WO2009113638A1 - ガラス搬送用ロールおよびその製造方法ならびにそれを用いた板ガラスの製造方法 - Google Patents
ガラス搬送用ロールおよびその製造方法ならびにそれを用いた板ガラスの製造方法 Download PDFInfo
- Publication number
- WO2009113638A1 WO2009113638A1 PCT/JP2009/054806 JP2009054806W WO2009113638A1 WO 2009113638 A1 WO2009113638 A1 WO 2009113638A1 JP 2009054806 W JP2009054806 W JP 2009054806W WO 2009113638 A1 WO2009113638 A1 WO 2009113638A1
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- WO
- WIPO (PCT)
- Prior art keywords
- glass
- roll
- spray coating
- thermal spray
- cermet
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims description 52
- 239000005357 flat glass Substances 0.000 title claims description 33
- 230000008569 process Effects 0.000 title claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 189
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 92
- 239000000919 ceramic Substances 0.000 claims abstract description 73
- 239000002243 precursor Substances 0.000 claims abstract description 54
- 239000011195 cermet Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000005507 spraying Methods 0.000 claims description 131
- 238000000576 coating method Methods 0.000 claims description 127
- 239000011248 coating agent Substances 0.000 claims description 124
- 239000000463 material Substances 0.000 claims description 43
- 238000004519 manufacturing process Methods 0.000 claims description 29
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- 229910003470 tongbaite Inorganic materials 0.000 claims description 12
- 238000005728 strengthening Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000003703 image analysis method Methods 0.000 claims description 5
- 230000002787 reinforcement Effects 0.000 claims description 3
- 238000007517 polishing process Methods 0.000 claims 1
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 55
- 239000007921 spray Substances 0.000 abstract description 14
- 238000011049 filling Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 49
- 239000002585 base Substances 0.000 description 47
- 239000011651 chromium Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 27
- 238000005498 polishing Methods 0.000 description 27
- 239000012071 phase Substances 0.000 description 25
- 229920001709 polysilazane Polymers 0.000 description 24
- 230000007797 corrosion Effects 0.000 description 23
- 238000005260 corrosion Methods 0.000 description 23
- 238000007789 sealing Methods 0.000 description 21
- 229910045601 alloy Inorganic materials 0.000 description 19
- 239000000956 alloy Substances 0.000 description 19
- 239000011148 porous material Substances 0.000 description 17
- 230000003746 surface roughness Effects 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 238000007750 plasma spraying Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000002093 peripheral effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 238000005422 blasting Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 238000007751 thermal spraying Methods 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 4
- 229910001120 nichrome Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000003426 chemical strengthening reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010285 flame spraying Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910001347 Stellite Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007372 rollout process Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B35/00—Transporting of glass products during their manufacture, e.g. hot glass lenses, prisms
- C03B35/14—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands
- C03B35/16—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands by roller conveyors
- C03B35/18—Construction of the conveyor rollers ; Materials, coatings or coverings thereof
- C03B35/181—Materials, coatings, loose coverings or sleeves thereof
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
Definitions
- the present invention relates to a glass transport roll used for transporting glass in a high temperature state in the manufacture of plate glass, a method for manufacturing the same, and a method for manufacturing plate glass using the glass transport roll.
- Many glass transport rolls such as rare rolls for gradually cooling while being used are used.
- the roll for glass conveyance is in direct contact with the high-temperature glass before being cooled and solidified, it affects the quality of the plate glass. For example, when the glass ribbon immediately after taking out from the tin bath is sufficiently hot, and the surface of the roll is an iron-based metal, microscopic adhesion easily occurs between the two. And when a glass ribbon moves on a roll, the glass of the adhere
- a small amount of metallic tin or tin oxide is attached to the lower surface of the glass ribbon pulled up from the tin bath.
- a part of the adhering matter adheres firmly to the surface of the transport roll, and there is a risk of causing scratches on the surface of the glass ribbon as in the case of the glass residue described above. .
- Patent Document 1 describes a transport roll in which a ceramic sprayed coating is formed on the surface of an iron-based alloy roll base material, and a base film made of cermet is provided between the ceramic sprayed coating and the base material.
- Patent Document 2 describes a ceramic sprayed coating is provided on the surface of the metal base material of the roll body portion, and between the metal base material and the ceramic sprayed coating, an intermediate thermal expansion coefficient is provided.
- Patent Document 3 describes that the sprayed coating such as ceramics and cermet is subjected to a sealing treatment to improve and improve the sprayed coating, although it is not a roll for transporting glass.
- a conventional transport roll having a base layer made of metal or cermet on the surface of a roll base material and laminated with a ceramic spray coating thereon has a high temperature at least when used in a plate glass production line. When the roll atmosphere temperature is 550 ° C.
- the present invention has been made in view of the above circumstances.
- a base layer and a ceramic spray coating are laminated on the surface of a roll base material. It is an object of the present invention to be able to suppress particle dropping and peeling of the sprayed coating itself.
- oxygen and corrosive gas in the plate glass production line As a result of earnest research on the phenomenon that particles fall off from the ceramic spray coating and the peeling of the ceramic spray coating itself after long-term use, the present inventors have found that the occurrence mechanism of these problems is oxygen and corrosive gas in the plate glass production line. It has been found that this is essentially related to the degradation of the ceramic sprayed coating due to aging, specifically the degradation caused by the underlying film. That is, oxygen and sulfur oxide (SO x ), which is a corrosive gas, are present in the atmosphere of the plate glass production line, and the ceramic spray coating forming the surface layer of the glass transport roll has through pores. Therefore, although oxygen and sulfur oxide are trace amounts, they pass through the ceramic sprayed coating and come into contact with the underlying layer.
- SO x oxygen and sulfur oxide
- Oxygen or sulfur oxide (SO x ) oxidizes or corrodes a metal spray coating or a cermet spray coating that constitutes the base layer, thereby expanding the volume of the base layer.
- the expanded underlayer pushes up the surface layer, and a crack penetrating from the underlayer to the surface occurs in the ceramic spray coating forming the surface layer.
- the state of oxidation and corrosion of the underlayer varies depending on the temperature and atmosphere surrounding the target roll, and also the composition of the underlayer itself. It can be classified into two types in which the peeling of the film itself is dominant. In the first aspect, the oxidation or corrosion of the underlayer proceeds relatively quickly, and the volume of the underlayer further expands.
- the second mode is that the corrosion rate of the underlayer is relatively slow due to various environmental conditions, and a thin reaction layer is formed at the interface between the underlayer and the ceramic sprayed coating.
- the dominant condition is that the ceramic sprayed coating itself peels from the vicinity.
- the other mode that is not dominant also occurs, and it is necessary to suppress them together. Such a problem may occur not only in the method for producing plate glass by the float method, but also in a glass conveying roll in other plate glass producing methods.
- the present inventors have further studied based on such knowledge, and by performing a sealing treatment on the surface of the ceramic sprayed coating using a silica precursor solution, the above-described particle dropping from the ceramic sprayed coating and the ceramics are performed.
- the inventors have found that the thermal spray coating itself can be prevented from peeling off, and have completed the present invention.
- this sealing treatment causes fine cracks to occur on the surface of the ceramic sprayed coating due to heat during use, but the present invention suppresses deterioration of the underlayer and the interface between the underlayer and the ceramic sprayed coating. By doing so, the problems of the first and second modes described above can be solved.
- the effect of the present invention is enhanced by changing the state of penetration of the silica precursor solution into the ceramic spray coating corresponding to the dominant mode in the glass transport roll of the present invention. That is, depending on the difference in the manner of progress of oxidation and corrosion of the underlayer, in the case where particle dropout, which is the first mode, is dominant, the bonding force between particles forming the coating on the surface of the sprayed coating is increased. In the case of exfoliating, which is the second mode of peeling, the sealing treatment that enhances the impregnating property of the ceramic sprayed coating is improved to penetrate the interface between the underlayer and the ceramic layer and protect the interface. It is preferable to select a hole treatment. Which mode is dominant can be determined by exposing the sprayed film to an environment of high temperature corrosive gas as described later.
- the present invention is a glass transport roll in which a first thermal spray coating made of cermet or metal is provided on the surface of a roll base material, and a second thermal spray coating made of ceramics is provided on the first thermal spray coating.
- a glass transport roll is provided in which the second thermal spray coating is sealed with a silica precursor solution.
- the present invention also provides a first film forming step of forming a first sprayed coating made of metal or cermet on the surface of a roll base material, and a second sprayed coating made of ceramics on the first sprayed coating.
- the manufacturing method of the roll for glass conveyance which has a process is provided. It is preferable that a polishing step for polishing the surface of the second thermal spray coating is provided between the second film forming step and the impregnation step.
- this invention provides the manufacturing method of plate glass which has the process of conveying glass using the roll for glass conveyance of this invention. Furthermore, it is preferable that the manufacturing method of the said plate glass includes the physical reinforcement
- the particles are removed from the ceramic sprayed coating and the ceramic sprayed coating is generated from the vicinity of the interface between the base layer and the ceramic surface layer.
- the peeling itself can be remarkably suppressed.
- high quality plate glass can be provided by the manufacturing method of plate glass and tempered plate glass using the roll for glass conveyance of this invention.
- FIG. 1 is a schematic view showing a test apparatus used for evaluating adhesion of particles to a glass plate.
- FIG. 2 is a graph showing the evaluation results of Examples 1 and 2 and Comparative Examples 1 to 4.
- FIGS. 3 (a) to 3 (c) are examples in which pores and particle boundaries of a zirconia-8 mass% yttria spray coating are filled with silica produced from polysilazane (the upper part is element mapping by EPMA, and the lower part is an SEM photograph). It is. The part where the color looks whitish in the upper part is the part where the amount of Si is large.
- FIG. 3 (a) to 3 (c) are examples in which pores and particle boundaries of a zirconia-8 mass% yttria spray coating are filled with silica produced from polysilazane (the upper part is element mapping by EPMA, and the lower part is an SEM photograph). It is. The part where the color looks whitish in the upper part is the part where the amount of Si is
- FIG. 4 is a diagram showing a state (Example 3) of a corrosion product in the cross section of the sprayed coating after exposure in a high temperature corrosive gas environment.
- FIG. 5 is a diagram showing a state of a corrosion product in the cross section of the sprayed coating after exposure in a high temperature corrosive gas environment (Comparative Example 5).
- FIG. 6 is a diagram showing a state (Example 4) of a corrosion product on a cross section of a sprayed coating after exposure in a high temperature corrosive gas environment.
- FIG. 7 is a view showing a state (Comparative Example 6) of the corrosion product on the cross section of the sprayed coating after exposure in a high temperature corrosive gas environment.
- the material of the roll base material is not particularly limited.
- a metal mainly composed of iron such as carbon steel or stainless steel is preferably used.
- the outer diameter of the roll base material is not particularly limited, but the outer diameter of the roll base material in a general glass transport roll is 200 to 500 mm.
- a first thermal spray coating is provided as a base film on the surface of the roll base material.
- the first spray coating is made of cermet or metal. Cermet is preferred because of its high adhesion to the roll base material. (cermet)
- the cermet forming the first thermal spray coating is not particularly limited, and a known cermet can be appropriately used as a base film in the glass transport roll. For example, chromium carbide cermet, boride cermet, oxide dispersion cermet and the like are preferably used.
- the chromium carbide cermet is composed of a ceramic phase mainly composed of chromium carbide and a metal phase serving as a binder.
- the ceramic phase is mainly composed of Cr 3 C 2 , but may contain Cr 23 C 6 , Cr 7 C 3, etc. as inevitable impurities.
- the metal phase is made of a heat-resistant alloy containing two or more metals selected from Co, Ni, and Cr.
- the ceramic phase content in the chromium carbide-based cermet is preferably 45 to 95% by mass, and the metal phase content is preferably 5 to 55% by mass.
- the ratio of the ceramic phase and the metal phase can be obtained by obtaining the area ratio of each phase based on the cross-sectional photograph and converting it to the mass ratio (the same applies hereinafter).
- a powder prepared by sintering a mixture of chromium carbide ceramics and a heat-resistant alloy as a binder, pulverizing and adjusting the particle size to about 30 to 150 ⁇ m is used. It is preferable to use it.
- a commercially available chromium carbide cermet sprayed material may be used.
- the boride-based cermet is composed of a ceramic phase mainly composed of a composite boride containing at least one of Mo and W, Co, Cr and B, and a metal phase mainly composed of Co and Cr.
- the preferable content of each element constituting the ceramic phase is Mo: 60 mass% or less, W: 74 mass% or less, Co: 15 to 36 mass%, Cr: 3 to 16 mass%, B: 4 to 7 mass%
- the total of Mo and W is 65% by mass or more.
- the ceramic phase may contain Nb, Ta, V, etc. as inevitable impurities.
- the total content of Co and Cr in the metal phase is preferably 75% by mass or more.
- the mass ratio of Cr content to Co content (Cr: Co) in the metal phase is preferably 1: 0.15 to 1: 0.40.
- the metal phase may contain Ti, Al, Ta, Nb, etc. as inevitable impurities.
- a preferable content of the ceramic phase in the boride-based cermet is 40 to 80% by mass, and more preferably 50 to 75% by mass.
- a preferable content of the metal phase is 20 to 60% by mass, and more preferably 25 to 50% by mass.
- the oxide-dispersed cermet is composed of a ceramic phase mainly composed of oxide and a metal phase serving as a binder.
- the ceramic phase is mainly composed of Al 2 O 3 , but may contain ZrO 2 , Cr 2 O 3 or the like that does not melt even at high temperatures.
- the metal phase is made of a heat-resistant alloy containing two or more metals selected from Co, Ni, and Cr.
- a Ni-based alloy, a Co-based alloy, or the like is preferably used.
- the Ni-based alloy include a Cr—Ni alloy containing about 20 to 70% by mass of Cr.
- Examples of the Co-based alloy include a Co alloy containing 15 to 30% by mass of Cr, 5 to 16% Al, and 0.1 to 1% by mass of Y.
- the oxide phase cermet preferably has a ceramic phase content of 5 to 20% by mass and a metal phase content of 80 to 95% by mass.
- a raw material for forming the oxide-dispersed cermet sprayed coating it is preferable to use a mixture of an oxide having a particle diameter adjusted to about 30 to 150 ⁇ m and a heat-resistant alloy as a binder.
- the thickness of the first sprayed coating is preferably 30 to 150 ⁇ m, more preferably 50 to 80 ⁇ m.
- the adhesion of the coating is easily obtained, and when it is at most the upper limit, the difference in thermal expansion between the base material and the second sprayed coating is easily relaxed.
- the metal that forms the first thermal spray coating is not particularly limited. From the known metal material as the base film in the glass transport roll, the thermal expansion coefficient of the roll base material and the thermal expansion coefficient of the second thermal spray coating are: A metal material having an intermediate thermal expansion coefficient can be used as appropriate.
- the metal material of the first thermal spray coating for example, a Ni-based alloy, a Co-based alloy, or the like is preferably used.
- the Ni-based alloy include a Cr—Ni alloy containing about 20 to 70% by mass of Cr.
- the Co-based alloy include a Co alloy containing 15 to 30% by mass of Cr, 5 to 16% Al, and 0.1 to 1% by mass of Y.
- a known cobalt-based alloy such as a stellite alloy or a trivalloy alloy can be used.
- the thickness of the first sprayed coating is preferably 30 to 150 ⁇ m, more preferably 50 to 80 ⁇ m. When it is at least the lower limit of the above range, the adhesion of the coating is easily obtained, and when it is at most the upper limit, the difference in thermal expansion between the base material and the second sprayed coating is easily relaxed.
- a second thermal spray coating is laminated on the first thermal spray coating.
- the second sprayed coating is made of ceramics.
- Various ceramics such as oxides, carbides, and nitrides are applied to the ceramic forming the second thermal spray coating.
- Specific examples of the material include zirconia ceramics mainly composed of zirconium oxide (ZrO 2 ) and alumina ceramics mainly composed of aluminum oxide (Al 2 O 3 ).
- Zirconia-based ceramics have the advantage that glass, tin, and tin oxide are difficult to adhere even at high temperatures.
- the zirconia ceramic is preferably stabilized zirconia or partially stabilized zirconia containing about 3 to 15% by mass of one or more of Y 2 O 3 , CaO, MgO, CeO and other oxides as additives. .
- a preferred example of the stabilized zirconia is 8% by mass yttrium oxide stabilized zirconium oxide (8YSZ).
- YSZ yttrium oxide stabilized zirconium oxide
- As the alumina-based ceramic in addition to high-purity Al 2 O 3 , gray alumina accompanied by about 2 to 3% of TiO 2 or the like is also effective.
- the mixed component system which consists of 2 or more types of ceramics may be sufficient.
- the second sprayed coating contains at least zirconium oxide in terms of preventing adhesion of glass, tin, tin oxide and the like.
- the content of zirconium oxide in the second sprayed coating is preferably 60% by mass or more.
- other components other than zirconium oxide include yttrium oxide, magnesium oxide, cerium oxide, aluminum oxide, and titanium oxide.
- the thickness of the second sprayed coating is preferably 50 to 500 ⁇ m, more preferably 100 to 400 ⁇ m.
- the thickness of the second thermal spray coating is 50 ⁇ m or more, a sufficient effect as a thermal shock buffer layer can be easily obtained, and peeling of the second thermal spray coating due to thermal cycling hardly occurs.
- the thickness is 500 ⁇ m or less, cracks due to mechanical force during maintenance or the like are unlikely to occur.
- the second thermal spray coating is sealed with a silica precursor solution.
- the silica precursor refers to a compound that generates silica (SiO 2 ) by physical and chemical changes.
- Examples of the silica precursor include alkoxysilane and oligomers thereof, polysilazane, alkali silicate, and polysilicic acid.
- the alkoxysilane oligomer refers to a partially hydrolyzed condensate of alkoxysilane.
- Examples of the alkoxysilane oligomer include dimer to 20mer obtained by partially hydrolyzing and condensing alkoxysilane.
- alkoxysilanes include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane (ethyl silicate), tetraisopropoxysilane, and oligomers thereof; organoalkoxysilanes such as methyltriethoxysilane, ethyltriethoxysilane, and oligomers thereof. Etc. These alkoxysilanes are preferably used in a hydrolyzed form in the precursor solution.
- polysilazane perhydropolysilazane is preferable.
- silica precursor solution a known coating solution containing a silica precursor can be appropriately used.
- specific examples include an alcoholic solution of alkoxysilane and its oligomer, an organic solvent solution of polysilazane, an aqueous alkali silicate solution (water glass), an aqueous polysilicic acid solution, and the like.
- the silica precursor solution may appropriately contain other components such as a catalyst, a surfactant, and a shrinkage inhibitor as necessary.
- Precursor solution consisting of alkali silicate aqueous solution (water glass) is applied to the surface of the ceramic sprayed coating and kept at an appropriate temperature in the atmosphere to deposit silicon dioxide, macroscopically becoming a surface coating, Some penetrate into the particle boundaries of the thermal spray coating.
- This infiltration effect can be increased by adjusting the concentration of the aqueous solution and the like, which is preferable for obtaining an effective result as compared with the case where the peeling as the second aspect described above is dominant.
- these silicon dioxide materials may have a slightly weak effect of improving the bonding force between the ceramic spray particles.
- a coating formed on the surface of the sprayed coating inevitably generates a tortoiseshell-like crack by holding at a high temperature, and a liquid phase easily appears in the structure.
- Alkoxysilane typically, tetramethoxysilane, tetraethoxysilane
- the silica precursor used in the present invention needs to be selected depending on the form of the problem, but is not limited to alkoxysilanes or oligomers thereof, polysilazane or alkali silicates, and other silica precursors may be used. I can do it.
- a first thermal spray coating made of metal or cermet is formed on the surface of a roll base material (first film forming step).
- a second thermal spray coating made of ceramic is formed on the first thermal spray coating (second film forming step).
- Each of the first thermal spray coating and the second thermal spray coating can be formed by a known thermal spraying method such as a plasma spraying method or a high-speed flame spraying method.
- the formation of the first thermal spray coating is preferably a high-speed flame spraying method in that since the thermal spray particles collide with the base material at a high speed, a high adhesion between the coating and the substrate can be obtained.
- the formation of the second sprayed coating is preferably a plasma spraying method in that a high melting temperature can be realized and the sprayed particles can be in a semi-molten state.
- the raw material used in the thermal spraying method is preferably a powder raw material, and the powder raw material is preferably used for thermal spraying as a granulated sintered powder or sintered pulverized powder by previously mixing, granulating, sintering, pulverizing, and classifying.
- the surface roughness (arithmetic average height Ra defined in JIS B0601: 2001, the same shall apply hereinafter) of the roll base material after the blast treatment is preferably 2.0 to 5.0 ⁇ m.
- the first thermal spray coating and the second thermal spray coating generally have pores because droplet particles in which the raw material is melted collide with the base material (roll base material surface) and rapidly solidify and laminate.
- the porosity of the second sprayed coating is preferably 1 to 10%, more preferably 1 to 5%. When the porosity is not less than the lower limit of the above range, peeling due to thermal expansion difference is suppressed, and when it is not more than the upper limit of the above range, it is easy to obtain the strength of the film, and furthermore, thermal expansion by impregnation with the silica precursor solution. It is easy to ease the difference.
- the porosity of the second sprayed coating is preferably 0.5 to 5%. Within this range, the penetration of oxygen and sulfur oxide into the base material can be suppressed over a relatively long period.
- the porosity of the first thermal spray coating is more preferably 1 to 3%. Within this range, the penetration of oxygen and sulfur oxide into the base material can be suppressed for a longer period.
- the porosity of the second sprayed coating need not be greater than the porosity of the first sprayed coating.
- the value of a porosity is calculated
- the porosity in the thermal spray coating can be adjusted by the thermal spraying method, the thermal spraying conditions, the particle diameter of the raw material powder, and the like.
- polishing step After forming the second thermal spray coating, it is preferable to polish the surface of the second thermal spray coating (polishing step).
- polishing step By performing polishing before the impregnation step described later, the occurrence of cracks in the coating after the silica precursor is cured can be suppressed.
- the surface roughness (Ra) of the second sprayed coating after polishing is preferably 0.2 to 0.8 ⁇ m, more preferably 0.4 to 0.6 ⁇ m.
- the polishing method is not particularly limited, and for example, hand polishing using water-resistant polishing paper, mechanical polishing with a diamond tool, or the like can be used.
- the second thermal spray coating is impregnated with the silica precursor solution (impregnation step).
- the impregnation conditions are preferably set so that the silica precursor solution penetrates into all pores present on the surface of the second sprayed coating.
- the penetration depth at which the silica precursor solution penetrates into the pores is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 50 ⁇ m or more in order to satisfactorily prevent permeation of oxygen and corrosive gas. It may penetrate through the entire thickness of the second sprayed coating.
- the penetration depth of the silica precursor solution can be adjusted by the viscosity of the silica precursor solution, the impregnation time, the atmospheric temperature, and the like.
- the silica precursor solution adhering onto the second thermal spray coating is wiped off, and the silica precursor solution layer remaining on the surface of the second thermal spray coating is cured and formed.
- the thickness of the silica film is preferably 5 ⁇ m or less. A region where the residual film thickness is zero on the surface of the second sprayed coating, that is, a region where the silica precursor solution has permeated into the pores and no silica precursor solution has adhered to the surface before curing. May be present.
- the wiping process of the silica precursor solution is not essential, but by performing wiping before the curing process of the silica precursor solution described later, generation of cracks in the silica precursor cured on the surface during heating is suppressed.
- the silica precursor solution is cured to seal the second sprayed coating (curing step).
- Curing of the silica precursor solution can be performed by a known method according to the type of the silica precursor used. Thereby, the silica precursor in the silica precursor solution is converted to silica.
- the glass transport roll thus obtained is provided with a first sprayed coating on the surface of the roll base material, a second sprayed coating is provided on the first sprayed coating, and pores of the second sprayed coating. Is sealed with silica. Moreover, in the area
- the voids of the second thermal spray coating are filled with silica, oxygen and corrosive gas in the atmosphere permeate the second thermal spray coating and contact the first thermal spray coating. Can be suppressed. As a result, the dropout of particles on the surface of the second sprayed coating and the peeling of the second sprayed coating itself due to oxidation and corrosion of the first sprayed coating are satisfactorily suppressed. Further, since the gaps between the particles constituting the second thermal spray coating are filled with silica, the strength between the particles itself is improved, and this also makes it difficult for the particles to fall off.
- the glass transport roll of the present invention hardly causes particle adhesion to the glass being transported, and it is possible to achieve high quality of the glass by manufacturing the glass using the glass transport roll. Further, since oxygen and corrosive gas in the atmosphere are prevented from passing through the second thermal spray coating and coming into contact with the first thermal spray coating, the first thermal spray coating can be made of metal.
- a sheet glass manufacturing method generally includes a melting step in which raw materials are melted to obtain molten glass, a molding step in which molten glass is molded, and slow cooling in which the glass after molding is gradually cooled to remove stress. And a cutting step of cutting the glass.
- molding processes such as a float process, a roll-out process, a down draw process, and a fusion process.
- the conveyance roll of the present invention can be used anywhere as long as it is in the process intended for conveyance in the above-mentioned process, and is mainly at a high temperature in each process after the molding process and between each process, preferably 550 to 750. It is used to transport glass ribbons in the atmosphere at 0 ° C and flat glass after cutting.
- the sheet glass after the above cutting is moved using a transport roll, heated to a temperature higher than the softening point in a strengthening furnace, and then rapidly cooled with cooling air or softened as necessary.
- the plate glass formed after heating to a point or higher is quenched with cooling air.
- the rapid cooling is usually performed by blowing cooling air from a plurality of nozzles opposed to the glass surface.
- compressive residual stress is applied to the surface of the glass, and a tempered glass sheet is obtained by a so-called physical strengthening method or an air cooling strengthening method.
- strengthening process may be continued with the said cutting process, may take out plate glass after storing plate glass, and may perform it after cutting
- the conveyance roll of the present invention can be used anywhere as long as it is intended for conveyance during the above process.
- chemical strengthening step in which compressive stress is chemically applied to the glass surface by ion exchange.
- the conveyance roll of the present invention can be used even for the purpose of conveyance during the chemical strengthening step.
- a high-quality plate glass can be provided by the above-described method for producing a plate glass using the glass transport roll of the present invention.
- Examples 1, 2, and 4 performed polysilazane treatment as a silica treatment (sealing treatment), and Example 3 treated an alkoxysilane oligomer as a silica treatment.
- evaluation of particle adhesion below, the result of having evaluated the particle adhesion of the thermal spray coating to the glass surface at the time of performing a polysilazane process as a silica process is demonstrated.
- Example 1 Porosity of second sprayed coating 8% + silica treatment (polysilazane)
- a roll base material made of stainless steel (SUS310 equivalent, for high temperature) containing about 24% by mass of Cr was prepared.
- the shape of the roll base material is a disk shape with an outer diameter of 150 mm ⁇ thickness of 20 mm for convenience in use in the test described later, and the radial cross section of the outer peripheral surface of the roll is an outwardly convex curved surface.
- the outer peripheral surface of the roll base material was blasted using alumina particles having an average particle diameter of about 500 ⁇ m, and the surface roughness (Ra) was set to 3.5 ⁇ m.
- a first sprayed coating made of chromium carbide cermet was formed by plasma spraying.
- a Cr 3 C 2 -20 mass% NiCr alloy (Ni 20 mass% Cr alloy) powder having a particle size of 50 to 150 ⁇ m was used as a thermal spray raw material.
- the film thickness of the obtained first sprayed coating was 80 ⁇ m and the porosity was 2%.
- the porosity was determined by a cross-sectional image analysis method (hereinafter the same).
- a second thermal spray coating made of zirconia ceramics was formed on the first thermal spray coating by plasma spraying.
- Yttria-stabilized zirconia (8YSZ) powder having a particle size of 50 to 100 ⁇ m was used as the thermal spray raw material.
- the film thickness of the obtained second thermal spray coating was 400 ⁇ m, the surface roughness (Ra) was 2.0 ⁇ m, and the porosity was 8%.
- the surface of the second sprayed coating was polished by hand polishing.
- the film thickness of the second sprayed coating after polishing was 300 ⁇ m, the surface roughness (Ra) was 0.5 ⁇ m, and the porosity was 8%.
- the silica precursor solution is a polysilazane-based perhydropolysilazane xylene solution (perhydropolysilazane containing) that easily impregnates the pores of the sprayed coating and easily reacts with atmospheric oxygen and moisture to form amorphous silica. Amount: 10% by mass).
- the coating method was performed by painting with a brush. The same results can be obtained even if the application method is a method such as spraying, roll coating, or liquid immersion.
- the application was performed until the solution was sufficiently infiltrated into the second thermal spray coating and the remaining of the solution on the second thermal spray coating was visually confirmed, and the coating amount was controlled by this visual observation.
- the silica precursor solution on the surface of the second thermal spray coating was wiped off using a wiping cloth, and the residual film thickness of the silica precursor solution on the surface of the second thermal spray coating was set to 1 ⁇ m or less.
- These operations were performed in an atmospheric environment with a temperature of 5 to 35 ° C. and a relative humidity of 35 to 60%. Thereafter, the silica precursor solution was cured by being kept at room temperature for 24 hours to obtain a thermal spray coating in which the pores of the second thermal spray coating were sealed with silica.
- atmosphere was obtained also by hold
- Example 2 Porosity 2% of the second thermal spray coating + silica treatment (polysilazane) Only the porosity of the second thermal spray coating of Example 1 was changed to 2%. Other conditions are the same as in the first embodiment.
- FIG. 1 is a schematic diagram for explaining a test apparatus used for the evaluation.
- This test apparatus is composed of a roll-on-disk type rolling friction tester 1 (manufactured by Takachiho Seiki Co., Ltd.) and an electric furnace (not shown).
- the roll-on-disk type rolling friction tester 1 the peripheral surface of a glass transport roll (hereinafter sometimes simply referred to as a roll) 3 is in contact with the upper surface of a disk-shaped glass plate 2 that rotates in the circumferential direction. It is provided to do.
- the roll 3 is rotatable in the circumferential direction, the rotation axis direction is the same as the radial direction of the glass plate 2, and is provided so as to be able to advance and retreat in the rotation axis direction.
- the upper surface of the glass plate 2 and the peripheral surface of the roll 3 are brought into contact with each other, and a constant load is applied to the roll 3 in the direction from the center of the roll 3 toward the glass plate 2.
- the roll 3 rotates so as to roll on the glass plate 2 along with the rotation.
- the roll 3 rolls forward while drawing a spiral friction mark on the upper surface of the glass plate 2 by advancing the roll 3 toward the center of the glass plate 2 in the rotation axis direction.
- the testing machine 1 is accommodated in an electric furnace, and the atmospheric temperature of the testing machine 1 is controlled to a predetermined temperature.
- the test conditions were an atmospheric temperature of 600 ° C., a load of 500 gf on the roll 3, a radius of the glass plate 2 of 90 mm, a rotation speed of the glass plate 2 of 0.5 rps, and a width of the friction trace (corresponding to a point contact diameter between the glass plate 2 and the roll 3
- the distance between the friction marks in the radial direction of the glass plate 2 was 0.125 mm.
- the glass plate 2 and the roll 3 were set in the testing machine 1.
- the temperature in the electric furnace was raised to 600 ° C. so that the glass plate 2 and the roll 3 were not in contact with each other. After holding at 600 ° C.
- the following method evaluated how much ZrO 2 particles were adhered to the upper surface of the glass plate 2 thus obtained.
- observation points were determined at intervals of 10 mm along the radial direction from the edge toward the center.
- a glass plate piece of an appropriate size including all of the observation points was cut out from the glass plate 2, and the upper surface thereof was carbon coated.
- a backscattered electron image centered on each observation point was photographed at a constant magnification by an electron microscope, and based on the area of ZrO 2 particles present in each photographed image (observation region) and the total area of the photographed image, The particle adhesion rate in each observation region was calculated according to equation (1).
- Particle adhesion rate (%) (total area of ZrO 2 particles / total area of photographed image) ⁇ 100 (1)
- the glass conveyance rolls of Comparative Examples 1 to 4 caused much adhesion of ZrO 2 particles from the roll to the glass plate, whereas the glass conveyance rolls of Examples 1 and 2 In the roll for use, the adhesion rate of such particles was 0.15% or less, and the adhesion was suppressed well.
- the difference between the example and the comparative example is large.
- the adhesion rate of particles to the glass plate at the initial stage of friction was reduced to 1/10 or less as compared with the roll of Comparative Example 1.
- Example 1 and Example 2 there is no significant difference in the adhesion rate between the cases where the porosity is 2% and 8%, and the effect is obtained even when the porosity is relatively small. It was. Furthermore, as can be seen from the results of Comparative Example 3 and Comparative Example 4, no significant effect was obtained in the polishing treatment after the sealing treatment.
- FIG. 3 shows an example in which the pores and particle boundaries of the ZrO 2 -8 mass% Y 2 O 3 sprayed coating are filled with silica produced from polysilazane.
- the upper part of FIG. 3 shows element mapping by EPMA, and the lower part shows an SEM (scanning electron microscope) photograph.
- the color image is a gray scale image, (a) is near the surface, (b) is 25 to 50 ⁇ m from the surface, (c) is a cross section at 125 to 150 ⁇ m from the surface. Show.
- the portion that appears whitish is the portion where the amount of Si is large.
- the polysilazane material penetrates well into the entire pores and particle boundaries inside the spray coating, and the spray coating particle boundaries in the region from the surface of the spray coating to a depth of 125 to 150 ⁇ m are filled with silica. .
- the flat plate was subjected to blasting using alumina particles having an average particle diameter of about 500 ⁇ m, and the surface roughness (Ra) was set to 3.5 ⁇ m.
- a first sprayed coating made of chromium carbide cermet was formed by plasma spraying.
- a Cr 3 C 2 -20 mass% NiCr alloy (Ni-20 mass% Cr) powder having a particle diameter of 50 to 150 ⁇ m was used as a thermal spray raw material.
- the film thickness of the obtained first sprayed coating was 80 ⁇ m and the porosity was 2%.
- a second thermal spray coating made of zirconia ceramics was formed on the first thermal spray coating by plasma spraying.
- Yttria-stabilized zirconia (8YSZ) powder having a particle size of 50 to 100 ⁇ m was used as the thermal spray raw material.
- the film thickness of the obtained second thermal spray coating was 400 ⁇ m, the surface roughness (Ra) was 2.0 ⁇ m, and the porosity was 8%.
- the surface of the second sprayed coating was polished by hand polishing.
- the film thickness of the second sprayed coating after polishing was 300 ⁇ m, the surface roughness (Ra) was 0.5 ⁇ m, and the porosity was 8%.
- the silica precursor solution was applied onto the second sprayed coating after polishing, and the pores of the second sprayed coating were impregnated with the silica precursor solution.
- a silica precursor solution As a silica precursor solution, the surface tension is high so as to penetrate deep into the pores of the sprayed coating, and a relatively low viscosity tetraethoxysilane oligomer isopropanol solution (tetraethoxysilane oligomer content 10 mass%) is crosslinked.
- a dispersion liquid in which 30 to 50% by mass of colloidal silica (average particle diameter of 10 to 80 nm) was dispersed was used.
- the amount applied was sufficient to cover the entire surface of the second sprayed coating with the silica precursor solution.
- the mixture is allowed to stand for 60 minutes to allow the silica precursor solution to penetrate into the pores.
- the silica precursor solution on the surface of the second thermal spray coating is wiped off, and on the surface of the second thermal spray coating after curing.
- the residual film thickness of the silica film was 5 ⁇ m or less.
- the silica precursor solution was cured at an atmospheric temperature of 100 ° C. for 1 hour to obtain a thermal spray coating in which the pores of the second thermal spray coating were sealed with silica.
- Example 4 Porosity 8% of second sprayed coating + silica treatment (polysilazane)
- a flat plate made of stainless steel (SUS310 equivalent, for high temperature) containing 24 mass% of Cr was prepared.
- the shape of the roll base material was a flat plate shape of 100 mm ⁇ 50 mm ⁇ thickness 5 mm for convenience in use for the test described later.
- the flat plate was subjected to blasting using alumina particles having an average particle diameter of about 500 ⁇ m, and the surface roughness (Ra) was set to 3.5 ⁇ m. After this blasting treatment, unlike the first to third embodiments described above, a first thermal spray coating made of oxide dispersion cermet was formed by plasma spraying.
- An Al 2 O 3 —CoNiCrAlTa powder having a particle diameter of 50 to 150 ⁇ m was used as a thermal spray raw material.
- the film thickness of the obtained first thermal spray coating was 80 ⁇ m and the porosity was 3%.
- a second thermal spray coating made of zirconia ceramics was formed on the first thermal spray coating by plasma spraying.
- Yttria-stabilized zirconia (8YSZ) powder having a particle size of 50 to 100 ⁇ m was used as the thermal spray raw material.
- the film thickness of the obtained second thermal spray coating was 400 ⁇ m, the surface roughness (Ra) was 2.0 ⁇ m, and the porosity was 8%.
- the surface of the second sprayed coating was polished by hand polishing.
- the film thickness of the second sprayed coating after polishing was 300 ⁇ m
- the surface roughness (Ra) was 0.5 ⁇ m
- the porosity was 8%.
- the subsequent silica treatment is the same as the polysilazane treatment of Examples 1 and 2.
- Example 6 The porosity of the second sprayed coating was 8% + no silica treatment. Unlike the above-described Examples 1 to 3, the first sprayed coating comprising an oxide-dispersed cermet was used. Then, in the same process as in Example 4, it was polished by hand polishing to a surface roughness (Ra) of 0.5 ⁇ m to obtain a sprayed coating.
- Ra surface roughness
- each sample obtained by cutting out the thermal spray coatings prepared in Examples 3 and 4 and Comparative Examples 5 and 6 into 25 mm squares was sealed in a sealed container at an ambient temperature of 700 ° C. and at ambient conditions SO 2 (3600 ppm) / After exposure for 480 hours based on N 2 , the specimen was removed from the sealed container.
- FIGS. 4, 5, 6 and 7 show the results of observation of the cross-sections of the sample pieces cut out from the respective samples taken out from the sealed containers after exposure in a high temperature corrosive gas environment by reflection electron images.
- FIG. 4 shows the state of the corrosion product on the cross section of the sprayed coating in Example 3.
- FIG. 5 shows the state of the corrosion product in the cross section of the sprayed coating in Comparative Example 5.
- FIG. 6 shows the state of the corrosion product in the cross section of the sprayed coating in Example 4.
- FIG. 7 shows the state of the corrosion product in the cross section of the sprayed coating in Comparative Example 6.
- a large crack that runs horizontally on the second sprayed coating is formed between the second sprayed coating and the first sprayed coating or the second sprayed coating and the base material when taken out from the sealed container. This is caused by the difference in thermal expansion. That is, it is caused by the sample take-out speed in this test and does not occur during the actual use of the glass transport roll.
- the reason why such a large crack does not occur in the sprayed coatings of FIGS. 5 and 7 is that the removal speed is the same, but the denseness is relatively lower than that of the sprayed coatings of FIGS. 4 and 6. Conceivable.
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Abstract
Description
また、錫浴から引き上げられたガラスリボンの下面には、微量の金属錫や酸化錫が付着している。このようなガラスリボンを金属ロールで搬送すると、該付着物の一部が搬送用ロール表面に強固に凝着し、前述のガラス残留物と同様にガラスリボンの表面に傷を発生させるおそれがある。
例えば下記特許文献1には、鉄基合金のロール母材の表面にセラミックス溶射皮膜を形成するとともに、該セラミックス溶射皮膜と母材との間にサーメットからなる下地膜を設けた搬送用ロールが記載されている。
また、下記特許文献2には、ロール胴部の金属基材の表面にセラミックの溶射皮膜を設けるとともに、該金属基材と該セラミック溶射皮膜との間に、両者の中間の熱膨張係数を有する金属溶射皮膜を設けたフロートガラス製造用ロールが記載されている。
さらに、下記特許文献3には、ガラス搬送用のロールではないが、セラミックス、サーメットなどの溶射皮膜に対して、封孔処理することにより溶射皮膜の改質強化をすることが記載されている。
しかしながら、ロール母材の表面上に金属またはサーメットからなる下地層を有し、その上にセラミックス溶射皮膜が積層された従来の搬送用ロールは、板ガラスの製造ラインで使用する際に、高温、少なくともロールの存在雰囲気温度が550℃以上の場合に、セラミックス溶射皮膜の表面の微細な亀裂が不可避であるため、セラミックス溶射皮膜を構成している粒子が脱落して、搬送されているガラスに付着するという不都合が生じやすい。
さらにガラスリボンの搬送工程では、搬送用ロールとリボンの摩擦による傷が発生することを防止するために、高温でしかも腐食性ガスを用いることが多く、この環境において該ロールを長期間使用するとセラミックス溶射皮膜自体が剥離することも少なくない。
特許文献3に記載の封孔処理では、溶射皮膜の気孔に封孔剤が充填され溶射皮膜が緻密化することによって溶射皮膜の強化をしている。
しかしながら、従来、ガラス製造に用いる溶射したロールには封孔処理は適用されてこなかった。これは、ロールが高温で利用されるため、前述のようにセラミックス溶射皮膜の表面の微細な亀裂が不可避であり、目的とする封孔処理により溶射膜が緻密化した結果、封孔後の高温での利用時にむしろ溶射膜表面に亀裂が入りやすくなって、想定した効果を奏することが難しいと考えられていたためである。
すなわち、板ガラスの製造ラインの雰囲気中には、酸素や、腐食性ガスである硫黄酸化物(SOx)が存在し、ガラス搬送用ロールの表面層を形成しているセラミックス溶射皮膜には貫通気孔が存在するため、酸素や硫黄酸化物が、微量ではあるが、セラミックス溶射皮膜を通り抜けて下地層に接触する。酸素または硫黄酸化物(SOx)は、下地層を構成している金属溶射皮膜やサーメット溶射皮膜を酸化または腐食し、これによって下地層の体積が膨張する。膨張した下地層は表面層を押し上げ、表面層をなすセラミックス溶射皮膜に下地層から表面に貫通する亀裂が発生する。次の現象として、下地層の酸化や腐食の状態は、対象となるロールを取り巻く温度や雰囲気、さらには下地層自体の組成によって異なり、セラミックス溶射皮膜の粒子脱落が支配的な様態と、セラミックス溶射皮膜自体の剥離が支配的な様態の2種類に分類できる。第1の様態は、下地層の酸化または腐食が比較的早く進行し、下地層の体積がさらに膨張する結果、セラミックス溶射皮膜表面に微細な亀裂が発生するとともに凹凸が発生し、ガラスとの接触によって表面開放端で微細な粒子の脱落を引き起こすことが支配的な状態である。一方、第2の様態は、種々の環境条件によって下地層の腐食速度が比較的遅く、下地層とセラミックス溶射皮膜との界面に薄い反応層が形成される結果、下地層とセラミックス溶射皮膜の界面近傍からセラミックス溶射皮膜の剥離自体が生じることが支配的な状態である。なお、第1と第2の各様態において、支配的ではない他方の様態も発生しており、これらを併せて抑制する必要がある。このような問題は、前記フロート法による板ガラスの製造方法のみならず、その他の板ガラスの製造方法におけるガラス搬送用ロールでも発生する場合がある。
本発明者等はかかる知見に基づいてさらに検討を重ね、セラミックス溶射皮膜の表面に対して、シリカ前駆体溶液を用いて封孔処理を行うことにより、前述したセラミックス溶射皮膜からの粒子脱落およびセラミックス溶射皮膜自体の剥離を防止できることを見出して本発明を完成するに至った。この封孔処理によって、セラミックス溶射皮膜表面には前述のように使用時の熱によって微細な亀裂は発生するが、本発明は下地層の劣化や下地層とセラミックス溶射皮膜との界面における劣化を抑制することによって上記の第1と第2の様態の問題を解決できる。
加えて、本発明のガラス搬送用ロールにおいては、支配的な様態に対応してシリカ前駆体溶液のセラミックス溶射皮膜への浸透状態をかえることによって本発明の効果が大きくなることもわかった。すなわち、下地層の酸化や腐食の進行の仕方の違いに応じて、第1の様態である粒子脱落が支配的な場合に対しては溶射皮膜表面での皮膜を形成する粒子同士の結合力を高める封孔処理を、第2の様態である剥離が支配的な場合に対しては下地層とセラミックス層の界面まで浸透し、その界面を保護するためにセラミックス溶射皮膜に対する含浸性が向上する封孔処理を、選択することが好ましい。どちらの様態が支配的かは、後述するように高温腐食ガスの環境下に溶射膜を暴露することによって判断できる。
前記第2の成膜工程と、前記含浸工程との間に、前記第2の溶射皮膜の表面を研磨する研磨工程を有することが好ましい。
また、本発明は、本発明のガラス搬送用ロールを用いてガラスを搬送する工程を有する、板ガラスの製造方法を提供する。
さらに、前記板ガラスの製造方法は、板ガラスを加熱した後、または加熱後に成形した後に、急冷してガラス表面に残留応力を付与する物理強化工程を含むことが好ましい。
ロール母材の材質は特に限定されないが、たとえば、炭素鋼、ステンレス鋼など鉄を主体とする金属が好適に用いられる。
ロール母材の外径は特に限定されないが、一般的なガラス搬送用ロールにおけるロール母材の外径は200~500mmである。
本発明のガラス搬送用ロールにおいて、ロール母材の表面上に、下地膜として第1の溶射皮膜が設けられている。第1の溶射皮膜はサーメットまたは金属からなる。ロール母材との密着力が高い点でサーメットが好ましい。
(サーメット)
第1の溶射皮膜をなすサーメットとしては、特に限定されず、ガラス搬送用ロールにおける下地膜として公知のサーメットを適宜用いることができる。
例えば炭化クロム系サーメット、硼化物系サーメット、酸化物分散系サーメット等が好適に用いられる。
炭化クロム系サーメットにおけるセラミックス相の含有率が45~95質量%で、金属相の含有率が5~55質量%であることが好ましい。セラミックス相および金属相の割合は、断面写真に基づき、各相の面積率を求め、質量率に換算することにより求めることができる(以下、同様)。
炭化クロム系サーメット溶射皮膜を形成するための原料としては、炭化クロムセラミックスと、バインダーとなる耐熱合金との混合物を焼結し、粉砕整粒して粒子径を30~150μm程度に調整した粉末を用いることが好ましい。市販の炭化クロム系サーメット溶射材料を用いてもよい。
セラミック相を構成する各元素の好ましい含有量は、Mo:60質量%以下、W:74質量%以下、Co:15~36質量%、Cr:3~16質量%、B:4~7質量%であり、MoとWの合計が65質量%以上である。セラミックス相には、これらの各元素のほかに、不可避不純物としてNb、Ta、Vなどが含まれてもよい。
金属相におけるCoとCrの含有量の合計は75質量%以上であることが好ましい。また該金属相における、Cr含有量とCo含有量の質量比(Cr:Co)は1:0.15~1:0.40であることが好ましい。金属相にはCoおよびCrのほかに、不可避不純物としてTi、Al、Ta、Nbなどが含まれてもよい。
硼化物系サーメットにおけるセラミックス相の好ましい含有率は、40~80質量%であり、50~75質量%がより好ましい。金属相の好ましい含有率は、20~60質量%であり、25~50質量%がより好ましい。
酸化物分散系サーメットにおけるセラミックス相の含有率が5~20質量%で、金属相の含有率が80~95質量%であることが好ましい。
酸化物分散系サーメット溶射皮膜を形成するための原料としては、粒子径を30~150μm程度に調整した酸化物と、バインダーとなる耐熱合金を混合して用いることが好ましい。
第1の溶射皮膜をなす金属としては、特に限定されず、ガラス搬送用ロールにおける下地膜として公知の金属材料から、ロール母材の熱膨張係数と、第2の溶射皮膜の熱膨張係数との中間の熱膨張係数を有する金属材料を適宜用いることができる。
第1の溶射皮膜が金属からなる場合、該第1の溶射皮膜の厚さは30~150μmが好ましく50~80μmがより好ましい。上記範囲の下限値以上であると皮膜の密着力が得られやすく、上限値以下であると母材と第2の溶射皮膜との熱膨張差を緩和しやすい。
本発明のガラス搬送用ロールにおいて、第1の溶射皮膜上に第2の溶射皮膜が積層形成されている。第2の溶射皮膜はセラミックスからなる。
第2の溶射皮膜をなすセラミックスは、酸化物系、炭化物系、窒化物系等の各種セラミックが適用される。その材質の具体例として、酸化ジルコニウム(ZrO2)を主成分とするジルコニア系セラミックス、酸化アルミニウム(Al2O3)を主成分とするアルミナ系セラミックス等が挙げられる。
ジルコニア系セラミックスは、高温においてもガラスや錫および酸化錫が付着し難いという利点を有する。ジルコニア系セラミックスは、添加剤としてY2O3、CaO、MgO、CeO、その他の酸化物の1種ないし2種以上を、3~15質量%程度含有する安定化ジルコニアまたは部分安定化ジルコニアが好ましい。安定化ジルコニアの好ましい例として8質量%酸化イットリウム安定化酸化ジルコニウム(8YSZ)が挙げられる。
アルミナ系セラミックスは、高純度のAl2O3のほか、2~3%程度のTiO2等を付随するグレイ・アルミナ等も有効である。
また、2種以上のセラミックスからなる混合成分系でもよい。
第2の溶射皮膜の厚みが50μm以上であると、熱衝撃の緩衝層としての効果が充分に得られやすく、熱サイクルによる第2の溶射皮膜の剥離が生じ難い。厚みが500μm以下であると、メンテナンスなどの際の機械的な力による亀裂が生じ難い。
本発明のガラス搬送用ロールにおいて、第2の溶射皮膜はシリカ前駆体溶液を用いて封孔処理されている。
シリカ前駆体とは、物理的、化学的変化によりシリカ(SiO2)を生じる化合物をいう。シリカ前駆体の例としてはアルコキシシランやそのオリゴマー、ポリシラザン、アルカリケイ酸塩、ポリケイ酸が挙げられる。ここでアルコキシシランのオリゴマーとは、アルコキシシランの部分加水分解縮合物をいう。アルコキシシランのオリゴマーとしては、例えばアルコキシシランを部分的に加水分解縮合して得られる2~20量体がある。ポリシラザンとしてはパーヒドロポリシラザンが好ましい。アルコキシシランの具体例としてはテトラメトキシシラン、テトラエトキシシラン(珪酸エチル)、テトライソプロポキシシラン等のテトラアルコキシシランやそのオリゴマー;メチルトリエトキシシラン、エチルトリエトキシシラン等のオルガノアルコキシシランやそれらのオリゴマー等が挙げられる。これらアルコキシシランは、前駆体溶液中で加水分解された形で用いることが好ましい。ポリシラザンの具体例としては、パーヒドロポリシラザンが好ましい。
シリカ前駆体溶液として、シリカ前駆体を含有する公知のコーティング液を適宜使用できる。具体例としては、アルコキシシランやそのオリゴマーのアルコール溶液、ポリシラザンの有機溶媒溶液、アルカリケイ酸塩水溶液(水ガラス)、ポリケイ酸水溶液等が挙げられる。シリカ前駆体溶液は、必要に応じて触媒、界面活性剤、収縮抑制剤等の他の成分を適宜含有してもよい。
アルカリケイ酸塩水溶液(水ガラス)からなる前駆体溶液はセラミック溶射皮膜表面に塗布し大気中で適当な温度で保持すると二酸化ケイ素を析出して、巨視的には表面の塗膜となるとともに、一部は溶射皮膜の粒子境界に滲入する。水溶液の濃度などを調整することによって、この滲入効果を大きくすることが可能であり、前述した第2の様態である剥離が支配的な場合に対し有効な結果を得るのに好ましい。しかし、これらの二酸化ケイ素物質はセラミック溶射粒子間の結合力を向上させる効果が若干弱い場合がある。また溶射皮膜表面に塗膜状に形成したものは、高温保持によって亀甲状のわれを不可避に生じるとともに、その組織内に容易に液相が出現する。
また、アルコキシシラン(代表的にはテトラメトキシシラン、テトラエトキシシラン)は加熱履歴によってシリカに転じるものの微細粉末のゲル状を呈する。これらは凝集性に乏しくかつ外力が働いたとき、その環境中にしばしば脱離する場合がある。ただし、アルコキシシランオリゴマーの使用やシリカゾルなどの収縮抑制剤の併用によりこれら問題を解決することができる。
一方、アルコキシシラン類から形成される酸化ケイ素に比較して、ポリシラザン類から形成される酸化ケイ素は緻密な構造を有し、高い機械的耐久性やガスバリヤ性を有し、セラミックス溶射被膜の封孔剤として用いた場合に、セラミックス粒子の結合力を高め、粒子の脱落防止への効果が大きいため、前述した第1の様態である粒子脱落が支配的な場合にはポリシラザンを用いるのが好ましい。
本発明で用いるシリカ前駆体は、問題の様態によって選定される必要があるが、アルコキシシランやそのオリゴマー、ポリシラザンまたはアルカリケイ酸塩に限定されるものではなく、他のシリカ前駆体を用いることが出来る。
本発明のガラス搬送用ロールの製造方法について説明する。
まず、ロール母材の表面に、金属またはサーメットからなる第1の溶射皮膜を形成する(第1の成膜工程)。次いで第1の溶射皮膜上にセラミックスからなる第2の溶射皮膜を形成する(第2の成膜工程)。
第1の溶射皮膜および第2の溶射皮膜はそれぞれ、プラズマ溶射法、高速フレーム溶射法などの公知の溶射法で形成できる。第1の溶射皮膜の形成は、高速度によって溶射粒子が母材に衝突するため皮膜と基材間の高い密着力が得られるという点で、高速フレーム溶射法が好ましい。一方、第2の溶射皮膜の形成は、高い溶融温度が実現でき、溶射粒子を半溶融状態にすることが出来るという点で、プラズマ溶射法が好ましい。
溶射法で用いる原料は粉末原料が好ましい、粉末原料は、予め混合、造粒、焼結、粉砕、分級などを行い造粒焼結粉や焼結粉砕粉として、溶射に用いることが好ましい。
溶射皮膜における気孔率は溶射法、溶射条件、原料粉末の粒子径等によって調整することができる。
研磨後の第2の溶射皮膜の表面の粗さ(Ra)は0.2~0.8μmが好ましく、0.4~0.6μmがより好ましい。
研磨方法は特に限定されず、例えば耐水性研磨紙を用いた手研磨、ダイヤモンド工具による機械的研磨等を用いることができる。
該シリカ前駆体溶液の拭き取り工程は必須ではないが、後述するシリカ前駆体溶液の硬化工程の前に拭き取りを行うことにより、加熱時に表面で硬化したシリカ前駆体の亀裂発生を抑制する。
シリカ前駆体溶液の硬化は、用いたシリカ前駆体の種類に応じた公知の方法で行うことができる。これによりシリカ前駆体溶液中のシリカ前駆体がシリカに転化する。
また第2の溶射皮膜を構成している粒子間の隙間がシリカで埋められた状態となるため粒子間強度自体が向上し、これによっても粒子の脱落が生じ難くなる。
したがって、本発明のガラス搬送用ロールは搬送中のガラスへの粒子付着が生じ難く、ガラス搬送用ロールを用いてガラスを製造することにより、ガラスの高品質化を実現することができる。
また雰囲気中の酸素や腐食性ガスが第2の溶射皮膜を透過して第1の溶射皮膜に接触するのが防止されるため、第1の溶射皮膜を金属で構成することもできる。
本発明の板ガラスの製造方法は、建築用板ガラス、自動車ガラス、ディスプレイ用板ガラスなどの公知の種々の製造方法や、ガラスの組成によらず利用できる。例えば、板ガラスの製造方法は一般に、原材料を溶解して溶融ガラスを得る溶融工程と、溶融ガラスを成形する成形工程と、成形後のガラスを移動させながら徐々に冷却して応力を除去する徐冷工程と、そのガラスを切断する切断工程と、を有する。上記成形工程は、フロート法、ロールアウト法、ダウンドロー法、フュージョン法など種々のものがある。本発明の搬送用ロールは、上記工程中の搬送を目的とする工程中であればどこでも利用することができ、おもに成形工程以降の各工程内および各工程間での高温、好ましくは550~750℃の雰囲気下にあるガラスリボンならびに切断後の板ガラスの搬送に利用する。
板ガラスの製造方法において物理強化工程以外に、イオン交換によって化学的にガラス表面に圧縮応力を付与するいわゆる化学強化工程がある。本発明の搬送用ロールは、この化学強化工程中の搬送を目的とするところでも利用することができる。
以上の本発明のガラス搬送用ロールを用いた板ガラスの製造方法によって、高品質の板ガラスを提供することができる。
(粒子の付着性の評価)
以下に、シリカ処理としてポリシラザン処理をした場合のガラス表面への溶射皮膜の粒子付着性を評価した結果について説明する。
(実施例1)第2の溶射皮膜の気孔率8%+シリカ処理(ポリシラザン)
まず、24質量%程度のCrを含有するステンレス(SUS310相当、高温用)からなるロール母材を用意した。ロール母材の形状は、後述する試験に用いるために便宜上、外径150mm×厚み20mmの円板状とし、ロール外周面の半径方向断面は外方に凸状の曲面とし、該曲面の曲率半径は50mmとした。
次に、ロール母材の外周面に対して、平均粒子径500μm程度のアルミナ粒子を用いてブラスト処理を施し、表面粗さ(Ra)を3.5μmとした。
ブラスト処理後、プラズマ溶射法により炭化クロム系サーメットからなる第1の溶射皮膜を形成した。溶射原料として、粒子径50~150μmのCr3C2-20質量%NiCr合金(Ni20質量%Cr合金)粉末を用いた。得られた第1の溶射皮膜の膜厚は80μm、気孔率は2%であった。なお、気孔率は、断面画像解析法によって求めた(以下、同様)。
続いて、第2の溶射皮膜の表面を手研磨にて研磨した。研磨後の第2の溶射皮膜の膜厚は300μm、表面粗さ(Ra)は0.5μm、気孔率は8%であった。
塗布後、ワイピングクロスを用いて第2の溶射皮膜の表面上のシリカ前駆体溶液を拭き取り、第2の溶射皮膜の表面上におけるシリカ前駆体溶液の残渣膜厚を1μm以下とした。これらの作業は、温度を5~35℃、相対湿度を35~60%の大気環境で実施した。この後、室温大気中で24時間保持してシリカ前駆体溶液を硬化させることにより、第2の溶射皮膜の気孔がシリカ封孔された溶射皮膜を得た。また、温度100℃の大気中で1時間保持することによっても、室温大気中24時間保持の場合と同様の結果を得た。
実施例1の第2の溶射皮膜の気孔率のみ2%に変更した。その他の条件は、実施例1と同様である。
上記実施例1と同様の工程で、手研磨にて研磨し、表面粗さ(Ra)を0.5μmとしたところまで行った。
上記実施例2と同様の工程で、手研磨にて研磨し、表面粗さ(Ra)を0.5μmとしたところまで行った。
上記実施例1と同様の工程でシリカ封孔を行った溶射皮膜の表面を手研磨にて20μm研磨し、表面粗さ(Ra)を0.5μmとした。
磨
上記実施例1と同様の工程でシリカ封孔を行った溶射皮膜の表面を手研磨にて200μm研磨し、表面粗さ(Ra)を0.5μmとした。
図1は該評価に用いた試験装置を説明するための概略図である。この試験装置はロール・オン・ディスク型転動摩擦試験機1(高千穂精機社製)と電気炉(図示略)とを組み合わせて構成されている。
ロール・オン・ディスク型転動摩擦試験機1は、周方向に回転する円板状のガラス板2の上面に、ガラス搬送用ロール(以下、単にロールということもある。)3の周面が接触するように設けられている。ロール3は周方向に回動自在であり、回転軸方向がガラス板2の径方向と同じであり、かつ回転軸方向に進退可能に設けられている。
該試験機1において、ガラス板2の上面とロール3の周面とを接触させ、ロール3に対して、ロール3の中心からガラス板2へ向かう方向に一定の荷重をかけた状態で、ガラス板2を回転させると、その回転に伴ってロール3がガラス板2上を転がるように回転する。そしてガラス板2を回転させつつ、ロール3をその回転軸方向にガラス板2の中心に向かって前進させることにより、ロール3はガラス板2上面に螺旋状の摩擦痕を描きながら転がる。また上記実施例および比較例ではロールの外周面を、外方に凸状の曲面としたため、ガラス板2の上面とロール3の周面との接触は点接触となり、摩擦痕は線状となる。
試験機1は電気炉内に収容されており試験機1の雰囲気温度が所定の温度に制御されるようになっている。
まず、ガラス板2とロール3を試験機1にセットした。ガラス板2とロール3とが接触しない状態として、電気炉内の温度を600℃に昇温した。600℃で30分保持後、ガラス板2およびロール3の温度が充分に均一になったところで、ガラス板2の上面の端縁にロール3の周面を接触させ、ロール3に所定の荷重をかけた状態で、ガラス板2の回転とロール3の軸方向への前進(軸送り)を同時に開始した。ロール3の軸送り速度は、摩擦痕の間隔が所定の値となるように設定する。ロール3がガラス板2の中心に達したら両者の接触を解除し、ガラス板2の回転を止めた。そしてガラス板2が割れないように電気炉内の温度を徐々に降下させ、室温まで下げてからガラス板2を取り出した。
得られたガラス板2の上面において、端縁から中心に向かう径方向に沿って、10mm間隔で観察点を決めた。ガラス板2から、該観察点の全部を含む適宜の大きさのガラス板片を切り出し、その上面をカーボンコートした。この後、電子顕微鏡により各観察点を中心とする反射電子像を一定倍率でそれぞれ撮影し、各撮影像(観察領域)中に存在するZrO2粒子の面積と撮影像の全面積に基づき、下式(1)により各観察領域における粒子付着率を算出した。
粒子付着率(%)=(ZrO2粒子の面積合計/撮影像の全面積)×100…(1)
図2において、横軸はガラス板2の端縁(外周)から各観察点までの距離を示し、縦軸はガラス板への粒子付着率(単位:%)を示す。
以下に、上記の評価とは別のサンプルを用いて、ポリシラザン処理でのセラミックス溶射皮膜への含浸性の評価をするために、溶射膜にポリシラザン処理をしたサンプルでの評価結果を示す。
ポリシラザン処理を気孔率8%のZrO2-8質量%Y2O3プラズマ溶射皮膜に施した。EPMA(X線マイクロアナライザー)を用いて断面の元素分布を精査した。図3に、この結果として、ZrO2-8質量%Y2O3溶射皮膜の気孔および粒子境界がポリシラザンから生成したシリカで充填されている様態例を示す。図3の上段にEPMAによる元素マッピング、下段にSEM(走査電子顕微鏡)写真を示す。ただし、上段の元素マッピングは、カラー画像をグレースケール画像にしたもので、(a)は表面近傍、(b)は表面から25~50μm、(c)は表面から125~150μmのところの断面を示す。上段の元素マッピングにおいて、白っぽく見えているところがSiの量が多い部分である。これより、ポリシラザン材は溶射皮膜内部の気孔および粒子境界の全体によく進入し、溶射皮膜の表面から125~150μmの深さまでの領域の溶射皮膜粒子境界がシリカで充填されていることがわかった。
以下に、シリカ処理の高温での耐腐食性の評価をするために、シリカ処理としてアルコキシシランオリゴマー処理とポリシラザン処理をしたサンプルでの評価結果を示す。
(実施例3)第2の溶射皮膜の気孔率8%+シリカ処理(アルコキシシランオリゴマー) Crを24質量%含有するステンレス(SUS310相当、高温用)からなる平板を用意した。ロール母材の形状は、後述する試験に用いるために便宜上、100mm×50mm×厚み5mmの平板状とした。
この平板に対して、平均粒子径500μm程度のアルミナ粒子を用いてブラスト処理を施し、表面粗さ(Ra)を3.5μmとした。
このブラスト処理後、プラズマ溶射法により炭化クロム系サーメットからなる第1の溶射皮膜を形成した。溶射原料として、粒子径50~150μmのCr3C2-20質量%NiCr合金(Ni-20質量%Cr)粉末を用いた。得られた第1の溶射皮膜の膜厚は80μm、気孔率は2%であった。
続いて、第2の溶射皮膜の表面を手研磨にて研磨した。研磨後の第2の溶射皮膜の膜厚は300μm、表面粗さ(Ra)は0.5μm、気孔率は8%であった。
研磨後の第2の溶射皮膜上にシリカ前駆体溶液を塗布し、第2の溶射皮膜の気孔にシリカ前駆体溶液を含浸させた。シリカ前駆体溶液としては、溶射皮膜の気孔の深くに浸入するように表面張力が高く、比較的低粘度なテトラエトキシシランオリゴマーのイソプロパノール溶液(テトラエトキシシランオリゴマーの含有量10質量%)に、架橋収縮を抑制するためコロイダルシリカ(平均粒径10~80nm)を30~50質量%分散させた、分散液を用いた。
塗布量は第2の溶射皮膜の表面全面がシリカ前駆体溶液で覆われるに充分な量とした。塗布後、60分間静置してシリカ前駆体溶液を気孔内へ浸透させた後、第2の溶射皮膜の表面上のシリカ前駆体溶液を拭き取り、硬化後の第2の溶射皮膜の表面上におけるシリカ皮膜の残渣膜厚を5μm以下とした。
この後、雰囲気温度100度で1時間保持しシリカ前駆体溶液を硬化させることにより、第2の溶射皮膜の気孔がシリカで封孔された溶射皮膜を得た。
上記実施例3と同様の工程で、手研磨にて研磨し、表面粗さ(Ra)を0.5μmとしたところまで行った溶射皮膜を得た。
Crを24質量%含有するステンレス鋼(SUS310相当、高温用)からなる平板を用意した。ロール母材の形状は、後述する試験に用いるために便宜上、100mm×50mm×厚み5mmの平板状とした。
この平板に対して、平均粒子径500μm程度のアルミナ粒子を用いてブラスト処理を施し、表面粗さ(Ra)を3.5μmとした。
このブラスト処理後、プラズマ溶射法により、前述の実施例1~3とは違い、酸化物分散系サーメットからなる第1の溶射皮膜を形成した。溶射原料として、粒子径50~150μmのAl2O3-CoNiCrAlTa粉末を用いた。得られた第1の溶射皮膜の膜厚は80μm、気孔率は3%であった。
第1の溶射皮膜上に、プラズマ溶射法によりジルコニア系セラミックスからなる第2の溶射皮膜を形成した。溶射原料として、粒子径50~100μmのイットリア安定化ジルコニア(8YSZ)粉末を用いた。得られた第2の溶射皮膜の膜厚は400μm、表面粗さ(Ra)は2.0μm、気孔率は8%であった。
続くシリカ処理については、実施例1と2のポリシラザン処理と同様である。
上記実施例4と同様に前述の実施例1~3とは違い、酸化物分散系サーメットからなる第1の溶射皮膜を形成し、実施例4と同様の工程で、手研磨にて研磨し、表面粗さ(Ra)を0.5μmとしたところまで行って溶射皮膜を得た。
他方、シリカによる封孔を行った図4に示す実施例3の溶射皮膜では、比較例5と異なり、第1の溶射皮膜と第2の溶射皮膜層との境界に、腐食生成物がほとんど確認できず、腐食生成物の発生が良好に抑えられることを確認した。同様にシリカによる封孔を行った図6に示す実施例4の溶射皮膜でも腐食生成物がほとんど確認できず、腐食生成物の発生が良好に抑えられることを確認した。なお、図4と図6において、第2の溶射膜に水平に走る大きな亀裂は、密閉容器から取り出す際に第2の溶射皮膜と第1の溶射皮膜または第2の溶射皮膜と母材との熱膨張差によって生じたものである。すなわち、本試験でのサンプルの取り出し速度に起因するもので、実際のガラス搬送用ロールの使用中に発生するものではない。図5と図7の溶射皮膜でこのような大きな亀裂が発生していないのは、取り出し速度は同じであるが、図4と図6の溶射皮膜に比べて緻密性が相対的に低いためと考えられる。
上記の観察とは別に、比較例5と比較例6のそれぞれの第1の溶射皮膜への硫黄の侵入の様態を確認するために、上記サンプルの断面についてEDXのマッピングで硫黄の存在位置を確認してその部位を撮影後、それを別途撮影した下地膜断面の反射電子像に合成した。その断面画像から、比較例5ではCr3C2-20質量%NiCr合金(Ni-20質量%Cr)粉末を用いた炭化クロム系サーメットからなる第1の溶射皮膜の場合には硫黄が層厚方向に渡って存在しているのが確認できた。他方の比較例6ではAl2O3-CoNiCrAlTa粉末を用いた酸化物分散系サーメットからなる第1の溶射皮膜の場合には硫黄が膜厚方向のある深さ以上は存在しないことが確認できた。これらは、比較例6の酸化物分散系サーメットの酸化物であるAl2O3がラメラ構造として積層しているため、腐食ガスを第1の溶射皮膜の深部まで浸入させることを抑制するフレークライニングの効果を発揮していることを示している。
本出願は、2008年3月13日出願の日本特許出願2008-064064に基づくものであり、その内容はここに参照として取り込まれる。
Claims (10)
- ロール母材の表面に、サーメットまたは金属からなる第1の溶射皮膜が設けられ、該第1の溶射皮膜上にセラミックスからなる第2の溶射皮膜が設けられたガラス搬送用ロールであって、該第2の溶射皮膜がシリカ前駆体溶液を用いて封孔処理されている、ガラス搬送用ロール。
- 前記第1の溶射皮膜のサーメットが、酸化物分散系サーメット、炭化クロム系サーメット、および硼化物系サーメットのいずれかである請求項1に記載のガラス搬送用ロール。
- 前記第2の溶射皮膜の気孔率が、断面画像解析法による測定で1~10%である請求項1または2に記載のガラス搬送用ロール。
- ロール母材の表面に、金属またはサーメットからなる第1の溶射皮膜を形成する第1の成膜工程と、
該第1の溶射皮膜上にセラミックスからなる第2の溶射皮膜を形成する第2の成膜工程と、
該第2の溶射皮膜に、シリカ前駆体溶液を含浸させる含浸工程と、
該シリカ前駆体溶液を硬化させて第2の溶射皮膜を封孔処理する硬化工程を有する、ガラス搬送用ロールの製造方法。 - 前記第2の成膜工程と、前記含浸工程との間に、前記第2の溶射皮膜の表面を研磨する研磨工程を有する、請求項4記載のガラス搬送用ロールの製造方法。
- 前記第1の溶射皮膜のサーメットが、酸化物分散系サーメット、炭化クロム系サーメット、または硼化物系サーメットのいずれかである請求項4または5に記載のガラス搬送用ロールの製造方法。
- 前記第2の溶射皮膜の気孔率が、断面画像解析法による測定で1~10%である請求項4から6のいずれかに記載のガラス搬送用ロールの製造方法。
- 請求項1から3のいずれかに記載のガラス搬送用ロールを用いてガラスを搬送する工程を有する、板ガラスの製造方法。
- 板ガラスを加熱した後、または加熱後に成形した後に、急冷してガラス表面に残留応力を付与する物理強化工程を含む、請求項8に記載の板ガラスの製造方法。
- 前記ガラス搬送用ロールを、550~750℃の雰囲気温度下で用いる請求項8または9に記載の板ガラスの製造方法。
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KR20160020438A (ko) | 2013-06-18 | 2016-02-23 | 아사히 가라스 가부시키가이샤 | 유리 반송용 롤 및 그 제조 방법, 및 그것을 사용한 판 유리의 제조 방법 |
JPWO2014203834A1 (ja) * | 2013-06-18 | 2017-02-23 | 旭硝子株式会社 | ガラス搬送用ロールおよびその製造方法ならびにそれを用いた板ガラスの製造方法 |
Also Published As
Publication number | Publication date |
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CN101970365A (zh) | 2011-02-09 |
JPWO2009113638A1 (ja) | 2011-07-21 |
JP5474760B2 (ja) | 2014-04-16 |
TW200951087A (en) | 2009-12-16 |
KR20100133975A (ko) | 2010-12-22 |
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