱性基材的细粒份的粒度分布以及粘合剂将尤其起决定作用。
实施例1的焙烧温度选为1450℃。由配料2和3制备(压制)的砖在1550℃下焙烧。
配料Nr.4用于制备所谓的ASC产品,即如上所述的含添加剂方英石的碳粘合的产品。通过方英石转变,由该配料制成的产品在退火(400℃)时引发结构中的微裂纹。
实施例5示出一种含氧化铝水泥的适于浇铸物料的配料。该配料与水混合,并由其制成模制件,该模制件在380℃下干燥或退火。此外,制备不含方英石添加剂的对比物料(Nr.6),并制成类似的试样,也在380℃下干燥或退火。为了补偿在配料Nr.6中所缺的4重量%的方英右,对配料Nr.5的所有其余基本组分均相对增加4%。
实施例(1)
耐火基材 | 粒度 | 重量% | 氧化物组成 | 重量% |
红柱石 | 1-3mm | 55 | SiO2 | 40.4 |
红柱石 | 125μm-<1mm | 16 | Al2O3 | 58.0 |
红柱石 | <125μm | 25 | Fe2O3 | 0.8 |
石英岩 | 0.5-1mm | 4 | TiO2 | 0.2 |
CaO+MgO | 0.2 | |||
K2O+Na2O | 0.3 |
实施例(2)
耐火基材 | 粒度 | 重量% | 氧化物组成 | 重量% |
熔融富铝红柱石 | 2-4mm | 18 | SiO2 | 24.3 |
熔融富铝红柱石 | 0.3-<2mm | 51 | Al2O3 | 74.3 |
熔融富铝红柱石 | <125μm | 22 | Fe2O3 | 0.8 |
煅烧氧化铝 | <0.1mm | 5 | TiO2 | 0.1 |
方英石 | 1-3mm | 4 | CaO+MgO | 0.1 |
K2O+Na2O | 0.4 |
实施例(3)
耐火基材 | 粒度 | 重量% | 氧化物组成 | 重量% |
白刚玉 | 3-5mm | 13 | SiO2 | 5.0 |
白刚玉 | 1-<3mm | 42 | Al2O3 | 94.6 |
白刚玉 | <1mm | 15 | Fe2O3 | 0.1 |
片状氧化铝 | <125μm | 15 | TiO2 | 0.1 |
煅烧氧化铝 | <0.1mm | 10 | CaO+MgO | 0.1 |
柯石英 | 1-3mm | 3 | K2O+Na2O | 0.2 |
柯石英 | 3-5mm | 2 |
实施例(4)
耐火基材 | 粒度 | 重量% | 氧化物组成* | 重量% |
白刚玉 | 2-4mm | 15 | SiO2 | 20.2 |
白刚玉 | 0.3-<2mm | 30 | Al2O3 | 78.7 |
铝矾土 | 0.3-2mm | 20 | Fe2O3 | 0.4 |
方英石 | 0.5-1mm | 4 | TiO2 | 0.5 |
片状氧化铝 | <125μm | 10 | CaO+MgO | 0.1 |
煅烧氧化铝 | <250μm | 5 | K2O+Na2O | 0.1 |
SiC | <125mm | 5 | ||
Si金属 | <50μm | 3 | ||
石墨 | <0.5mm | 8 | ||
含硬化剂的酚醛清漆树脂 | +1.5 | |||
可熔性酚醛树脂 | +3.5 |
*按氧化性灼烧样品计
实施例(5)
耐火基材 | 粒度 | 重量% | 氧化物组成 | 重量% |
铝矾土 | 1-3mm | 44 | SiO2 | 14.9 |
铝矾土 | 125μm-<1mm | 22 | Al2O3 | 81.0 |
铝矾土 | <125μm | 10 | Fe2O3 | 1.3 |
方英石 | 0.5-1.5mm | 4 | TiO2 | 1.6 |
煅烧氧化铝 | <250μm | 8 | CaO+MgO | 1.2 |
反应性氧化铝 | <125μm | 4 | K2O+Na2O | 0.1 |
微二氧化硅 | <125μm | 4 | ||
氧化铝水泥 | 4 | |||
分散剂 | +0.2 | |||
柠檬酸 | +0.1 |
机械断裂检验表明,微裂纹的引发可降低脆性。产品脆性的数值可以不同的方式得到。例如该数值是特征长度:
在此方程中,GF为比断裂能(N/m),E为弹性模量(Pa),ft(Pa)为拉伸强度。该特征长度越大,耐火工程材料的脆性越小。通常发现脆性随比断裂能GF与拉伸强度ft的比值GF/ft上升而下降。为表征本发明的产品,应用比值GF/σKZ。测定比断裂能GF和标称切口拉伸强度σKZ的楔形缝试验的基本功能原理描述于K.Rieder等人的“Bruchmechanische Kalt-und Heissprüfung feuerfestergrobkeramischer Werkstoffe”,Fortschrittsberichte der DeutschenKeramischen Gesellschaft,Werkstoffe-Verfahren-Anwendung-Band 10(1995),Heft 3,ISSN 0177-6983,62-70。该检验方法进一步阐述如下:
楔形缝试验在对产品进行热处理(例如干燥、退火或灼烧产品)后在室温下进行。
说明书最后给出的表列举出与原始产品相关的楔形缝试验的条件。“未成形产品”是指配料,视需要是加有粘合剂和/或调制液体的配料。术语“成形产品”包括所有的形状和成形方法,这时该产品至少必需具有下面所述的检验体的大小。这里区别开未经热处理和热处理后的成形产品以及其相应的不同粘合类型。“原始未成形产品”例如浇铸物料或注塑物料可在制成整块物体(如炉衬里)后在使用时固化,并可因此称为“模制件”。这也适用于至少在使用时经受较高温度的成品构件。
对每一产品至少检验三个试样,取其结果平均值用于评定。试样的形状示于图1。矩形试样的尺寸为:宽B:110mm,长L:75mm,高H:100mm。其上面可见具有下列尺寸的凹槽A:宽b:24mm,长l:75mm,高h:22mm。该凹槽A用于容纳用于传力的条棒、辊和楔形块。宽b’为3mm且高h’为2mm的切口K1从凹槽A的底部向下向基面G方向延伸。在切口K1的端面上总是连按另一切口K2、K3,K2、K3延伸到试样的基面G。K2、K3的宽b”为3mm,高h”为6mm。
为进行试验,在将两条捧LS从外侧呈镜像引入凹槽A中,该条棒的形状和大小示于图2。在条棒LS之间的中心放置图3(上)所示的楔形块Kl,该楔形块经两辊R(图3,下)支承该条棒LS,如图4所示。如果产品制备的成形过程是通过单轴压机完成,则该试样的取出方式是应使压制力的方向平行于韧带面(其为在检验时产生断裂的面)的平面。楔形块K和条棒LS的长度相应于试样长度即75mm。辊R稍长些。楔形块Kl、条棒LS和辊R由钢制成。检验时试样支撑在线性支座上。该支座是边长为5mm的四边形的钢棒S,其长度至少相应于试样宽度即75mm,并延伸到试样的总长度。棒S以两边均匀地覆盖切口K2、K3的宽度。该检验的过程示于图5。往该图的上部可见到测力计KM。通过检验机向楔形块Kl加载而产生的垂直力导致产生水平力,在检验过程中该水平力导致稳定发展的裂纹形成。期间测定垂直负荷FV和垂直位移δV。记录该测定值,直到负荷下降到10%或小于最大荷载。断裂能GF由负荷/位移图下的面积确定。因此为:
在此方程(II)中,A是韧带面积即66×63mm2[(100-22-12)×(75-6-6)],δmax是测量过程中的最大位移。标称切口拉伸强度由下列方程计算:
在此方程(III)中,B是韧带长(63mm),W是韧带高(66mm)。值y表示通过辊产生的水平力的作用线离该韧带面的重心的垂直距离。为此,作为足够近似使用值62mm(图1和4)。在关系式(III)中用的水平最大负荷FHmax可按下式由垂直最大负荷FVmax求得:
在此式(IV)中,α意指楔形角,选为10°。该检验控制在检验机冲头垂直速度为0.5mm/min下进行。
对于在某个产品中未能遵循这些检验参数的情况,例如因为不能制备足够大的试样或由于源自疑虑测定的绝对值的准确性等其它原因,则测定本发明产品以及类似制备和检验的不含SiO2载体的产品的比值GF/σKZ。这时,缺少的SiO2含量按比例加入到该产品的所有其它组分中。因此,脆性降低以本发明产品的比值GF/σKZ与类似制备的不含SiO2载体的产品的比值GF/σKZ的比来确定。该比>1,通常>1.5或>1.8。力求该比值>2。下面的实施例(7)、(8)的值几乎达3。
下表中结出比断裂能GF、标称切口拉伸强度σKZ以及两者的比值。本发明的产品的特征是比值GF/σKZ>40。力求>50的值。
实施例(5) | 对比例(6) | |
GF[N/m] | 243 | 255 |
σKZ[MPa] | 4.6 | 10.7 |
GF/σKZ[μm] | 52.8 | 238 |
本发明产品的比断裂能与标称切口拉伸强度的比值要高出一倍以上,由此可明显降低脆性。
实施例(7) | 对比例(8) | |
氧化镁烧结体1-5mm | 55 | 55 |
氧化镁烧结体0.125-1mm | 14 | 18 |
氧化镁烧结体<0.125mm | 27 | 27 |
石英岩0.5-1mm | 4 | |
焙烧温度℃ | 1400 | 1400 |
SiO2[重量%] | 4.13 | 0.18 |
Fe2O3[重量%] | 0.48 | 0.49 |
Al2O3[重量%] | 0.10 | 0.09 |
CaO[重量%] | 0.78 | 0.8 |
MgO(约)[重量%] | 94.5 | 98.4 |
Edyn[GPa] | 14.9 | 75.8 |
GF[N/m] | 210 | 264 |
σKZ[MPa] | 4.6 | 14.8 |
GF/σKZ[μm] | 45.6 | 17.9 |
σKZ/Edyn[10-3] | 0.31 | 0.20 |
为证明脆性下降也进行了所述的楔形缝试险。
图6示出楔形缝试验(在室温下进行)的负荷/位移图,并表明本发明配料(7)有明显小的脆性。这可由上述表中的比断裂能GF与标称切口拉伸强度σKZ的较高比值看出。
此外,动态弹性摸量Edyn可由外延波的共振频率测定[Hennicke,Leers:Die Bestimmung elastischer Konstanten mit dynamischenMethoden,Tonindustrie-Zeitung 89Nr.23/24,539-543(1976)]。
如上表所示,在氧化镁组分中添加粒状SiO2载体可明显降低弹性模量,即从75.8Gpa降到14.9Gpa。
从表中还看出,在本发明方案中,标称切口拉伸强度与动态弹性模量之比明显较高。按Kingery[W.D.Kingery等人:Introduction toCeramics,John Wiley&Sons,1960;ISBN 0-471-47860-1],可推测出热应力参数R增加。
虽然本发明除耐火基本组分外用简单而廉价的添加剂(粒状SiO2载体)解决了问题,所述配料证实为用于制备具有较小脆性的耐火产品的优良基础,因此显示优良的耐热冲击性,并且是耐腐蚀的,但与现有技术的其它产品相比却仍未减小耐热性。配料组分和制备条件的选择要使产品的GF/σKZ之比>40。
与不含粒状SiO2载体的氧化镁产品相比,本发明产品的优点是在热冲击下的较高的机械稳定性或热机稳定性或明显的变形性。与氧化镁铬铁产品相比,其显示出是无铬衬里材料的优点,由此可避免形成Cr6+的危险。与尖晶石产品相比,一方面通过较廉价可得的SiO2载体达到成本上的优点。另一方面在CaO-MgO-SiO2体系中CaO与SiO2的重量比(C/S比)低于0.93的工程材料,正如本发明的产品所预计的,其不变化点至少为1502℃,在C/S比低于约0.25(镁橄榄石混晶作为唯一的硅酸副相存在)时,该不变化点随C/S比的下降还可升高直到最大约1860℃。
与此相反,相应于现有技术的C/S比超过1.87的含尖晶石(MgAl2O3)的氧化镁砖的不变点为1325℃。在本发明产品情况下的较高不变点可用于改进热性能,只要在顾及产品组成以及使用中的实际渗入情况下熔融相量也是较有利的。与含ZrO2添加剂的产品相比,由于较低的SiO2载体成本,无论如何在经济上是有利的。
在非碱性产品情况下,与使用富铝红柱石或锆富铝红柱石相比,其优点是不引入含玻璃相的并由此产生对软化性能的有害影响的组分。本发明的产品可以是一种仅由晶相组成的材料组合物。另一优点在于,在应用方英石时,在270℃下即己开始出现微裂纹并由此使脆性降低。所以也可制备或使用在较低温度下就有小脆性的未焙烧的产品。如浇铸物料和成品构件均属此列。也可例如以这种方法降低碳粘合的未焙烧产品的脆性。
不含碳的未成形产品 | 不含碳的成形产品 | 经使用时的热处理固化后的原始未成形产品(不含碳粘合剂) | 含陶瓷粘合剂的经热处理的成形产品 | |
方英石/鳞石英8 | 1 | 3 | 5 | 7 |
其余的SiO2载体9 | 2 | 4 | 6 | 7 |
含碳的未成形产品 | 含碳的成形产品 | 经使用时的热处理固化后的原始未成形产品(含碳粘合剂) | 含碳粘合剂的经热处理的成形产品 | |
方英石/鳞石英8 | 1* | 3* | 5* | 3* |
其余的SiO2载体9 | 2* | 4* | 6* | 4* |
经使用时的热处理固化后的原始未成形产品(含化学粘合剂) | 含化学粘合剂的经热处理的成形产品 | |||
方英石/鳞石英8 | 5 | 3 | ||
其余的SiO2载体9 | 6 | 4 | ||
经使用时的热处理固化后的原始未成形产品(含水粘合剂) | 含水粘合剂的经热处理的成形产品 | |||
方英石/鳞石英8 | 5 | 3 | ||
其余的SiO2载体9 | 6 | 4 |
表中各符号意义如下:
1:由配料,需要时加入粘合剂和/或水(如化学粘合剂或水粘合剂)后成形试样,并在350℃下热处理。
2:由配料,需要时加入粘合剂和/或水(如化学粘合剂或水粘合剂)后成形试样,并在650℃或在≥1350℃下热处理。
3:由产品截出试样,并在350℃下热处理,只要该产品未预先在≥350℃下经热处理。
4:由产品截出试样,并在650℃或在≥1350℃下热处理,只要该产品未预先在≥650℃或在≥1350℃下经热处理。
5:由在使用时形成的产品截出试样,并在350℃下热处理,只要该产品在使用时未经≥350℃下的热处理。
6:由在使用时形成的产品截出试样,并在650℃或在1350℃下热处理,只要该产品在使用时未经≥650℃或在≥1350℃下的热处理。
7:由产品截出试样。
8:该SiO2载体至少50重量%由方英石和/或鳞石英构成。
9:该SiO2载体少于50重量%由方英石和/或鳞石英构成。
在4和6的情况下,热处理通常在1350℃下进行。如果1350℃太高而不能实现脆性降低,则热处理在650℃下进行,这超过石英破裂的温度。
*:在热处理时降低大气压。
Claims (20)
1.一种适于耐火应用的陶瓷配料,其含:
A:83-99.5重量%的至少一种粒级<8mm的耐火基材,和
B:0.5-12重量%的至少一种单独的粒状SiO2载体,以及
C:可能的余料;其它组分。
2.权利要求1的配料,其耐火基材至少部分是非碱性基材。
3.权利要求1的配料,其耐火基材至少部分由煅烧白云石和/或氧化镁组成。
4.权利要求1的配料,其含:
A)90-99重量%的耐火基材,和
B)1-7重量%的粒状SiO2载体。
5.权利要求1的配料,其粒状SiO2载体由至少一种下列SiO2变体组成:方英石、鳞石英、柯石英、粗密度小于2.65g/cm3的经预处理的产品。
6.权利要求1的配料,其SiO2载体的粒度d50大于耐火基材细粒份的95重量%。
7.权利要求1的配料,其SiO2载体的粒度d05大于耐火基材细粒份的95重量%。
8.权利要求1的配料,其耐火基材的细粒份的95重量%<250μm。
9.权利要求1的配料,其耐火基材的细粒份的95重量%<125μm。
10.权利要求8或9的配料,其耐火基材的细粒份占总配料的10-30重量%。
11.权利要求1的配料,其SiO2载体的粒度不超过6mm。
12.权利要求1的配料,其SiO2载体的粒度不超过3mm。
13.权利要求1的配料,其SiO2载体的粒度为0.5-3mm。
14.权利要求1的配料,其耐火基材的粒度小于6mm。
15.权利要求1的配料,其耐火基材有下列粒度分布:
a)50-60重量%为1-6mm,
b)10-25重量%为0.25-小于1mm,
c)25-30重量%为小于0.25mm,
其中总量为100重量%。
16.权利要求1的配料,其含下列组分中的至少一种非碱性耐火基材:耐火粘土、硅线石、红柱石、蓝晶石、富铝红柱石、铝矾土、刚玉原材料如白刚玉或褐刚玉、片状氧化铝、煅烧氧化铝、石英岩、含氧化锆的基材如锆富铝红柱石、锆刚玉、硅酸锆或氧化锆、氧化钛、Mg-Al尖晶石、碳化硅。
17.权利要求1的配料,其含MgO基材,该MgO基材按总混合物计达3-20重量%,该MgO基材由Herzynit型尖晶石、锰尖晶石型尖晶石或其混合物组成。
18.权利要求1的配料,其含至少一种下列组分作为其余成分:碳、石墨、树脂、沥青、炭黑、焦碳、焦油。
19.一种基于权利要求1-18之一的配料的产品,其比断裂能GF(N/m)和标称切口拉伸强度σKZ(MPa)之比大于40,其均采用如本文所述的试样楔形缝试验测定。
20.一种基于权利要求1-18之一的配料的产品,其采用如本文所述的试样楔形缝试验测定的比断裂能GF(N/m)和标称切口拉伸强度σKZ(MPa)之比至少是对不含单独的粒状SiO2载体的类似产品同样测定的比值的1.5倍,其余基本组分按比例由缺少的SiO2含量调节到总共为100重量%。
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DE102004010740.8 | 2004-03-05 | ||
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Cited By (9)
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CN102712541A (zh) * | 2009-12-24 | 2012-10-03 | 法商圣高拜欧洲实验及研究中心 | 用于玻璃陶瓷干燥耐火材料的粉末 |
TWI492915B (zh) * | 2012-01-11 | 2015-07-21 | Saint Gobain Ceramics | 耐火物件及使用耐火物件形成玻璃板之方法 |
CN104860656A (zh) * | 2015-05-04 | 2015-08-26 | 安徽省亚欧陶瓷有限责任公司 | 一种高耐火陶瓷砖及其制备方法 |
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CN104926323A (zh) * | 2015-05-18 | 2015-09-23 | 浙江长兴银兴窑业有限公司 | 一种含有碳化硅的耐火材料 |
CN104944926A (zh) * | 2015-05-18 | 2015-09-30 | 浙江长兴银兴窑业有限公司 | 一种碳化硅耐火材料 |
CN105016745A (zh) * | 2015-05-18 | 2015-11-04 | 浙江长兴银兴窑业有限公司 | 含有碳化硅的耐火材料 |
CN105683124A (zh) * | 2013-07-26 | 2016-06-15 | 圣戈班研究中心与欧洲研究院 | 具有高氧化铝含量的产品 |
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DE2323486A1 (de) * | 1973-05-10 | 1974-11-21 | Bosch Gmbh Robert | Verfahren zur herstellung von weissen brennkapseln zum brennen von keramischen formteilen |
DE2605950B2 (de) * | 1976-02-14 | 1978-08-24 | Vereinigte Grossalmeroder Thonwerke, 3432 Grossalmerode | Feuerfestes Erzeugnis mit verbesserter Temperaturwechselbeständigkeit |
US4391917A (en) * | 1980-10-27 | 1983-07-05 | Dresser Industries, Inc. | Alumino-silicate refractory brick |
-
2004
- 2004-03-05 DE DE200410010739 patent/DE102004010739B4/de not_active Withdrawn - After Issue
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- 2005-03-03 CN CNB2005800144882A patent/CN100528807C/zh not_active Expired - Fee Related
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CN102712541A (zh) * | 2009-12-24 | 2012-10-03 | 法商圣高拜欧洲实验及研究中心 | 用于玻璃陶瓷干燥耐火材料的粉末 |
CN102712541B (zh) * | 2009-12-24 | 2014-08-27 | 法商圣高拜欧洲实验及研究中心 | 用于干燥耐火材料的包括玻璃陶瓷颗粒的粉末 |
US8980775B2 (en) | 2009-12-24 | 2015-03-17 | Saint-Gobain Centre De Recherches Et D'etudes European | Powder for glass-ceramic dry refractory material |
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US10590041B2 (en) | 2012-01-11 | 2020-03-17 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object and process of forming a glass sheet using the refractory object |
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CN100528807C (zh) | 2009-08-19 |
DE102004010739A1 (de) | 2005-09-22 |
UA90469C2 (ru) | 2010-05-11 |
DE102004010739B4 (de) | 2006-05-18 |
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