JP2010260782A - 高ジルコニア質耐火物及び溶融窯 - Google Patents
高ジルコニア質耐火物及び溶融窯 Download PDFInfo
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- JP2010260782A JP2010260782A JP2010087737A JP2010087737A JP2010260782A JP 2010260782 A JP2010260782 A JP 2010260782A JP 2010087737 A JP2010087737 A JP 2010087737A JP 2010087737 A JP2010087737 A JP 2010087737A JP 2010260782 A JP2010260782 A JP 2010260782A
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002844 melting Methods 0.000 title claims abstract description 32
- 230000008018 melting Effects 0.000 title claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 97
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000005388 borosilicate glass Substances 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 abstract description 7
- 239000002585 base Substances 0.000 abstract 6
- 238000000605 extraction Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 44
- 239000006060 molten glass Substances 0.000 description 34
- 239000011819 refractory material Substances 0.000 description 21
- 239000013078 crystal Substances 0.000 description 17
- 229910052845 zircon Inorganic materials 0.000 description 17
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 150000001340 alkali metals Chemical class 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 238000005323 electroforming Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000009466 transformation Effects 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 3
- 238000009792 diffusion process Methods 0.000 description 3
- 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 description 3
- 229910052863 mullite Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 oxygen ion Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 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
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 230000007704 transition Effects 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
- C04B35/48—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
- C04B35/481—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 containing silicon, e.g. zircon
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- 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
- C03B5/02—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating
- C03B5/027—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating by passing an electric current between electrodes immersed in the glass bath, i.e. by direct resistance heating
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
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Abstract
【解決手段】化学成分として、質量%で、ZrO2を内掛けで85〜95%、SiO2を内掛けで3.0〜10%、Al2O3を内掛けで0.85〜3.0%、Na2Oを実質的に含まず、K2Oを外掛けで0.01〜0.5%、SrOを内掛けで1.5〜3.0%、並びにNb2O5及び/又はTa2O5を「(Nb2O5の含有量)+(Ta2O5の含有量/1.66)」で得られる値として内掛けで0.1〜2.0%含有する高ジルコニア質耐火物。
【選択図】なし
Description
なお、本明細書において、成分の含有量の「%」は質量%を意味する。また、本明細書において、耐火物に含まれる成分量について使用されている、「内掛け」とは、耐火物全体(外掛け表示成分を含まない)を100%としたとき、100%の中でのそれぞれの成分割合をいう。例えば、ZrO2を内掛けで90%含むとは、該ZrO2の含有量を含めた耐火物全体(外掛け表示成分を含まない)を100%とし、かかる100%中、ZrO2を90%含むことをいう。一方、「外掛け」とは、耐火物全体(外掛け表示成分を含まない)を100%としたとき、かかる100%に含まれていない成分の耐火物全体(外掛け表示成分を含まない)を基準にした割合をいう。例えば、K2Oを外掛けで0.1%含むとは、該K2Oの含有量を含まない耐火物全体(外掛け表示成分を含まない)を100%として、K2Oを付加的に0.1%含むことをいう。
焼結法で耐火物を得るために、原料であるZrO2、SiO2、Al2O3、K2CO3、SrCO3、Nb2O5、Ta2O5、ZrB2、AlPO4などとエタノールを電子天秤で秤量し、これを樹脂製ポットの中に、アルミナ製の粉砕ボールと一緒に投入して、ボールミルにて混合した。得られた原料とエタノールの混合液から、減圧蒸留してエタノールを除去して均質に混合された原料粉末を得た。
また、電融鋳造法で耐火物を得るために、ジルコニア原料である脱珪ジルコンに低ソーダアルミナ、シリカ、SrCO3、K2CO3、Nb2O5、Ta2O5、BPO4、B2O3などの原料を調合して混合原料とし、この混合原料を2本の黒鉛電極を備えた出力500kVAの単相アーク電気炉に装入して、2200〜2400℃の温度で完全に溶融した。
表1〜4記載の製造方法により、それぞれの成分割合(質量%)となるように耐火物を製造した。こうして、焼結法又は電鋳法で得られた種々の高ジルコニア質溶融鋳造耐火物の化学分析値と調べた諸性質を、表1〜4に併せて示す。なお、表中、CaO、MgO、K2O、B2O3、P2O5及びNa2Oは外掛け表示であり、それ以外の成分は内掛け表示である。
また、高温電気抵抗率(1500℃)は次のように算出した。まず、耐火物から直径20mm、厚さ3〜5mmの円板状のサンプルを切り出した。サンプルの片面に主電極とガード電極を、残りの面に対電極のみを白金ペーストを用いて焼き付けた。最高温度1700℃まで昇温可能な電気炉の内部にサンプルの電気抵抗を測定するための白金電極をセットした後、サンプルを電気炉内に入れた。5℃/分で昇温加熱しながら、絶縁抵抗測定装置で周波数120Hzの交流電圧(一定)を印加しながらJIS C2141に準じた3端子法で連続的に体積抵抗を測定した。得られた体積抵抗から体積抵抗率を算出して初期の高温電気抵抗率(Ω・cm)とした。
例28(比較例)は、SrOが含有されていないために、製造時にクラックの無い耐火物が得られなかった。
例29(比較例)は、SrOの含有量が少ないため、耐火物の一部にクラックが発生した。また、高温電気抵抗率も低い値を示した。例30及び例31(共に実施例)では、電鋳法でMgOとCaOを含有した耐火物を製造した。クラックのないものが得られたが、1500℃での電気抵抗率がやや低く、SrOを4%以上含有する溶融ガラス中に浸漬したときにわずかであるがジルコンの生成が確認された。例32、例33及び例34(いずれも比較例)では、Na2Oを含有するため1500℃での電気抵抗率が低かった。また、溶融ガラスへのNa流出に起因すると思われる、1500℃での電気抵抗率の経時変化が観察された。また、K2Oを含有していない例32及び例33では、SrOを4%以上含有する溶融ガラス中に浸漬したときにジルコンの顕著な生成が確認された。
例5、6(実施例)では、SrOの含有量を2.9%まで増加させたが、製造時にクラック発生は無く、電気抵抗率も高く、溶融ガラスと接触してもジルコンの生成の無い耐火物が得られた。しかし、SrOの増加にともない電気抵抗率が下がる傾向が確認された。
例9、10(実施例)ではK2Oを増量し、0.2%まで含有したが、電気抵抗率の低下はほとんど無く、十分高い電気抵抗率を持つ耐火物が得られた。
例11、12、13(いずれも実施例)では、B2O3やP2O5を含有しても、請求の範囲内であれば、クラックの発生が無く、高温での高い電気抵抗率を示す耐火物を得られた。例15〜22(いずれも実施例)は、電鋳法で製造し、クラックの発生もなく、1500℃で電気抵抗率が高かった。例17〜例19では、1500℃の電気抵抗率の初期と、SrOを4%以上含有する無アルカリホウケイ酸系の溶融ガラスと接触後とを観察したが、ほとんど変化がなく、耐久性に優れていることが確認された。また、耐火物中にジルコンの生成も確認されなかった。ただし、SrO含有量が4%未満の無アルカリホウケイ酸系の溶融ガラスに浸漬後は、例19を除き若干ではあるが、耐火物中にジルコンの生成が観察された。例19はSrO含有量が1.7%と多いため、SrO含有量が4%未満の無アルカリホウケイ酸系の溶融ガラスに対しても耐火物中のジルコン生成が抑制されたことが観察された。
Claims (8)
- 化学成分として、質量%で、ZrO2を内掛けで85〜95%、SiO2を内掛けで3.0〜10%、Al2O3を内掛けで0.85〜3.0%、Na2Oを実質的に含まず、K2Oを外掛けで0.01〜0.5%、SrOを内掛けで1.5〜3.0%、並びにNb2O5及び/又はTa2O5を「(Nb2O5の含有量)+(Ta2O5の含有量/1.66)」で得られる値として内掛けで0.1〜2.0%含有することを特徴とする高ジルコニア質耐火物。
- B2O3を外掛けで0.03〜1.0%含有する請求項1記載の高ジルコニア質耐火物。
- P2O5を外掛けで0.03〜1.0%含有する請求項1又は2記載の高ジルコニア質耐火物。
- BaOを内掛けで0.1〜1.5%含有する請求項1〜3のいずれか1項記載の高ジルコニア質耐火物。
- 原料を溶融鋳造することにより得られる請求項1〜4のいずれか1項記載の高ジルコニア質耐火物。
- SrOを含む低アルカリガラスを溶融する溶融窯に用いられる請求項1〜5のいずれか1項記載の高ジルコニア質耐火物。
- 前記低アルカリガラスが、SrOを内掛けで4%以上含むホウケイ酸ガラスである請求項6記載の高ジルコニア質耐火物。
- 請求項1〜7のいずれか1項記載の高ジルコニア質耐火物を用いてなることを特徴とするガラス溶融窯。
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RU2006124609A (ru) | 2004-01-02 | 2008-01-20 | Везувиус Крусибл Компани (Us) | Огнеупорный материал |
FR2897862B1 (fr) * | 2006-02-24 | 2008-05-09 | Saint Gobain Ct Recherches | Produit refractaire fondu et coule a forte teneur en zircone, presentant une resistivite electrique amelioree. |
JP4658870B2 (ja) | 2006-06-28 | 2011-03-23 | サンゴバン・ティーエム株式会社 | 高電気抵抗高ジルコニア鋳造耐火物 |
FR2913013B1 (fr) * | 2007-02-23 | 2009-12-18 | Saint Gobain Ct Recherches | Bloc refractaire fondu et coule a forte teneur en zircone |
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2010
- 2010-04-02 EP EP10761659.1A patent/EP2418189B1/en not_active Not-in-force
- 2010-04-02 KR KR1020117020424A patent/KR101706397B1/ko active IP Right Grant
- 2010-04-02 WO PCT/JP2010/056097 patent/WO2010116960A1/ja active Application Filing
- 2010-04-02 CN CN201080015907.5A patent/CN102369170B/zh not_active Expired - Fee Related
- 2010-04-06 JP JP2010087737A patent/JP5468448B2/ja active Active
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JPS63285173A (ja) * | 1987-05-18 | 1988-11-22 | Toshiba Monofuratsukusu Kk | 高ジルコニア鋳造耐火物 |
WO2007099253A2 (fr) * | 2006-02-24 | 2007-09-07 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Refractaire a forte teneur en zircone a grande resistivite |
JP2009527454A (ja) * | 2006-02-24 | 2009-07-30 | サン−ゴベン・セントル・ドゥ・レシェルシェ・エ・デチュード・ユーロペアン | 高ジルコニア含有量を有する高抵抗率耐火物 |
Cited By (9)
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JP5894923B2 (ja) * | 2010-10-06 | 2016-03-30 | 旭硝子株式会社 | 高ジルコニア質電鋳耐火物 |
WO2012132474A1 (ja) * | 2011-03-31 | 2012-10-04 | AvanStrate株式会社 | ガラス基板の製造方法 |
JP5668066B2 (ja) * | 2011-03-31 | 2015-02-12 | AvanStrate株式会社 | ガラス基板の製造方法 |
KR101799166B1 (ko) * | 2013-08-21 | 2017-11-17 | 산고반.티에무 가부시키가이샤 | 고지르코니아 용융 주조 내화물 |
WO2015029870A1 (ja) * | 2013-08-26 | 2015-03-05 | 旭硝子株式会社 | 無アルカリガラスの製造方法 |
JP2019048761A (ja) * | 2017-09-08 | 2019-03-28 | Agc株式会社 | 高ジルコニア質電鋳耐火物及びその製造方法 |
JP7099898B2 (ja) | 2017-09-08 | 2022-07-12 | Agcセラミックス株式会社 | 高ジルコニア質電鋳耐火物及びその製造方法 |
JP2022520068A (ja) * | 2019-02-11 | 2022-03-28 | サン-ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | 高含量のジルコニアを有する耐火性製品 |
JP7274590B2 (ja) | 2019-02-11 | 2023-05-16 | サン-ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | 高含量のジルコニアを有する耐火性製品 |
Also Published As
Publication number | Publication date |
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CN102369170B (zh) | 2014-11-12 |
TW201040124A (en) | 2010-11-16 |
WO2010116960A1 (ja) | 2010-10-14 |
KR101706397B1 (ko) | 2017-02-13 |
US20120036895A1 (en) | 2012-02-16 |
EP2418189B1 (en) | 2016-08-17 |
CN102369170A (zh) | 2012-03-07 |
KR20120022715A (ko) | 2012-03-12 |
EP2418189A4 (en) | 2012-10-10 |
US8268742B2 (en) | 2012-09-18 |
JP5468448B2 (ja) | 2014-04-09 |
EP2418189A1 (en) | 2012-02-15 |
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