TWI551564B - A refractory for molten glass, and a glass manufacturing apparatus using a refractory glass for holding glass, and a glass manufacturing method using the glass manufacturing apparatus - Google Patents
A refractory for molten glass, and a glass manufacturing apparatus using a refractory glass for holding glass, and a glass manufacturing method using the glass manufacturing apparatus Download PDFInfo
- Publication number
- TWI551564B TWI551564B TW101110886A TW101110886A TWI551564B TW I551564 B TWI551564 B TW I551564B TW 101110886 A TW101110886 A TW 101110886A TW 101110886 A TW101110886 A TW 101110886A TW I551564 B TWI551564 B TW I551564B
- Authority
- TW
- Taiwan
- Prior art keywords
- refractory
- coating layer
- glass
- platinum
- molten glass
- Prior art date
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- 239000006060 molten glass Substances 0.000 title claims description 90
- 239000011521 glass Substances 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 46
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 140
- 239000011247 coating layer Substances 0.000 claims description 125
- 229910052697 platinum Inorganic materials 0.000 claims description 70
- 229910010293 ceramic material Inorganic materials 0.000 claims description 63
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 44
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 42
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 30
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 239000011819 refractory material Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000005352 clarification Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- C03B5/167—Means for preventing damage to equipment, e.g. by molten glass, hot gases, batches
- C03B5/1672—Use of materials therefor
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- 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
- C03B5/425—Preventing corrosion or erosion
-
- 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
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
- C04B35/10—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 aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
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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
- C04B35/10—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 aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
- C04B35/1015—Refractories from grain sized mixtures containing refractory metal compounds other than those covered by C04B35/103 - C04B35/106
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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
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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
- C04B35/482—Refractories from grain sized mixtures
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- 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
- C04B35/486—Fine ceramics
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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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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Description
本發明係關於一種玻璃製造裝置中之玻璃熔解槽、澄清槽、熔融玻璃搬送管之類的與熔融玻璃接觸之用途中所使用之熔融玻璃保持用耐火物。
又,本發明係關於一種使用該熔融玻璃保持用耐火物之玻璃製造裝置。
又,本發明係關於一種使用該玻璃製造裝置之製造方法。
於使用熔融玻璃製造玻璃之玻璃製造裝置中,於玻璃熔解槽、澄清槽、熔融玻璃搬送管之類的與熔融玻璃接觸之部位使用耐火物。已知:上述部位所使用之耐火物可藉由以鉑或鉑合金被覆與熔融玻璃接觸之部位而提昇耐熱性及對於熔融玻璃之耐蝕性。
於專利文獻1中,揭示有於耐火性陶瓷(即,耐火物)基材上沈積貴金屬或金屬合金之被覆膜,將該被覆膜設為50~350 μm之厚度之陶瓷製品。於專利文獻1中,一般認為較佳為上述被覆膜含有鉑或鉑合金。就可於高溫及腐蝕環境下較佳地使用之方面而言,該陶瓷製品可較佳地用作玻璃製造裝置中之與熔融玻璃接觸之部位之耐火物。
專利文獻1:日本專利特開平5-339082號公報
如上所述,可認為於玻璃製造裝置中,與熔融玻璃接觸之部位所使用之耐火物可藉由以鉑或鉑合金被覆與熔融玻璃接觸之部位而提昇耐熱性及對於熔融玻璃之耐蝕性。
然而,本申請案發明者等人努力研究,結果發現:於玻璃製造裝置中,於以鉑或鉑合金被覆與熔融玻璃接觸之部位所使用之耐火物之情形時,自被覆層揮散之鉑混入熔融玻璃中,有使利用該熔融玻璃製造之玻璃製品產生缺陷之虞。
即,通過玻璃製造裝置之熔融玻璃之液面通常並不一定固定,有時該液面上下波動。於熔融玻璃之液面下降之情形時,耐火物之被覆層之一部分暴露於氣體環境中。由於熔融玻璃通過之部位之氣體環境成為超過1200℃之高溫,故若該氣體環境中之氧濃度較高,則微量之鉑作為氧化物而自暴露於氣體環境中之被覆層揮散。該氧化物並不穩定,可因微妙之環境之變化而還原並再次晶化為微小之金屬粒子(鉑粒子)。如此,再析出之微小金屬粒子(鉑粒子)併入熔融玻璃中。並且,未完全固溶之微少金屬粒子(鉑粒子)殘存於使用熔融玻璃所製造之玻璃製品中而成為品質方面之缺陷。
又,於長時間使用玻璃製造裝置之過程中,由於鉑之揮散而使被覆層之厚度減少,依據情形有產生耐火物暴露之部位之虞。於引起該等現象之情形時,因熔融玻璃造成之
耐火物之腐蝕成為問題,且有產生被覆層之剝離之虞。
本發明之目的在於:為解決上述先前技術中之問題而提供一種可抑制鉑自被覆層之揮散的熔融玻璃保持用耐火物、及使用熔融玻璃保持用耐火物之玻璃製造裝置、以及使用該玻璃製造裝置之玻璃製造方法。
為達成上述目的,本發明提供一種熔融玻璃保持用耐火物,其特徵在於:其係以含有5~20%之鉑、銠或銥之鉑合金被覆耐火物之與熔融玻璃接觸之面,進而以陶瓷材料被覆該鉑或鉑合金之被覆層者,以合計含量計,上述耐火物含有50~98質量%之氧化鋁及氧化鋯中之至少1種,剩餘部分含有氧化矽,上述鉑或鉑合金之被覆層之厚度為0.05~0.5 mm,上述陶瓷材料含有80~95質量%之氧化鋯,剩餘部分含有選自氧化釔、氧化鉺及氧化鈰中之至少1種,上述陶瓷材料之被覆層之厚度為0.1 mm以上,上述陶瓷材料之被覆層之孔隙率為5~20%。
依據本發明,可抑制鉑自玻璃製造裝置之與熔融玻璃接觸之部位所使用之耐火物的被覆層之揮散。藉此,可製造使因鉑揮散所造成之缺陷受到抑制之品質優異之玻璃製品。
由於鉑自耐火物之被覆層之揮散受到抑制,故而長時間使用玻璃製造裝置時之被覆層之損耗或剝離之虞下降。藉
此,可長時間穩定地使用玻璃製造裝置。
又,於本發明中,由於係藉由熱膨脹係數彼此接近之耐火物及陶瓷材料之被覆層夾持與該等相比熱膨脹係數較大之鉑或鉑合金之被覆層之構造,故而可利用玻璃製造裝置中之溫度變化防止被覆層之剝離。
於本發明中,使鉑或鉑合金之被覆層與電極連接而進行通電加熱,藉此可控制本發明之熔融玻璃保持用耐火物之溫度。
以下,針對本發明之熔融玻璃保持用耐火物進行說明。
本發明之熔融玻璃保持用耐火物可廣泛用作保持熔融玻璃之用途之耐火物。此處,所謂保持熔融玻璃,意指保持熔融玻璃而不使其流出於外部,例如,玻璃熔解槽或澄清槽之類的收容熔融玻璃之用途、或熔融玻璃搬送管之類的搬送熔融玻璃之用途係適合上述情況者。
於將耐火物用於熔融玻璃保持用途之情形時,為提昇耐熱性及對於熔融玻璃之耐蝕性,使用時與熔融玻璃接觸之面必需以鉑或鉑合金被覆。於將耐火物用於玻璃熔解槽、澄清槽、熔融玻璃搬送管等之情形時,玻璃熔解槽、澄清槽、熔融玻璃搬送管等之內面係符合上述情況者。
本發明之熔融玻璃保持用耐火物係於構成基材之耐火物中,以鉑或鉑合金被覆使用時與熔融玻璃接觸之面,進而以陶瓷材料被覆該鉑或鉑合金。
於本發明之熔融玻璃保持用耐火物中,對構成基材之耐
火物所要求的特性為於玻璃熔融溫度下之充分之耐熱性、耐氧化性及機械強度,於對鉑或鉑合金之被覆層進行通電加熱之情形時,亦要求充分之絕緣性。
為滿足該等特性,於本發明之熔融玻璃保持用耐火物中,作為構成基材之耐火物,使用以合計含量計含有50~98質量%之氧化鋁及氧化鋯中之至少1種且剩餘部分含有氧化矽者。
繼而,對構成基材之耐火物之各成分之含量的較佳範圍及其原因進行說明。
氧化鋁及氧化鋯為構成耐火物之主體之成分。若該等之合計含量未達50質量%,則於玻璃熔融溫度下之充分之耐熱性、耐氧化性及機械強度等變得不充分。另一方面,若該等之合計含量超過98%,則玻璃基質成分之含量變得不充分,有於耐火物中產生龜裂之虞。
構成基材之耐火物可僅含有氧化鋁及氧化鋯中之任一者,亦可含有兩者。於僅含有任一者之情形時,本發明之熔融玻璃保持用耐火物可依據使用時所接觸之熔融玻璃之溫度區域而適當選擇。具體而言,例如在用於玻璃熔解槽之情形時,由於使用時所接觸之熔融玻璃之溫度較高而為1400~1800℃、較佳為1500~1800℃,故而構成基材之耐火物較佳為含有對於熔融玻璃之耐蝕性更優異之氧化鋯。於該情形時,構成基材之耐火物使用含有50~98質量%之氧化鋯且剩餘部分含有氧化矽者。氧化鋯之含量較佳為60~97質量%,更佳為65~95質量%。
另一方面,在用於熔融玻璃搬送管之情形時,與玻璃熔解槽相比使用時所接觸之熔融玻璃之溫度較低而為1200~1500℃,故而構成基材之耐火物較佳為含有加工性更加優異之氧化鋁。又,於用作熔融玻璃搬送管之情形時,將耐火物之鉑或鉑合金之被覆層與電極連接而進行通電加熱,藉此控制熔融玻璃搬送管之溫度之例亦較多,於該情形時構成基材之耐火物較佳為含有具有更加優異之絕緣性之氧化鋁。於該情形時,構成基材之耐火物使用含有50~98質量%之氧化鋁且剩餘部分含有氧化矽者。氧化鋁之含量較佳為60~95質量%,更佳為75~92質量%。
又,於用作澄清槽或在相對較低之溫度下操作之熔解槽之情形時,使用時所接觸之熔融玻璃之溫度為1300~1600℃,故而就成本及對於熔融玻璃之耐蝕性之觀點而言,構成基材之耐火物可使用含有氧化鋁及氧化鋯兩者之耐火物。於該情形時,構成基材之耐火物較佳為使用氧化鋁及氧化鋯之合計含量為65~95質量%且剩餘部分含有氧化矽者。氧化鋁及氧化鋯之合計含量更佳為70~90質量%。
氧化矽係構成耐火物之玻璃基質之成分,且為生成以氧化鋁或氧化鋯為主之組成相化合物之成分。氧化矽之含量較佳為3~50質量%,更佳為5~45質量%。
上述組成之耐火物亦可含有不可避免之雜質作為剩餘部分。不可避免之雜質係由於製造耐火物時所使用之原料而不可避免地包含者。作為如上所述之不可避免之雜質之具
體例,例如可列舉:氧化鎂、氧化鐵、氧化鈦等。
構成基材之耐火物較佳為孔隙率為30%以下。若構成基材之耐火物之孔隙率過高,則該耐火物之透氣性變高,故而藉由與源自耐火物之背面側之氣體成分之接觸而使鉑或鉑合金之被覆層氧化,提昇該被覆層之耐熱性或對於熔融玻璃之耐蝕性的作用有下降之虞。又,鉑或鉑合金之被覆層自耐火物之背面側揮散,故抑制該被覆層之揮散之作用有下降之虞。再者,此處所謂耐火物之背面側,係指耐火物之相對於形成有鉑或鉑合金之被覆層之側的背面側。
再者,耐火物之孔隙率例如可藉由對利用金屬顯微鏡所拍攝之耐火物之剖面照片進行圖像處理而求出。
如上所述,構成基材之耐火物之與熔融玻璃接觸之面係以鉑或鉑合金被覆。作為鉑合金,可使用含有5~20%之銠或銥之鉑合金。
於本發明之熔融玻璃保持用耐火物中,鉑或鉑合金之被覆層之厚度為0.05~0.5 mm。若被覆層之厚度未達0.05 mm,則無法充分發揮提昇作為基材之耐火物對於熔融玻璃之耐蝕性之效果,且使用玻璃製造裝置時之被覆層之損耗成為問題。
於本發明之熔融玻璃保持用耐火物中,藉由使鉑或鉑合金之被覆層之厚度較小,並且將鉑或鉑合金之被覆層夾於熱膨脹係數彼此接近之耐火物及陶瓷材料之被覆層之間而抑制由使用玻璃製造裝置時之溫度變化所導致的鉑或鉑合金之被覆層之熱膨脹或收縮,藉此防止該被覆層之剝離,
但若鉑或鉑合金之被覆層之厚度超過0.5 mm,則無法抑制由使用玻璃製造裝置時之溫度變化所導致的鉑或鉑合金之被覆層之熱膨脹或收縮,有被覆層自耐火物上剝離之虞。
於本發明之熔融玻璃保持用耐火物中,鉑或鉑合金之被覆層之厚度較佳為0.1~0.4 mm,更佳為0.15~0.35 mm。
於本發明之熔融玻璃保持用耐火物中,在使用耐火物時與玻璃接觸之面上形成鉑或鉑合金之被覆層的方法無特別限定,較佳為藉由噴敷而形成,其原因在於:可形成與耐火物之密接性優異之被覆層,可形成較厚之被覆層,可對大面積形成被覆層等。噴敷方法可使用利用線材原料之框架噴敷或利用粉末原料之大氣電漿噴敷,但並不限定於該等。
對於鉑或鉑合金之被覆層上所形成之陶瓷材料的被覆層要求有耐熱性及對於熔融玻璃之耐蝕性。又,為防止被覆層自耐火物之剝離,要求熱膨脹係數與構成基材之耐火物接近。
又,由於下述原因,要求孔隙率為5~20%之被覆層。
為滿足該等特性,於本發明之熔融玻璃保持用耐火物中,作為構成被覆層之陶瓷材料,使用含有80~95質量%之氧化鋯且剩餘部分含有選自氧化釔、氧化鉺及氧化鈰中之至少1種者。
於本發明之熔融玻璃保持用耐火物中,氧化鋯為構成陶瓷材料之被覆層之主體之成分。
若構成被覆層之陶瓷材料中之氧化鋯之含量未達80質量
%,則對於熔融玻璃之耐蝕性下降。另一方面,若氧化鋯之含量超過95質量%,則有因於高溫下伴隨相變之體積變化而產生大規模龜裂之虞。
又,於利用以氧化鋯為主體之陶瓷材料形成被覆層之情形時,所形成之被覆層形成包含微細之層間龜裂之層狀組織,故而與於利用以氧化鋁為主體之陶瓷材料形成被覆層之情形時所形成之緻密的被覆層相比,亦有不易因使用玻璃製造裝置時之溫度變化而產生致命之龜裂的優點。
於本發明之熔融玻璃保持用耐火物中,氧化釔、氧化鉺及氧化鈰為構成被覆層之陶瓷材料之穩定劑。構成被覆層之陶瓷材料可僅含有該等中之1種,或亦可含有2種以上。於該等中,就易於控制被覆層之組織之方面而言,較佳為含有氧化釔。
於本發明之熔融玻璃保持用耐火物中,作為陶瓷材料之穩定劑之氧化釔、氧化鉺及氧化鈰之合計含量較佳為5~20質量%。若未達5質量%,則有於高溫下產生相變,且於被覆層上產生大規模龜裂之虞。另一方面,若超過20質量%,則有對於熔融玻璃之耐蝕性下降之虞。
作為陶瓷材料之穩定劑之該等之合計含量較佳為8~15質量%。
上述陶瓷材料亦可含有不可避免之雜質作為剩餘部分。不可避免之雜質係由於製造陶瓷材料時所使用之原料而不可避免地含有者。作為上述不可避免之雜質之具體例,例如可列舉:氧化鐵、氧化鉿等。
於本發明之熔融玻璃保持用耐火物中,陶瓷材料之被覆層之孔隙率為5~20%。藉由使陶瓷材料之被覆層之孔隙率為上述範圍而使抑制鉑自鉑或鉑合金之被覆層之揮散的效果提昇。關於該方面,亦示於下述實施例中。
雖然於陶瓷材料之被覆層之孔隙率為上述範圍之情形時,鉑自被覆層之揮散受到抑制之理由尚不明確,但可認為係由於以下之原因。
於陶瓷材料之被覆層之孔隙率為上述範圍之情形時,鉑或鉑合金之被覆層表面係藉由由於通過存在於陶瓷材料之被覆層上之空隙的移動或擴散而到達之氧(O2)而輕微地氧化,並作為鉑之氧化物(PtO2)而自鉑或鉑合金之被覆層表面揮散。藉由揮散之鉑之氧化物而使陶瓷材料之被覆層中之PtO2之分壓(partial pressure)上升。其結果,未進行鉑或鉑合金之被覆層表面之鉑的氧化,故而使鉑自被覆層之揮散受到抑制。
再者,如下述實施例所示般,陶瓷材料之被覆層之孔隙率可藉由對利用金屬顯微鏡所拍攝之被覆層之剖面照片進行圖像處理而求出。
於本發明之熔融玻璃保持用耐火物中,陶瓷材料之被覆層之孔隙率更佳為8~20%,進而較佳為10~20%。
於本發明之熔融玻璃保持用耐火物中,於鉑或鉑合金之被覆層上形成陶瓷材料之被覆層之方法無特別限定,較佳為藉由噴敷而形成,其原因在於:與鉑或鉑合金之被覆層之密接性優異;於形成以氧化鋯為主體之陶瓷材料之被覆
層之情形時,可將被覆層之孔隙率設為上述範圍;可形成較厚之被覆層;可對大面積形成被覆層等。噴敷方法特佳為使用大氣壓電漿噴敷法或水電漿噴敷法,但並不限定於該等。
又,為將被覆層之孔隙率設為上述範圍,較佳為使用具有中空結構之原料粉,且取較大之噴敷距離進行噴敷,但並不限定於該等方法。
再者,於藉由噴敷而形成陶瓷材料之被覆層之情形時,使被覆層之孔隙率成為上述範圍者係形成以氧化鋯為主體之陶瓷材料的被覆層之情況,於形成以除氧化鋯以外者為主體之陶瓷材料、例如以氧化鋁為主體之陶瓷材料之被覆層之情形時,被覆層之孔隙率變低,於下述實施例中亦可確認未成為上述範圍。
於本發明之熔融玻璃保持用耐火物中,陶瓷材料之被覆層之厚度為0.1 mm以上。若陶瓷材料之被覆層之厚度未達0.1 mm,則無法充分發揮抑制鉑自鉑或鉑合金之被覆層之揮散的效果,且使用玻璃製造裝置時之被覆層之損耗成為問題。
陶瓷材料之被覆層之厚度較佳為0.2 mm以上,更佳為0.3 mm以上。陶瓷材料之被覆層之厚度之上限無特別限定,但於利用噴敷法形成之情形時,較佳為1 mm以下,更佳為0.5 mm以下。
繼而,針對本發明之玻璃製造裝置、及玻璃製造方法進行說明。
於本發明之玻璃製造裝置中,於玻璃製造裝置之與熔融玻璃接觸之部位所使用之耐火物中,可使用上述本發明之熔融玻璃保持用耐火物。
於玻璃製造裝置中,作為與熔融玻璃接觸之部位之具體例,可列舉:玻璃熔解槽、澄清槽、熔融玻璃搬送管等。於本發明之玻璃製造裝置中,使用本發明之熔融玻璃保持用耐火物作為構成該等之耐火物。此處,本發明之熔融玻璃保持用耐火物係以鉑或鉑合金被覆,進而使以陶瓷材料被覆之面於使用玻璃製造裝置時成為與熔融玻璃接觸之面。
於本發明之玻璃製造裝置中,本發明係使鉑或鉑合金之被覆層與電極連接而進行通電加熱,藉此可控制本發明之熔融玻璃保持用耐火物之溫度。
繼而,針對本發明之玻璃製造方法進行說明。
於本發明之玻璃製造方法中,使用上述本發明之玻璃製造裝置,除此以外與先前之玻璃製造方法相同。本發明之玻璃製造方法可製造各種玻璃。就可製造使由鉑揮散所導致的缺陷受到抑制之品質優異之玻璃製品之方面而言,本發明之玻璃製造方法可較佳地用於製造液晶顯示器基板等之平板顯示器基板玻璃、光學用玻璃、電子用玻璃等玻璃製品。
以下,利用實施例詳細說明本發明。但是,本發明並不限定於該等。
準備含有94質量%之氧化鋯、剩餘部分含有氧化矽(5質量%)及不可避免之雜質(氧化鐵、氧化鈦等)、且其尺寸為75×75×15 mm之耐火物。
於該耐火物之一主表面上,藉由噴敷而形成鉑被覆層(0.25 mm)。
繼而,使用含有87質量%之氧化鋯、含有12質量%之作為穩定劑之氧化釔、剩餘部分為不可避免之雜質(氧化鐵、氧化鉿等)之陶瓷材料,並藉由噴敷法於鉑被覆層上形成陶瓷材料之被覆層(0.4 mm)而獲得試樣D。
將所獲得之試樣D切斷,利用金屬顯微鏡拍攝經研磨之剖面之照片,並對陶瓷材料之被覆層之剖面照片進行圖像處理,藉此求出陶瓷材料之被覆層之孔隙率,結果為12.6%。再者,將試樣D之陶瓷材料之被覆層之剖面照片示於圖2中。
將試樣D暴露於1600℃下、大氣中,利用精密天秤測定經時之質量減少。將以該測定結果作為被覆層之每單位面積之減少量之結果示於圖1中。於該條件下,未引起耐火物、及陶瓷材料之被覆層之質量減少,故而質量減少均為由鉑自鉑被覆層之揮散所造成者。
改變形成陶瓷材料之被覆層時之條件(噴敷條件)而實施,藉此使陶瓷材料之被覆層之孔隙率不同,除此以外,實施與試樣D相同之工序而製成試樣C。陶瓷材料之被覆層之孔隙率為3.2%。再者,將試樣D之陶瓷材料之被覆層之剖面照片示於圖3中。
又,改變形成陶瓷材料之被覆層時之條件(噴敷條件)而實施,藉此使陶瓷材料之膜厚及被覆之孔隙率不同,除此以外,實施與試樣D相同之工序而製成試樣B。陶瓷材料之被覆層之膜厚為0.2 mm,孔隙率為3.8%。
使用含有97質量%之氧化鋁且含有3質量%之作為用以使噴敷變得容易之添加劑之氧化鈦的陶瓷材料,藉由噴敷法於鉑被覆層上形成陶瓷材料之被覆層(0.2 mm),除此以外,實施與試樣D相同之工序而製成試樣A。陶瓷材料之被覆層之孔隙率為1.8%。
將以與試樣D相同之工序於耐火物上形成鉑被覆層後,未形成陶瓷材料之被覆層者設為試樣E。
亦將試樣A~C、及E暴露於1600℃下、大氣中,測定經時之質量減少。將結果示於圖1中。
如圖1所明確般,關於在鉑被覆層上形成孔隙率為5%以上(12.6%)之氧化鋯系被覆層的試樣D,可確認:可歷經長時間將暴露於1600℃下、大氣中時之質量減少抑制為較低,抑制鉑自鉑被覆層之揮散之效果優異。關於氧化鋯系被覆層之孔隙率未達5%之試樣B、C,可確認,與未於鉑被覆層上形成陶瓷材料之被覆層之試樣E相比,暴露於1600℃下、大氣中時之質量減少較低,但是與試樣D相比質量減少較大,尤其是,於暴露100小時以上時之質量減少較大,抑制鉑自鉑被覆層之揮散之效果較差。關於形成氧化鋁系被覆層代替氧化鋯系被覆層之試樣A,可確認藉由噴敷所形成之被覆層之孔隙率較低,暴露於1600℃下、
大氣中時之質量減少較大,抑制鉑自鉑被覆層之揮散之效果較差。
詳細地且參照特定之實施態樣對本發明進行了說明,但業者明白:可於不脫離本發明之範圍及精神之情況下進行各種修正或變更。
本申請案係基於2011年3月28日提出申請之日本專利申請案2011-070738者,其內容係作為參照而併入於此。
圖1係表示於實施例中將熔融玻璃保持用耐火物保持於高溫環境下(1600℃,空氣中)時之經時之質量減少之圖。
圖2係實施例中之試樣D之陶瓷材料之被覆層的剖面照片。
圖3係實施例中之試樣C之陶瓷材料之被覆層的剖面照片。
Claims (9)
- 一種熔融玻璃保持用耐火物,其特徵在於:其係以含有5~20%之鉑、銠或銥之鉑合金被覆耐火物之與熔融玻璃接觸之面,進而以陶瓷材料被覆該鉑或鉑合金之被覆層者,且以合計含量計,上述耐火物含有50~98質量%之氧化鋁及氧化鋯中之至少1種,且剩餘部分含有氧化矽,上述鉑或鉑合金之被覆層之厚度為0.05~0.5mm,上述陶瓷材料含有80~95質量%之氧化鋯,剩餘部分含有選自氧化釔、氧化鉺及氧化鈰中之至少1種,上述陶瓷材料之被覆層之厚度為0.1mm以上,上述陶瓷材料之被覆層之孔隙率為5~20%。
- 如請求項1之熔融玻璃保持用耐火物,其中上述鉑或鉑合金之被覆層係藉由噴敷而形成。
- 如請求項1或2之熔融玻璃保持用耐火物,其中上述陶瓷材料之被覆層係藉由噴敷而形成。
- 如請求項1或2之熔融玻璃保持用耐火物,其中上述耐火物含有50~98質量%之氧化鋯,且剩餘部分含有氧化矽。
- 如請求項1或2之熔融玻璃保持用耐火物,其中上述耐火物含有50~98質量%之氧化鋁,且剩餘部分含有氧化矽。
- 如請求項1或2之熔融玻璃保持用耐火物,其中上述陶瓷材料之被覆層之厚度為0.1mm以上且1mm以下。
- 如請求項1或2之熔融玻璃保持用耐火物,其中上述耐火物之孔隙率為30%以下。
- 一種玻璃製造裝置,其係使用如請求項1至7中任一項之熔融玻璃保持用耐火物。
- 一種玻璃製造方法,其係使用如請求項8之玻璃製造裝置。
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2012
- 2012-03-22 EP EP12763083.8A patent/EP2692703B1/en not_active Not-in-force
- 2012-03-22 CN CN201280016546.5A patent/CN103476717B/zh not_active Expired - Fee Related
- 2012-03-22 JP JP2013507457A patent/JP5821948B2/ja not_active Expired - Fee Related
- 2012-03-22 KR KR1020137025563A patent/KR101859247B1/ko active IP Right Grant
- 2012-03-22 WO PCT/JP2012/057337 patent/WO2012133107A1/ja active Application Filing
- 2012-03-28 TW TW101110886A patent/TWI551564B/zh not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200902457A (en) * | 2006-08-31 | 2009-01-16 | Corning Inc | Method and apparatus for minimizing oxidation pitting of refractory metal vessels |
Also Published As
Publication number | Publication date |
---|---|
EP2692703B1 (en) | 2018-04-25 |
JP5821948B2 (ja) | 2015-11-24 |
CN103476717B (zh) | 2015-11-25 |
WO2012133107A1 (ja) | 2012-10-04 |
KR101859247B1 (ko) | 2018-05-18 |
CN103476717A (zh) | 2013-12-25 |
KR20140021582A (ko) | 2014-02-20 |
EP2692703A4 (en) | 2014-12-10 |
EP2692703A1 (en) | 2014-02-05 |
TW201245071A (en) | 2012-11-16 |
JPWO2012133107A1 (ja) | 2014-07-28 |
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