JP2009155150A - 高電気抵抗高ジルコニア鋳造耐火物 - Google Patents
高電気抵抗高ジルコニア鋳造耐火物 Download PDFInfo
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- JP2009155150A JP2009155150A JP2007334026A JP2007334026A JP2009155150A JP 2009155150 A JP2009155150 A JP 2009155150A JP 2007334026 A JP2007334026 A JP 2007334026A JP 2007334026 A JP2007334026 A JP 2007334026A JP 2009155150 A JP2009155150 A JP 2009155150A
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000011521 glass Substances 0.000 claims abstract description 81
- 238000007496 glass forming Methods 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 claims description 36
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 239000011819 refractory material Substances 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract 1
- 230000035882 stress Effects 0.000 description 65
- 239000003607 modifier Substances 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 30
- 229910052845 zircon Inorganic materials 0.000 description 21
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- 239000013078 crystal Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- 230000009466 transformation Effects 0.000 description 11
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 10
- 230000007547 defect Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000005382 thermal cycling Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000006060 molten glass Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction 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
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- -1 respectively Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
【解決手段】化学成分として、ZrO2が85〜95重量%、Al2O3が0.1〜0.8重量%未満、SiO2が4〜12重量%、Na2Oが0.04重量%未満、K2Oが0.01〜0.15重量%、B2O3が0.1〜1.5重量%、CaOが0.01〜0.2重量%、BaOが0.4重量%未満、SrOが0.2重量%未満、Y2O3が0.05〜0.4重量%、Fe2O3とTiO2の合量が0.3重量%以下、P2O5とCuOは実質的に含まず(0.01重量%未満)、且つ、ガラス形成酸化物とガラス修飾酸化物のモル数の比、すなわちガラス形成酸化物/ガラス修飾酸化物が、20〜100であり、1500℃で12時間保持後の電気抵抗が200Ωcm以上である高ジルコニア鋳造耐火物。
【選択図】図2
Description
また、高ジルコニア鋳造耐火物を使用してガラス溶解炉を築炉した場合、築炉後の昇温途中で高ジルコニア鋳造耐火物のコーナー部が割れて飛んだり、炉内面として使用された高ジルコニア鋳造耐火物の表面の一部が貝殻状となって剥離する事故などが起こることがある。従って、昇温中に剥離のない安定した高ジルコニア鋳造耐火物が求められている。(課題2)
このような高ジルコニア鋳造耐火物の破損が起きた場合は、破損した部分において溶融ガラスに対する侵食性が非常に弱くなる。その為に、溶融ガラス中にストーンやコードなどの欠陥を生じるという問題がある。
熱サイクルに対する安定性は、ジルコニア結晶の1150℃付近の急激な体積変化を吸収できるガラス相が、熱サイクルを受けても、変化しない事が重要である。ガラス相にジルコンが析出すると、ジルコニアの体積変化を吸収できず、熱サイクルテスト後の残存体積膨張率が大きくなり、耐火物が紛化したりクラックが発生する場合がある。そして、熱サイクルテスト後の残存体積膨張率とガラス相の安定性には、以下の関係がある。
Claims (6)
- 化学成分として、ZrO2が85〜95重量%、Al2O3が0.1〜0.8重量%未満、SiO2が4〜12重量%、Na2Oが0.04重量%未満、K2Oが0.01〜0.15重量%、B2O3が0.1〜1.5重量%、CaOが0.01〜0.2重量%、BaOが0.4重量%未満、SrOが0.2重量%未満、Y2O3が0.05〜0.4重量%、Fe2O3とTiO2の合量が0.3重量%以下であり、P2O5とCuOは実質的に含まず(0.01重量%未満)、且つ、ガラス形成酸化物(例えば、SiO2、B2O3)を構成する各酸化物のモル数の和とガラス修飾酸化物(例えば、Na2O、K2O、CaO、MgO、SrO、BaO)を構成する各酸化物のモル数の和の比、すなわちガラス形成酸化物/ガラス修飾酸化物が、20〜100であり、1500℃で12時間保持後の電気抵抗が200Ωcm以上である事を特徴とする高ジルコニア鋳造耐火物。
- 化学成分として、ZrO2が85〜92重量%、Al2O3が0.4〜0.8重量%未満、SiO2が6〜12重量%、Na2Oが0.02重量%未満、K2Oが0.01〜0.1重量%、B2O3が0.3〜1.2重量%、CaOが0.01〜0.2重量%、BaOが0.3重量%未満、SrOが0.1重量%未満、Y2O3が0.05〜0.2重量%、Fe2O3とTiO2の合量が0.3重量%以下であり、P2O5とCuOは実質的に含まず(0.01重量%未満)、且つ、ガラス形成酸化物(例えば、SiO2、B2O3)を構成する各酸化物のモル数の和とガラス修飾酸化物(例えば、Na2O、K2O、CaO、MgO、SrO、BaO)を構成する各酸化物のモル数の和の比、すなわちガラス形成酸化物/ガラス修飾酸化物が、25〜100であり1500℃で12時間保持後の電気抵抗が300Ωcm以上である事を特徴とする高ジルコニア鋳造耐火物。
- 1650℃12時間保持後の電気抵抗が90Ωcm以上である事を特徴とする請求項1又は2に記載の高ジルコニア鋳造耐火物。
- 1650℃12時間保持後の電気抵抗が150Ωcm以上である事を特徴とする請求項1又は2に記載の高ジルコニア鋳造耐火物。
- 熱サイクルテスト後の残存体積膨張率が10%以下である事を特徴とする請求項1〜4のいずれか1項に記載の高ジルコニア鋳造耐火物。
- 熱サイクルテスト後の残存体積膨張率が5%以下である事を特徴とする請求項1〜4のいずれか1項に記載の高ジルコニア鋳造耐火物。
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