JP2017145452A - Thermal spray material - Google Patents
Thermal spray material Download PDFInfo
- Publication number
- JP2017145452A JP2017145452A JP2016027746A JP2016027746A JP2017145452A JP 2017145452 A JP2017145452 A JP 2017145452A JP 2016027746 A JP2016027746 A JP 2016027746A JP 2016027746 A JP2016027746 A JP 2016027746A JP 2017145452 A JP2017145452 A JP 2017145452A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- thermal spray
- mass
- oxide
- spray material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 89
- 239000007921 spray Substances 0.000 title claims abstract description 78
- 239000000843 powder Substances 0.000 claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 claims abstract description 65
- 239000002184 metal Substances 0.000 claims abstract description 65
- 238000002485 combustion reaction Methods 0.000 claims abstract description 64
- 239000010456 wollastonite Substances 0.000 claims abstract description 35
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 230000008439 repair process Effects 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000011863 silicon-based powder Substances 0.000 claims description 22
- 238000007751 thermal spraying Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- 229910010100 LiAlSi Inorganic materials 0.000 claims description 6
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 229910052642 spodumene Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 4
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052670 petalite Inorganic materials 0.000 claims description 4
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 239000004343 Calcium peroxide Substances 0.000 claims description 3
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 3
- 235000019402 calcium peroxide Nutrition 0.000 claims description 3
- 229910000174 eucryptite Inorganic materials 0.000 claims description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 3
- 229960004995 magnesium peroxide Drugs 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 2
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 83
- 238000010276 construction Methods 0.000 abstract description 53
- 239000000377 silicon dioxide Substances 0.000 abstract description 35
- 239000011449 brick Substances 0.000 abstract description 34
- 239000000203 mixture Substances 0.000 abstract description 31
- 239000004575 stone Substances 0.000 abstract description 3
- 230000009970 fire resistant effect Effects 0.000 abstract description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 59
- 239000002245 particle Substances 0.000 description 36
- 239000000292 calcium oxide Substances 0.000 description 31
- 235000012255 calcium oxide Nutrition 0.000 description 31
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 12
- 239000000395 magnesium oxide Substances 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- -1 alkali metal salt Chemical class 0.000 description 11
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 150000004706 metal oxides Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000000571 coke Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 229910052604 silicate mineral Inorganic materials 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 238000000280 densification Methods 0.000 description 6
- 150000004972 metal peroxides Chemical class 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910018068 Li 2 O Inorganic materials 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004974 alkaline earth metal peroxides Chemical class 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Ceramic Products (AREA)
- Coating By Spraying Or Casting (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Abstract
Description
本発明は、コークス炉や熱風炉に代表される珪石れんがで築造された工業窯炉等の炉壁の補修材料に関し、具体的には、含有する金属粉末の酸化反応熱を利用して耐火性粉末を溶融し補修面（部位）に溶着させることで炉壁を補修する溶射材料に関する。 The present invention relates to a repair material for a furnace wall of an industrial kiln or the like built with silica bricks typified by a coke oven or a hot air furnace, and specifically, it is refractory by utilizing the oxidation reaction heat of the contained metal powder. The present invention relates to a thermal spray material for repairing a furnace wall by melting powder and welding it to a repair surface (part).
工業窯炉や溶融金属容器等においては、その使用に伴って、耐火物からなる内張り等に損傷が発生する。このような損傷に対しては、適宜、補修が実施される。例えば、製鉄所のコークス炉は、建設してから２０年以上のものが多く、特に、炭化室の壁は補修を繰り返しながら操業を継続している。 In industrial kilns, molten metal containers, and the like, damage is caused to the lining made of refractory material with the use thereof. For such damage, repairs are performed as appropriate. For example, many coke ovens in steel works have been in operation for more than 20 years, and in particular, the walls of the carbonization chamber continue to be operated with repeated repairs.
操業を継続しながら補修を実施する技術として溶射補修法がある。この溶射補修法には、例えば、プラズマ溶射、レーザ溶射、火炎溶射がある。しかしながら、これらの溶射法には大掛かりな装置が必要である。そのため、近年、比較的簡易な装置で実現可能な、金属の酸化発熱反応を利用した溶射法が利用されている。例えば、特許文献１〜６では、金属粉末（燃焼剤）と耐火性粉末の混合物である溶射材料を酸素で搬送し、高温の補修面に吹き付ける溶射方法についての記載がある。吹き付けられた混合物は、補修面からの受熱により起こる金属粉末の酸化発熱反応により耐火性組成物を形成するとともに溶融し、補修面に付着する。 There is a thermal spray repair method as a technique for performing repairs while continuing operations. Examples of the thermal spray repair method include plasma spraying, laser spraying, and flame spraying. However, these spraying methods require a large apparatus. Therefore, in recent years, a thermal spraying method using a metal oxidation exothermic reaction that can be realized with a relatively simple apparatus has been used. For example, Patent Documents 1 to 6 describe a thermal spraying method in which a thermal spray material that is a mixture of a metal powder (combustion agent) and a refractory powder is transported with oxygen and sprayed onto a high-temperature repair surface. The sprayed mixture forms a refractory composition by an oxidative exothermic reaction of the metal powder caused by heat received from the repair surface and melts and adheres to the repair surface.
一般に、耐火物ライニングを補修する場合、補修によって形成される施工体と被施工部の補修される耐火物の熱膨張は近いほど好ましい。特にコークス炉や熱風炉等、建設後にれんがの積替え修理が実施されないまま数十年にわたって稼働し続ける窯炉においては、補修材が数ヵ月から数年にわたって施工部に残存し補修部を保護する効果が要求される。すなわち、熱膨張が被施工部の熱膨張と一致し、かつ緻密で高強度な施工体が要求される。ほとんどの場合、このような長期間にわたって操業する窯炉には７００℃以上における熱膨張係数がほぼゼロの珪石れんがが使用されている。したがって、このような窯炉では、熱膨張が珪石れんがと一致する溶射材料を使用することがほとんどの場合、好ましい。 Generally, when repairing a refractory lining, it is preferable that the thermal expansion of the construction body formed by the repair and the refractory to be repaired of the construction target is closer. Especially in kiln furnaces such as coke ovens and hot blast furnaces that have been in operation for several decades without brick transshipment after construction, the repair material remains in the construction department for several months to several years and protects the repair area. Is required. That is, a dense and high-strength construction body is required in which the thermal expansion coincides with the thermal expansion of the work portion. In most cases, silica bricks having a coefficient of thermal expansion of nearly zero at 700 ° C. or higher are used in such furnaces that operate for a long period of time. Therefore, in such a kiln, it is almost always preferable to use a thermal spray material whose thermal expansion matches that of silica brick.
加えて、溶射材料は溶射補修時に良好な作業性を示す必要がある。作業性が悪い場合、補修に要する時間が長時間になり、施工コストが上昇する。また、補修に要する時間が長時間になる結果、施工作業者は、高温で粉塵の多い環境に長時間曝されることになる。良好な作業性を実現するため、溶射材料には、例えば、点火のしやすさ、燃焼の継続しやすさ、付着率の高さ、発塵の少なさ等が求められる。さらに、自ら燃焼して補修する特性上、溶射材料には、施工中の予期せぬ爆発的燃焼（発火）や燃焼先端が燃焼源に向って逆流伝播する逆火現象の発生抑制が求められる。これらの現象は、作業者を危険に曝す上、現象が生じた後の装置の整備や復旧に多くの時間が必要になってしまう。 In addition, the thermal spray material needs to exhibit good workability during thermal spray repair. When workability is poor, the time required for repair becomes long and the construction cost increases. In addition, as a result of the long time required for repair, the construction worker is exposed to a high temperature and dusty environment for a long time. In order to realize good workability, the sprayed material is required to be, for example, easy to ignite, easy to continue combustion, high adhesion rate, and low dust generation. Furthermore, the thermal spray material is required to suppress the occurrence of unexpected explosive combustion (ignition) during construction and the backfire phenomenon in which the combustion tip propagates backward toward the combustion source due to the characteristics of self-combustion and repair. These phenomena endanger workers and require a lot of time for maintenance and restoration of the apparatus after the phenomenon occurs.
以上のような要求特性をより高いレベルで満足させるために多くの発明が開示されている。例えば、特許文献１は、混合物として溶射する粒体の粒子径を、耐火性粒体（シリマナイト、ムライト、ジルコン、二酸化ケイ素、二酸化ジルコニウム、酸化アルミニウム、酸化マグネシウム等）の８０％及び２０％粒径の平均が酸化性粒体（シリコン、アルミニウム、マグネシウム、ジルコニウム等）の８０％及び２０％粒径の平均よりも大きく、耐火性粒体の粒径分布範囲率が１．２以上になるようにした溶射材料を開示している。この溶射材料によれば、信頼性及び堅牢性を向上させることができ、高い耐久性を有する耐火性溶着層が実現できるとされている。また、耐火性材料の少なくともいくつかを、ケルビン温度において、温度がその融点の０．７倍を越える前に着火させることで耐火性材料の結晶構造を改善し高品質の溶射耐火性溶着層が形成できるとされている。 Many inventions have been disclosed in order to satisfy the above required characteristics at a higher level. For example, Patent Document 1 discloses that the particle diameter of particles sprayed as a mixture is 80% and 20% particle diameter of refractory particles (silimanite, mullite, zircon, silicon dioxide, zirconium dioxide, aluminum oxide, magnesium oxide, etc.). Is larger than the average of 80% and 20% particle diameters of oxidizing particles (silicon, aluminum, magnesium, zirconium, etc.), and the particle size distribution range ratio of the refractory particles is 1.2 or more. A thermal spray material is disclosed. According to this thermal spray material, it is said that reliability and fastness can be improved, and a fire-resistant weld layer having high durability can be realized. In addition, by igniting at least some of the refractory material before the temperature exceeds 0.7 times its melting point at the Kelvin temperature, the crystal structure of the refractory material is improved, and a high-quality sprayed refractory weld layer is formed. It can be formed.
また、特許文献２は、耐火原料粉（マグネシア質粉３〜３０質量％、シリカ質粉５０〜９０質量％）と金属Ｓｉ粉５〜３０質量％を含み、化学成分値で組成全体に占めるＭｇＯ成分を１〜２５質量％とした溶射材料を開示している。さらに、特許文献３は、耐火原料粉（ＣａＯ含有量７５質量％超のカルシア質粉２〜２５質量％、シリカ質粉５０〜９０質量％）と金属Ｓｉ粉５〜３０質量％を含む溶射材料を開示している。これらの技術では、マグネシア質粉やカルシア質粉との反応によってシリカ質粉の溶融が促進され、付着性及び接着性が向上するとされている。 Patent Document 2 includes refractory raw material powder (magnesia powder 3 to 30% by mass, siliceous powder 50 to 90% by mass) and metal Si powder 5 to 30% by mass, and MgO occupies the entire composition in terms of chemical component values. The thermal spray material which made the component 1-25 mass% is disclosed. Furthermore, Patent Document 3 discloses a thermal spray material containing refractory raw material powder (2 to 25 mass% of calcia powder having a CaO content exceeding 75 mass%, 50 to 90 mass% of siliceous powder) and 5 to 30 mass% of metal Si powder. Is disclosed. In these techniques, melting of siliceous powder is promoted by reaction with magnesia powder or calcia powder, and adhesion and adhesion are improved.
また、特許文献４は、溶射材料として、耐火性添加材粒子と、金属粒子と、金属過酸化物含有粒子とからなる耐火性組成物生成用化学物質の粉状混合物を開示している。金属過酸化物含有粒子は、この金属過酸化物の生成に用いた塩基の酸化物と、該金属過酸化物の該金属の水酸化物及び炭酸塩のような分解生成物とを含有している。また、金属過酸化物含有粒子は、過酸化カルシウム含有量が０重量％より多くて多くとも７５重量％及び又は過酸化マグネシウム含有量が０重量％より多くて多くとも３０重量％である。この溶射材料によれば、溶射補修中の反応を段階的に制御することができ、発火や逆火を抑制できるとされている。 Moreover, patent document 4 is disclosing the powdery mixture of the chemical substance for refractory composition production | generation which consists of a refractory additive particle | grain, a metal particle, and a metal peroxide containing particle | grain as a thermal spray material. The metal peroxide-containing particles contain the base oxide used to produce the metal peroxide and the decomposition products of the metal peroxide, such as the metal hydroxide and carbonate. Yes. Also, the metal peroxide-containing particles have a calcium peroxide content greater than 0 wt% and at most 75 wt% and / or a magnesium peroxide content greater than 0 wt% and at most 30 wt%. According to this thermal spray material, it is said that the reaction during thermal spray repair can be controlled in stages, and ignition and flashback can be suppressed.
また、特許文献５は、耐火性粉末（珪石れんがの２０００μｍ以下の粉砕粉が主成分）と酸化性粉体である金属粉末（金属シリコン）とを含有する溶射材料を開示している。さらに、特許文献５は、結晶化促進剤としてナトリウム塩、カリウム塩、リチウム塩の１種又は複数を溶射材料に対して外掛けで０．３〜５重量％添加すること、及び着火促進剤として、発火点が３００〜８００℃の炭素系粉末（コークス粉、木炭粉、コーンスターチ粉等）又は金属粉末（鉄粉、マンガン粉、バナジウム粉等）を溶射材料に対して外掛けで０．３〜５重量％添加することを開示している。この溶射材料によれば、コークス炉の炭化室に使用されている珪石れんがと補修材の熱膨張率を近似させることができるため、長期間使用時のれんが面からの剥離損耗を抑制できるとされている。また、結晶化促進剤の添加により溶射と同時に結晶化させることができるため、溶射施工完了後の使用中に材料が膨張を伴って結晶化することを防止でき、れんがと補修材の接着強度低下を防止できるとされている。 Patent Document 5 discloses a thermal spray material containing a refractory powder (a crushed powder of silica brick of 2000 μm or less as a main component) and a metal powder (metal silicon) as an oxidizing powder. Further, Patent Document 5 discloses that one or more of a sodium salt, a potassium salt, and a lithium salt are added as a crystallization accelerator in an amount of 0.3 to 5% by weight, and an ignition accelerator. In addition, a carbon-based powder (coke powder, charcoal powder, corn starch powder, etc.) or a metal powder (iron powder, manganese powder, vanadium powder, etc.) having an ignition point of 300-800 ° C. is applied to the thermal spray material by 0.3- The addition of 5% by weight is disclosed. According to this thermal spray material, the coefficient of thermal expansion of the silica brick used in the coking chamber of the coke oven and the repair material can be approximated, so that it is possible to suppress delamination wear from the brick surface during long-term use. ing. In addition, since it can be crystallized simultaneously with thermal spraying by adding a crystallization accelerator, it is possible to prevent the material from crystallizing with expansion during use after completion of thermal spraying, and the adhesive strength of bricks and repair materials is reduced. Can be prevented.
特許文献６は、結晶化促進剤としてリチウム塩を、溶射材料に対して外掛けで、酸化物換算で０．３〜１．０質量％添加すること、着火促進剤として金属粉末（鉄粉、マンガン粉、バナジウム粉等）を溶射材料に対して外掛けで１．５質量％未満添加すること、及び燃焼補助剤として金属酸化物（酸化スカンジウム、酸化チタン、酸化バナジウム、酸化クロム、酸化マンガン、酸化鉄、酸化コバルト、酸化ニッケル、酸化銅）を溶射材料に対して外掛けで０．３〜２．０質量％添加することを開示している。この溶射材料によれば、分解時に吸熱して燃焼効率を低下させる硫酸リチウムのようなアルカリ金属塩を結晶化促進剤として添加していても、多量の着火促進剤を添加することなく点火性と燃焼継続性を安全に確保できるとされている。 Patent Document 6 discloses that lithium salt is added as a crystallization accelerator to the thermal spray material in an amount of 0.3 to 1.0% by mass in terms of oxide, and metal powder (iron powder, Manganese powder, vanadium powder, etc.) is added to the thermal spray material as an outer coating less than 1.5% by mass, and metal oxides (scandium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, It discloses that 0.3 to 2.0 mass% of iron oxide, cobalt oxide, nickel oxide, copper oxide) is added as an outer coating to the thermal spray material. According to this thermal spray material, even if an alkali metal salt such as lithium sulfate that absorbs heat during decomposition and lowers the combustion efficiency is added as a crystallization accelerator, it can be ignited without adding a large amount of ignition accelerator. It is said that combustion continuity can be secured safely.
ところで、上述の溶射材料による補修対象の１つであるコークス炉炭化室は、コークスを押出す際に扉を開閉するため、その扉近くでは、例えば、９００℃〜１３００℃間で炉内温度が変動する。また、炭化室を補修する際には扉を長時間開放するため、炉内温度が４００℃近くまで低下することもある。このような大きな温度変動に曝される部位では、被施工体である炉壁の熱膨張率と補修に使用される溶射施工体の熱膨張率が大きく異なると、温度変動によって溶射施工体が炉壁から剥離損耗してしまう。そのため、被施工体である炉壁の熱膨張率と同等の熱膨張率を有する溶射施工体を使用することにより耐用性を確保する必要がある。 By the way, since the coke oven carbonization chamber which is one of the repair targets by the above-mentioned sprayed material opens and closes the door when extruding coke, the furnace temperature is, for example, between 900 ° C. and 1300 ° C. near the door. fluctuate. In addition, when repairing the carbonization chamber, the door temperature is opened for a long time, so that the furnace temperature may decrease to nearly 400 ° C. In parts exposed to such large temperature fluctuations, if the thermal expansion coefficient of the furnace wall, which is the workpiece, and the thermal expansion coefficient of the thermal spraying construction body used for repair are significantly different, It will be worn away from the wall. Therefore, it is necessary to ensure the durability by using a thermal sprayed construction body having a thermal expansion coefficient equivalent to the thermal expansion coefficient of the furnace wall that is the work body.
また、金属の酸化発熱反応を利用した溶射に使用される溶射材料は、金属粉末の酸化により生成される酸化物（結合相）や一部溶融した耐火性粉末がガラス質になっている。このような施工体に含まれるガラス質は、補修施工後の使用中に徐々に結晶化が進行する。この結晶化は膨張を伴うため、施工体が被施工体の補修面から剥離損耗してしまう。そのため、結晶化促進剤を添加し、溶射後速やかに結晶化させることが必要になる。 In addition, a thermal spray material used for thermal spraying utilizing the oxidation exothermic reaction of a metal has a vitreous oxide (binding phase) generated by oxidation of metal powder or a partially molten refractory powder. The vitreous contained in such a construction body gradually crystallizes during use after repair construction. Since this crystallization is accompanied by expansion, the construction body is peeled away from the repair surface of the work body. Therefore, it is necessary to add a crystallization accelerator and quickly crystallize after spraying.
結晶化を促進するために、溶射材料にアルカリ金属イオン源が添加される。このようなアルカリ金属イオン源には、特許文献５が開示するように、爆発等の危険性のない安全な化合物であり、工業的にも入手が容易なアルカリ金属塩が利用されている。しかしながら、アルカリ金属塩は分解時に吸熱するため、４００℃程度に温度が低下した扉付近の補修では、アルカリ金属塩を含む溶射材料では、着火が困難であったり、着火した場合でも燃焼の継続が困難であったりする。 In order to promote crystallization, an alkali metal ion source is added to the thermal spray material. As such an alkali metal ion source, as disclosed in Patent Document 5, an alkali metal salt, which is a safe compound without danger of explosion or the like and easily available industrially, is used. However, since the alkali metal salt absorbs heat during decomposition, it is difficult to ignite with the sprayed material containing the alkali metal salt in the repair of the vicinity of the door whose temperature has dropped to about 400 ° C., or the combustion continues even when ignited. It may be difficult.
これに対し、特許文献６は、受熱した際に金属シリコンへの酸素供給源となる燃焼補助剤（金属酸化物）を使用することで、耐用性を維持しつつ、着火促進剤を無添加又は少量の添加で、着火性及び燃焼継続性を確保する構成を開示している。また、特許文献６は、溶射層間の一体性の向上を目的に、ＣａＯ純度が９０％以上である酸化カルシウム粉末及びＭｇＯ純度が９０％以上である酸化マグネシウム粉末のうち１種類以上を、４．０質量％以下添加することを開示している。 On the other hand, Patent Document 6 uses a combustion auxiliary agent (metal oxide) that becomes an oxygen supply source to metal silicon when receiving heat, so that no ignition accelerator is added while maintaining durability. The structure which ensures ignition property and combustion continuity with a small amount of addition is disclosed. Patent Document 6 describes at least one type of calcium oxide powder having a CaO purity of 90% or more and magnesium oxide powder having an MgO purity of 90% or more for the purpose of improving the integrity between the thermal spray layers. The addition of 0% by mass or less is disclosed.
上述した従来の溶射材料は、溶射材料に求められる上述のような特性のすべてを満足できるものではなく、十分に満足できるものではない。すなわち、特許文献１が開示する溶射材料は、酸化性粒体として金属シリコンを使用する場合、当該金属シリコンのみが燃焼材として機能するため、上述のような４００℃程度に温度が低下した箇所の補修では着火し難く、また燃焼継続性も不足する可能性がある。 The above-mentioned conventional thermal spray material does not satisfy all the above-mentioned properties required for the thermal spray material, and is not fully satisfactory. That is, in the thermal spray material disclosed in Patent Document 1, when metal silicon is used as the oxidizing particles, only the metal silicon functions as a combustion material. It is difficult to ignite by repair, and there is a possibility that the continuity of combustion may be insufficient.
また、特許文献２及び特許文献３が開示する溶射材料は、溶射層間の一体性の向上が期待できるが、１０００℃以上での熱膨張が大きい。そのため、ＭｇＯやＣａＯの添加により溶射層間の一体性を向上させようとしても、添加量が多量になると十分な耐用性を確保することができなくなる。加えて、特許文献３が開示する溶射材料ではＣａＯ成分の含有量が７０％以上あるため、製造時や保管時に一部又は全部が炭酸化したり水酸化したりする可能性があり、炭酸化や水酸化する部分が微量であっても点火性や燃焼継続性を著しく低下させる。ＭｇＯ成分が高い場合でも同様のことがいえる。 Moreover, although the thermal spray material which patent document 2 and patent document 3 disclose can anticipate the improvement of the integrity between thermal spray layers, the thermal expansion at 1000 degreeC or more is large. Therefore, even if an attempt is made to improve the integrity between the thermal spray layers by adding MgO or CaO, sufficient durability cannot be ensured if the amount added is large. In addition, since the thermal spray material disclosed in Patent Document 3 has a CaO component content of 70% or more, there is a possibility that a part or all of the CaO component may be carbonated or hydroxylated during production or storage. Even if the portion to be hydroxylated is very small, the ignitability and the combustion continuity are significantly reduced. The same is true even when the MgO component is high.
特許文献４が開示する溶射材料においても、金属過酸化物含有粒子は水酸化物や炭酸塩を含んでおり、緻密質施工体が得られる添加量まで増量すると点火性や燃焼の継続性等の作業性に問題が生じる。 Also in the thermal spray material disclosed in Patent Document 4, the metal peroxide-containing particles contain hydroxide and carbonate, and when the amount is increased to an addition amount to obtain a dense construction body, such as ignitability and continuity of combustion, etc. Problems arise in workability.
特許文献５が開示する溶射材料は、アルカリ金属塩が分解時に吸熱するため、上述のような４００℃程度に温度が低下した箇所の補修では、アルカリ金属塩を含む溶射材料では、着火が困難であったり、着火した場合でも燃焼の継続が困難であったりする。その結果、被施工体への溶射材料の付着率が低下し、施工効率が低下するという問題が発生する。また、被施工体表面において溶射材料の燃焼が継続し、結合相が十分に溶融した状態を実現できなければ、溶射層間の一体性が乏しくなるという問題も発生する。 Since the thermal spray material disclosed in Patent Document 5 absorbs heat when the alkali metal salt is decomposed, it is difficult to ignite the thermal spray material containing the alkali metal salt in the repair of the portion where the temperature is lowered to about 400 ° C. as described above. Or it may be difficult to continue combustion even when ignited. As a result, the adhesion rate of the thermal spray material to a construction object falls, and the problem that construction efficiency falls arises. Further, if the sprayed material continues to burn on the surface of the workpiece and the bonded phase cannot be sufficiently melted, there is a problem that the integrity between the sprayed layers becomes poor.
特許文献６が開示する溶射材料においても、ＣａＯやＭｇＯの利用で溶射層間の一体性は確保されるが、製造時や保管時に炭酸化や水酸化の可能性があり、点火性や燃焼継続性を著しく低下させる。 Also in the thermal spray material disclosed in Patent Document 6, the use of CaO or MgO ensures the integrity between the thermal spray layers, but there is a possibility of carbonation or hydroxylation during production or storage, and the ignitability and combustion continuity. Is significantly reduced.
本発明は、上記従来の事情を鑑みて提案されたものであって、熱膨張が珪石れんがと一致する緻密な施工体を形成することができ、かつ、作業性、安全性に優れる溶射材料を提供することを目的とする。 The present invention has been proposed in view of the above-described conventional circumstances, and is a thermal spray material that can form a dense construction body whose thermal expansion matches that of silica brick and is excellent in workability and safety. The purpose is to provide.
本発明は、耐火性粉末と燃焼剤である金属粉末とを含み、酸素とともに吹き付けて被補修面を補修する溶射法に使用する溶射材料を前提とする。そして、本発明に係る溶射材料は、耐火性粉末と金属粉末とウォラストナイト（ＣａＯ・ＳｉＯ２）とを主原料とし、ウォラストナイトを、主原料の全量に対して内掛けで０．１〜９．０質量％含有する溶射材料である。 The present invention is premised on a thermal spray material used for a thermal spraying method that includes a refractory powder and a metal powder as a combustion agent and that is sprayed with oxygen to repair a repaired surface. The spraying material according to the present invention, the refractory powder and metal powder and wollastonite (CaO · SiO 2) as a main raw material, wollastonite, an inner seat with respect to the total amount of the main raw material 0.1 It is a thermal spray material containing ˜9.0% by mass.
上記主原料は、金属粉末として金属シリコン粉末を含むことができる。この場合、耐火性粉末は、主原料の全量に対して７１．０〜８９．９質量％、金属シリコン粉末は、主原料の全量に対して１０〜２０質量％とすることができる。 The main raw material may include metal silicon powder as the metal powder. In this case, the refractory powder can be 71.0-89.9% by mass with respect to the total amount of the main raw material, and the metal silicon powder can be 10-20% by mass with respect to the total amount of the main raw material.
また、結晶化促進剤として、リチウムを含有する珪酸塩又はリチウムを含有する珪酸塩鉱物を、さらに添加することもできる。この場合、添加量は、主原料の全量に対して外掛けで、Ｌｉ２Ｏ換算で０．２〜０．７質量％とすることが好ましい。リチウム含有珪酸塩としては、例えば、珪酸リチウムを使用することができる。また、リチウム含有珪酸塩鉱物としては、例えば、スポジュメン（ＬｉＡｌＳｉ２Ｏ６）、ペタライト（ＬｉＡｌＳｉ４Ｏ１０）、ユークリプタイト（ＬｉＡｌＳｉＯ３）、レピドライト(ＬｉＫＡｌ２Ｆ２Ｓｉ３Ｏ９)等を使用することができる。これらのリチウム含有珪酸塩、リチウム含有珪酸塩鉱物は単体で使用してもよく、２種以上を組み合わせて使用してもよい。 Moreover, a silicate containing lithium or a silicate mineral containing lithium can be further added as a crystallization accelerator. In this case, it is preferable that the addition amount is an outer portion with respect to the total amount of the main raw material and is 0.2 to 0.7% by mass in terms of Li 2 O. As the lithium-containing silicate, for example, lithium silicate can be used. Further, as lithium-containing silicate mineral, for example, spodumene (LiAlSi 2 O 6 ), petalite (LiAlSi 4 O 10 ), eucryptite (LiAlSiO 3 ), lipidite (LiKAl 2 F 2 Si 3 O 9 ) and the like are used. can do. These lithium-containing silicates and lithium-containing silicate minerals may be used alone or in combination of two or more.
さらに、点火促進剤として、金属シリコン粉末の酸化反応に必要な初期の熱量を補助する機能を有する金属粉末を、主原料の全量に対して外掛けで０．１〜１．５質量％、さらに配合することができる。このような金属粉末としては、例えば、鉄粉、マンガン粉、バナジウム粉、マグネシウム粉、チタン粉、あるいはこれらの合金の粉末等を好適に使用することができる。これらの金属粉末は、単体で使用してもよく、２種以上を組み合わせて使用してもよい。 Furthermore, as an ignition accelerator, a metal powder having a function of assisting the initial amount of heat necessary for the oxidation reaction of the metal silicon powder is 0.1 to 1.5% by mass based on the total amount of the main raw material, Can be blended. As such a metal powder, for example, iron powder, manganese powder, vanadium powder, magnesium powder, titanium powder, or a powder of these alloys can be preferably used. These metal powders may be used alone or in combination of two or more.
また、燃焼補助剤として、溶射材料の燃焼中に酸素を供給して被施工体上で、燃焼剤である金属シリコン粉末を酸化させる機能を有する金属酸化物を、主原料の全量に対して外掛けで０．３〜２．０質量％、さらに配合することができる。このような金属酸化物としては、例えば、遷移金属酸化物、特に、第一遷移金属酸化物（酸化スカンジウム、酸化チタン、酸化バナジウム、酸化クロム、酸化マンガン、酸化鉄、酸化コバルト、酸化ニッケル、酸化銅）やアルカリ土類金属過酸化物（過酸化リチウム、過酸化カルシウム、過酸化マグネシウム、過酸化ストロンチウム、過酸化バリウム）を好適に使用することができる。なお、これらの金属酸化物は、単体で使用してもよく、２種以上を組み合わせて使用してもよい。 In addition, as a combustion aid, a metal oxide having a function of supplying oxygen during combustion of the thermal spray material to oxidize the metal silicon powder as the combustion agent on the workpiece is excluded from the total amount of the main raw material. It can be further blended by 0.3 to 2.0% by mass. Examples of such metal oxides include transition metal oxides, particularly first transition metal oxides (scandium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, oxidation Copper) and alkaline earth metal peroxides (lithium peroxide, calcium peroxide, magnesium peroxide, strontium peroxide, barium peroxide) can be preferably used. In addition, these metal oxides may be used alone or in combination of two or more.
本発明によれば、主原料に含まれるウォラストナイトが緻密化に寄与し、ＣａＯ粉末のように炭酸カルシウムや消石灰に変化して点火性や燃焼継続性といった作業性を低下させることはない。その結果、緻密化を目的にＣａＯ粉末を添加した従来の構成と比較して付着率が向上し、作業が効率化することができる。また、従来に比べて、耐用性、安全性が低下することもない。 According to the present invention, wollastonite contained in the main raw material does not contribute to densification, and does not change to calcium carbonate or slaked lime like CaO powder, thereby reducing workability such as ignition performance and combustion continuity. As a result, compared with the conventional structure which added CaO powder for the purpose of densification, an adhesion rate improves and work can be made efficient. In addition, the durability and safety are not lowered as compared with the conventional case.
従来、ＣａＯ粉末は緻密化を目的に添加されることがあった。しかしながら、上述のように、ＣａＯ粉末は炭酸カルシウムや消石灰に変化し点火性や燃焼継続性といった作業性を低下させることが懸念された。そこで、本願発明者らは、溶射施工体の焼結促進による緻密化方法、及び施工体の鉱物組成と熱膨張の関係を鋭意研究し、ＣａＯをウォラストナイトとして添加するという手法を発案した。そして、実際に、ウォラストナイト（Wollastonite：ＣａＯ・ＳｉＯ２）を適当量含有する場合に、施工体が緻密になり、しかもその施工体の熱膨張が珪石れんがから外れることがないかを検証した。その結果、施工体の熱膨張特性が珪石れんがの熱膨張特性から外れることなく施工体が緻密化するという知見を得た。本願発明者らは、以上のようにして得られた新たな知見に基づいて本発明に至った。 Conventionally, CaO powder has been added for the purpose of densification. However, as described above, there is a concern that the CaO powder may be changed to calcium carbonate or slaked lime to reduce workability such as ignition performance and combustion continuity. Therefore, the inventors of the present application have intensively studied the densification method by promoting the sintering of the thermal sprayed construction body and the relationship between the mineral composition of the construction body and thermal expansion, and have devised a method of adding CaO as wollastonite. And in fact, when a suitable amount of wollastonite (Wollastonite: CaO · SiO 2 ) was contained, the construction body became dense, and it was verified whether the thermal expansion of the construction body would not come off from the silica brick. . As a result, the knowledge that the construction body is densified without the thermal expansion characteristics of the construction body deviating from the thermal expansion characteristics of the silica brick is obtained. The inventors of the present application have arrived at the present invention based on the new findings obtained as described above.
本発明に係る溶射材料は、燃焼剤としての金属粉末と、耐火性粉末と、ウォラストナイトの混合物（以下、耐火性粉末と金属粉末と、ウォラストナイトとの混合物を主原料という。）から構成されており、さらに、特性を制御するために各種微量の添加物が加えられている。このように、ＣａＯをウォラストナイトの形で添加することで、ＣａＯが炭酸化や水酸化（水和）することがなく、点火性や燃焼継続性の低下を回避することができる。その結果、形成された施工体の熱膨張特性が珪石れんがの熱膨張特性から外れることがなく、また、施工時の熱による施工体の焼結が短時間に進行して緻密質施工体を得ることができ、かつ良好な作業性を長期間維持することができる。以下、本発明の原理について簡単に説明する。 The thermal spray material according to the present invention is a mixture of a metal powder as a combustion agent, a refractory powder, and wollastonite (hereinafter, a mixture of the refractory powder, metal powder, and wollastonite is referred to as a main raw material). In addition, various trace amounts of additives are added to control the characteristics. Thus, by adding CaO in the form of wollastonite, CaO is not carbonated or hydroxylated (hydrated), and a decrease in ignitability and combustion continuity can be avoided. As a result, the thermal expansion characteristics of the formed construction body do not deviate from the thermal expansion characteristics of the silica brick, and the construction body is sintered by heat during construction in a short time to obtain a dense construction body. And good workability can be maintained for a long time. The principle of the present invention will be briefly described below.
ＣａＯは珪石れんがに一般的に使用される成分であり、珪石れんがの焼結に有効であることが知られている。珪石れんがはクオーツと石灰、場合によっては少量の粘土等からなるプレス成形体を乾燥し、１４００℃程度で長時間焼成することによって得られる。焼成中にクオーツはクリストバライトに相転位し、その後安定なトリジマイトに変化する。トリジマイトはれんが内に部分的に形成されたＣａＯ−ＳｉＯ２系の融液を介して溶解析出反応で成長する。すなわち、ＣａＯ−ＳｉＯ２系の融液組成が、トリジマイトに関してＳｉＯ２が過飽和になりトリジマイトが析出する。また、トリジマイトを析出させる液相はクリストバライトに関してＳｉＯ２が不飽和なので、クリストバライトが液相に溶解する反応が進行する。このような反応は焼成中のみならず、炉の稼働中も進行し続けると考えられている。このとき、ＣａＯはある程度の量までは熱膨張に悪影響を及ぼさないため、珪石れんがの焼結助剤成分として適している。 CaO is a component generally used for silica bricks and is known to be effective for sintering of silica bricks. Silica brick is obtained by drying a press-molded body made of quartz and lime, and in some cases a small amount of clay, and firing it at about 1400 ° C. for a long time. During firing, quartz undergoes a phase transition to cristobalite and then changes to stable tridymite. Tridymite grows by a dissolution precipitation reaction through a CaO—SiO 2 melt partially formed in the brick. That is, in the CaO—SiO 2 melt composition, SiO 2 becomes supersaturated with respect to tridymite, and tridymite is precipitated. In addition, since the liquid phase in which tridymite is precipitated is SiO 2 unsaturated with respect to cristobalite, a reaction in which cristobalite is dissolved in the liquid phase proceeds. Such reactions are believed to continue not only during firing but also during operation of the furnace. At this time, CaO is suitable as a sintering aid component of silica brick because it does not adversely affect thermal expansion up to a certain amount.
このような観点からＳｉＯ２を主体とする溶射材料もＣａＯを含有することで、熱膨張に影響を及ぼさずに焼結による緻密化を促進できる可能性が容易に推定でき、ＣａＯ粉末を含有する溶射材料も種々提案されている。しかしながら、ＣａＯは単体では活性であり、大気中の二酸化炭素と反応して炭酸カルシウムになったり、水分と反応して消石灰に変化したりする場合があった。これらが生成すると、その量が微量であっても溶射作業中に分解吸熱し、点火性や燃焼継続性といった作業性が低下していた。 From this point of view, the thermal spray material mainly composed of SiO 2 can easily estimate the possibility that densification by sintering can be promoted without affecting thermal expansion by containing CaO, and contains CaO powder. Various thermal spray materials have been proposed. However, CaO is active as a simple substance, and may react with carbon dioxide in the atmosphere to form calcium carbonate or react with moisture to change to slaked lime. When these are generated, even if the amount is very small, they decompose and absorb heat during the thermal spraying work, and workability such as ignitability and combustion continuity is reduced.
これに対して、ＣａＯをウォラストナイトとして適当量添加することで、施工体が緻密になり、しかもその施工体の熱膨張は珪石れんがに近く好適であることが実験事実として分かった。ウォラストナイトの融点は１５４０℃であり融点が２８５０℃のＣａＯと比較してＣａＯ−ＳｉＯ２系の融液を形成しやすくなり、焼結を促進、緻密化に寄与しているものと考えられる。溶射は施工部が１７００℃を超える高温に達した後、比較的急速に冷却されるが、その間に融液の形成と融液を介した適切な物質移動が生じていると考えられる。また、ウォラストナイトは比較的安定であるため炭酸塩や水和物を生じることがなく、作業性の低下が生じることもない。 On the other hand, by adding an appropriate amount of CaO as wollastonite, the construction body became dense, and it was found as an experimental fact that the thermal expansion of the construction body was close to that of silica brick. The melting point of wollastonite is 1540 ° C., and it is easier to form a CaO—SiO 2 -based melt than CaO having a melting point of 2850 ° C., which is considered to promote sintering and contribute to densification. The thermal spraying is cooled relatively rapidly after the construction part reaches a high temperature exceeding 1700 ° C., and it is considered that the formation of the melt and the appropriate mass transfer through the melt occur during that time. Further, since wollastonite is relatively stable, carbonates and hydrates are not generated, and workability is not deteriorated.
ウォラストナイトの添加量は、主原料の全量に対し内掛けで０．１〜９．０質量％（０．１質量％以上かつ９．０質量％以下）である。より好ましくは０．５〜５．０質量％（０．５質量％以上かつ５．０質量％以下）である。ここで、主原料の全量は、耐火性粉末と金属粉末とウォラストナイトからなる１００質量％の混合物を意味する。 The added amount of wollastonite is 0.1 to 9.0% by mass (0.1% by mass or more and 9.0% by mass or less) based on the total amount of the main raw material. More preferably, it is 0.5-5.0 mass% (0.5 mass% or more and 5.0 mass% or less). Here, the total amount of the main raw material means a 100% by mass mixture composed of refractory powder, metal powder and wollastonite.
添加量が０．１質量％より少ないと、十分な焼結促進効果を得ることができないため好ましくない。一方、添加量が９．０質量％より多いと、施工時の融液生成量が多くなりすぎ、施工体が流動することで狙いの施工形状を得にくくなるとともに、施工体組成変化の影響が強くなり珪石れんがとの熱膨張の乖離が許容範囲を超えるため好ましくない。 If the amount added is less than 0.1% by mass, a sufficient sintering promoting effect cannot be obtained, which is not preferable. On the other hand, when the addition amount is more than 9.0% by mass, the amount of melt generated at the time of construction increases too much, and it becomes difficult to obtain a target construction shape due to the flow of the construction body, and the influence of the construction body composition change is also affected. It is not preferable because the difference in thermal expansion from the silica brick exceeds the allowable range.
使用するウォラストナイト粒子の成分は特に限定されないが、ＣａＯが４３〜５３質量％（４３質量％以上かつ５３質量％以下）、ＳｉＯ２が４７〜５７質量％（４７質量％以上かつ５７質量％以下）のもので、フリーのＣａＯや炭酸カルシウム、水酸化カルシウムはそれぞれ５質量％未満のものが好ましい。また、ウォラストナイトの粒径は２００μｍ以下であることが好ましい。粒径が２００μｍより大きいと反応性が乏しくなり、溶融促進の効果が低下する傾向にあるからである。 Component of wollastonite particles to be used is not particularly limited, CaO is (less 43 mass% or more and 53 wt%) 43 to 53 wt%, SiO 2 is 47-57 wt% (47 wt% or more and 57 wt% The free CaO, calcium carbonate, and calcium hydroxide are each preferably less than 5% by mass. The particle size of wollastonite is preferably 200 μm or less. This is because if the particle size is larger than 200 μm, the reactivity becomes poor and the effect of promoting the melting tends to decrease.
以下、ウォラストナイト以外の成分について詳述する。 Hereinafter, components other than wollastonite will be described in detail.
（耐火性粉末）
上述のように、本発明に係る溶射材料は、耐火性粉末と金属粉末とウォラストナイトの混合物を主原料とする。当該耐火性粉末には、珪石、珪石れんが粉、溶融シリカ、シャモット、コージエライト等を用途に応じて用いることができる。特に限定されないが、耐火性粉末の最大粒子径は２．０ｍｍ以下であることが好ましい。最大粒子径が２．０ｍｍより大きいと、施工時に大きい粒子が跳ね返るため被施工体への付着が困難となり、溶射効率が低下するからである。
(Fireproof powder)
As described above, the thermal spray material according to the present invention is mainly composed of a mixture of refractory powder, metal powder and wollastonite. As the refractory powder, silica stone, silica brick powder, fused silica, chamotte, cordierite, or the like can be used depending on the application. Although not particularly limited, the maximum particle size of the refractory powder is preferably 2.0 mm or less. If the maximum particle size is larger than 2.0 mm, large particles will rebound during construction, making it difficult to adhere to the work piece and lowering the thermal spraying efficiency.
（金属粉末）
本発明に係る溶射材料では、燃焼剤としての金属粉末が配合される。燃焼剤は、燃焼後に上述の耐火性粉体を結合する結合相を形成する酸化物となる。例えば、補修対象である被施工体がシリカ主体である珪石れんがからなる場合、当該燃焼剤として金属シリコン粉末を使用することができる。
(Metal powder)
In the thermal spray material according to the present invention, a metal powder as a combustion agent is blended. A combustion agent turns into an oxide which forms the binder phase which couple | bonds the above-mentioned refractory powder after combustion. For example, when the work object to be repaired is made of silica brick mainly composed of silica, metal silicon powder can be used as the combusting agent.
主原料の全量に対して、金属シリコン粉末の添加量は１０〜２０質量％（１０質量％以上かつ２０質量％以下）であり、好ましくは１３〜１７質量％（１３質量％以上かつ１７質量％以下）である。 The addition amount of the metal silicon powder is 10 to 20% by mass (10 to 20% by mass), preferably 13 to 17% by mass (13 to 17% by mass) with respect to the total amount of the main raw material. The following).
添加量が１０質量％より少ないと、燃焼反応が弱くなり燃焼の継続性と被施工体への付着が著しく悪化するため、溶射材料として成立しない。また、添加量が２０質量％を超えると、燃焼による発熱量が多く高温になりすぎる。その結果、溶射した材料の粘性が低下して溶射した材料が被施工体から流れ落ちてしまい良好な施工体を得ることができなくなるため、溶射材料として成立しない。金属シリコン粉末に含まれる金属Ｓｉ成分の質量割合（Ｓｉ純度）は９０％以上であることが好ましい。Ｓｉ純度が低い場合、シリカの結晶化を阻害するアルミニウム等の元素が多く含まれることになるため好ましくない。なお、主原料の金属シリコン粉末及びウォラストナイト以外の残部は耐火性粉末である。 If the addition amount is less than 10% by mass, the combustion reaction is weakened, and the continuity of combustion and the adhesion to the workpiece are significantly deteriorated. On the other hand, if the amount added exceeds 20% by mass, the amount of heat generated by combustion is too high and the temperature becomes too high. As a result, since the viscosity of the sprayed material decreases and the sprayed material flows down from the work body and a good work body cannot be obtained, it is not established as a sprayed material. The mass ratio (Si purity) of the metal Si component contained in the metal silicon powder is preferably 90% or more. A low Si purity is not preferable because it contains a large amount of elements such as aluminum that inhibit crystallization of silica. The remainder other than the main raw material metal silicon powder and wollastonite is refractory powder.
金属粉末の粒子径は、溶射材料全体において、７５μｍ以上が５質量％以下、２０μｍ以下が３〜１４質量％（３質量％以上かつ１４質量％以下）、残部を２０〜７５μｍ（２０μｍより大きく、かつ７５μｍ未満）とすることが好ましい。より好ましくは、７５μｍ以上が３．０質量％以下、２０μｍ以下が５〜１２質量％（５質量％以上かつ１２質量％以下）である。粒子径が７５μｍ以上の金属粉末は、燃焼反応が弱く、配合量が多くなると燃焼継続性が低下するため、５質量％以下とすることが好ましい。２０μｍ以下の金属粉末が３質量％未満である場合も、燃焼反応が弱くなり燃焼継続性が低下するため好ましくない。２０μｍ以下の金属粉末が１４質量％を超えると、粉体流動性が低下して脈動を引き起こして逆火の危険性が大きくなるため好ましくない。 As for the particle diameter of the metal powder, 75 μm or more is 5% by mass or less, 20 μm or less is 3 to 14% by mass (3% by mass or more and 14% by mass or less), and the remainder is 20 to 75 μm (greater than 20 μm). And less than 75 μm). More preferably, 75 μm or more is 3.0 mass% or less, and 20 μm or less is 5 to 12 mass% (5 mass% or more and 12 mass% or less). The metal powder having a particle size of 75 μm or more has a weak combustion reaction, and the combustion continuity is lowered when the blending amount is increased. Even when the metal powder of 20 μm or less is less than 3% by mass, the combustion reaction becomes weak and the combustion continuity is lowered, which is not preferable. When the metal powder of 20 μm or less exceeds 14% by mass, the powder fluidity is lowered, causing pulsation and increasing the risk of backfire, which is not preferable.
（結晶化促進剤）
本発明に係る溶射材料では、リチウムを含有する珪酸塩（以下、Ｌｉ含有珪酸塩という。）又はリチウムを含有する珪酸塩鉱物（以下、Ｌｉ含有珪酸塩鉱物という。）の結晶化促進剤を必要に応じて配合できる。結晶化促進剤を適当量添加することで、溶射後速やか（補修施工後の被施工体の冷却中）に結晶化させ、被施工体との膨張乖離に起因した施工体の被施工体から剥離を回避することができる。
(Crystallization accelerator)
The thermal spray material according to the present invention requires a crystallization accelerator for lithium-containing silicate (hereinafter referred to as Li-containing silicate) or lithium-containing silicate mineral (hereinafter referred to as Li-containing silicate mineral). It can be blended according to. By adding an appropriate amount of crystallization accelerator, it crystallizes immediately after spraying (during cooling of the work piece after repair work), and peels off the work piece from the work piece due to expansion divergence from the work piece. Can be avoided.
Ｌｉ含有珪酸塩としては、例えば、珪酸リチウムを使用することができる。また、Ｌｉ含有珪酸塩鉱物としては、例えば、スポジュメン（ＬｉＡｌＳｉ２Ｏ６）、ペタライト（ＬｉＡｌＳｉ４Ｏ１０）、ユークリプタイト（ＬｉＡｌＳｉＯ３）、レピドライト(ＬｉＫＡｌ２Ｆ２Ｓｉ３Ｏ９)等を使用することができる。これらの中でも、スポジュメン、ペタライトは工業的に比較的安価に入手可能であり、経済的である。なお、これらの、Ｌｉ含有珪酸塩、Ｌｉ含有珪酸塩鉱物は単体で使用してもよく、２種以上を組み合わせて使用してもよい。 As the Li-containing silicate, for example, lithium silicate can be used. Moreover, as Li-containing silicate minerals, for example, spodumene (LiAlSi 2 O 6 ), petalite (LiAlSi 4 O 10 ), eucryptite (LiAlSiO 3 ), lipidite (LiKAl 2 F 2 Si 3 O 9 ), etc. are used. can do. Among these, spojumen and petalite are economically available industrially and are economical. These Li-containing silicates and Li-containing silicate minerals may be used alone or in combination of two or more.
結晶化促進剤を添加する場合の添加量は、酸化物（Ｌｉ２Ｏ）換算で、主原料の全量に対して外掛けで、０．２〜０．７質量％（０．２質量％以上かつ０．７質量％以下）である。添加量がＬｉ２Ｏ換算で０．２質量％未満であると、十分な結晶化促進効果が得られない。一方、添加量がＬｉ２Ｏ換算で０．７質量％を超えると、融液中のアルカリ濃度が高くなることで粘性が低下して溶射体が流下するため好ましくない。Ｌｉを含有する結晶化促進剤の粒径は特には限定されないが、溶射時に速やかに融解して結合相と混ざるためには最大粒子径が１．０ｍｍ以下とすることが望ましい。 When the crystallization accelerator is added, the amount added is 0.2 to 0.7% by mass (over 0.2% by mass or more) in terms of oxide (Li 2 O), which is an external amount with respect to the total amount of the main raw material. And 0.7% by mass or less). When the addition amount is less than 0.2% by mass in terms of Li 2 O, a sufficient crystallization promoting effect cannot be obtained. On the other hand, if the amount added exceeds 0.7% by mass in terms of Li 2 O, the alkali concentration in the melt increases, so that the viscosity decreases and the sprayed material flows down, which is not preferable. The particle size of the crystallization accelerator containing Li is not particularly limited, but it is desirable that the maximum particle size be 1.0 mm or less in order to melt quickly and mix with the binder phase during thermal spraying.
（点火促進剤）
本発明に係る溶射材料では、金属シリコン粉末の酸化反応に必要な初期の熱量を補助する機能を有する金属粉末の点火促進剤を必要に応じて配合できる。点火促進剤を配合することにより、被施工体温度が８００℃以下の比較的低温である場合でも、溶射開始時の点火を促進することができる。
(Ignition accelerator)
In the thermal spray material according to the present invention, an ignition accelerator for metal powder having a function of assisting the initial amount of heat necessary for the oxidation reaction of the metal silicon powder can be blended as necessary. By blending the ignition accelerator, it is possible to promote ignition at the start of thermal spraying even when the temperature of the workpiece is a relatively low temperature of 800 ° C. or less.
このような金属粉末としては、例えば、鉄粉、マンガン粉、バナジウム粉、マグネシウム粉、チタン粉、あるいはこれらの合金の粉末等を好適に使用することができる。これらの金属粉末は、単体で使用してもよく、２種以上を組み合わせて使用してもよい。点火促進剤は発火点が３００〜８００℃であれば使用できるが、発火点が４００℃以下である鉄粉が最も好ましく使用できる。 As such a metal powder, for example, iron powder, manganese powder, vanadium powder, magnesium powder, titanium powder, or a powder of these alloys can be preferably used. These metal powders may be used alone or in combination of two or more. The ignition accelerator can be used if its ignition point is 300 to 800 ° C, but iron powder having an ignition point of 400 ° C or less can be most preferably used.
点火促進剤を添加する場合の添加量は、主原料の全量に対して外掛けで０．１〜１．５質量％（０．１質量％以上かつ１．５質量％以下）であることが好ましい。添加量が０．１質量％未満であると、点火促進剤の添加効果（点火促進効果）が十分得られなくなる。一方、添加量が１．５質量％より多いと、シリカの結晶化を阻害する上、爆発や逆火等の作業上の危険性が高まるため好ましくない。また、点火促進剤として金属粉末の粒子径は１００μｍ以下であることが好ましい。粒子径が１００μｍより大きいと反応性が乏しくなり、点火促進の効果が得られなくなるからである。 When the ignition accelerator is added, the addition amount is 0.1 to 1.5% by mass (0.1% by mass to 1.5% by mass) based on the total amount of the main raw material. preferable. When the addition amount is less than 0.1% by mass, the effect of adding the ignition accelerator (ignition promotion effect) cannot be obtained sufficiently. On the other hand, when the amount added is more than 1.5% by mass, it is not preferable because it inhibits crystallization of silica and increases the risk of work such as explosion and flashback. Moreover, it is preferable that the particle diameter of a metal powder as an ignition accelerator is 100 micrometers or less. This is because if the particle size is larger than 100 μm, the reactivity becomes poor, and the effect of promoting ignition cannot be obtained.
（燃焼補助剤）
本発明に係る溶射材料では、溶射材料の燃焼中に酸素を供給して、被施工体上で、燃焼剤である金属シリコン粉末を酸化させる機能を有する燃焼補助剤を必要に応じて配合することができる。燃焼補助剤は、金属シリコンに付着していると、被施工体に付着した際の受熱により酸素供給源となる金属酸化物の粉末からなる。
(Combustion aid)
In the thermal spray material according to the present invention, oxygen is supplied during combustion of the thermal spray material, and a combustion auxiliary agent having a function of oxidizing the metal silicon powder as the combustion agent is blended as necessary on the workpiece. Can do. When the combustion auxiliary agent is attached to the metal silicon, the combustion auxiliary agent is made of a metal oxide powder that becomes an oxygen supply source by receiving heat when attached to the workpiece.
このような金属酸化物としては、例えば、遷移金属酸化物、特に、第一遷移金属酸化物（酸化スカンジウム、酸化チタン、酸化バナジウム、酸化クロム、酸化マンガン、酸化鉄、酸化コバルト、酸化ニッケル、酸化銅）を好適に使用することができる。これらの金属酸化物は、金属シリコンに付着していると、被施工体上における燃焼中に自身の酸化数を低下させることで金属シリコンを酸化する。燃焼剤である金属シリコン粉末が酸化されるため、被施工体上での燃焼が継続されることになる。なお、これらの金属酸化物は、単体で添加されてもよく、２種以上が組み合わされて添加されてもよい。金属シリコン粉末を効率よく酸化させる観点からは、酸化鉄（Ｆｅ２Ｏ３）が、金属シリコン粉末が酸化されて生成したシリカガラスに固溶した場合に酸素透過速度を上昇させる効果もあるため特に好適に使用できる。 Examples of such metal oxides include transition metal oxides, particularly first transition metal oxides (scandium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, oxidation Copper) can be preferably used. When these metal oxides adhere to the metal silicon, the metal silicon is oxidized by lowering the oxidation number of the metal oxide during combustion on the workpiece. Since the metal silicon powder that is the combustion agent is oxidized, the combustion on the workpiece is continued. These metal oxides may be added alone or in combination of two or more. From the viewpoint of efficiently oxidizing metal silicon powder, iron oxide (Fe 2 O 3 ) has an effect of increasing the oxygen permeation rate when dissolved in silica glass produced by oxidation of metal silicon powder. It can be used suitably.
燃焼補助剤を添加する場合の添加量は、主原料の全量に対して外掛けで０．３〜２．０質量％（０．３質量％以上かつ２．０質量％以下）である。添加量が０．３質量％より少ないと燃焼剤の燃焼継続効果が少なくなる。また、添加量が２．０質量％より多いと、不純物が多くなり、組成が変化し過ぎて熱膨張特性等の設計特性が発揮できなくなるため好ましくない。また、金属酸化物粉末の粒子径は１００μｍ以下であることが好ましい。粒子径が１００μｍより大きいと反応性が乏しくなり、燃焼の継続性を向上する効果が得られなくなる。 When the combustion auxiliary agent is added, the amount added is 0.3 to 2.0% by mass (0.3% by mass or more and 2.0% by mass or less) based on the total amount of the main raw material. When the addition amount is less than 0.3% by mass, the combustion continuation effect of the combustor is reduced. On the other hand, when the addition amount is more than 2.0% by mass, impurities are increased and the composition changes so much that design characteristics such as thermal expansion characteristics cannot be exhibited. Moreover, it is preferable that the particle diameter of metal oxide powder is 100 micrometers or less. When the particle size is larger than 100 μm, the reactivity becomes poor and the effect of improving the continuity of combustion cannot be obtained.
（その他の添加物）
上述の各成分に加えて、本発明の効果を阻害しない範囲において、流動性改善や鉱物組成の調整を目的として、ヒュームドシリカや、マグネシウム、カルシウム、鉄から選択された元素の酸化物、炭化物、窒化物等を添加することもできる。
(Other additives)
In addition to the above-described components, oxides and carbides of elements selected from fumed silica, magnesium, calcium, and iron for the purpose of improving fluidity and adjusting the mineral composition within a range that does not impair the effects of the present invention. A nitride or the like can also be added.
以下に実施例及び比較例を提示して、本発明の溶射材料を説明する。 Examples and comparative examples are presented below to describe the thermal spray material of the present invention.
表１、表２に示す配合割合で溶射材料を作成し、各溶射材料を使用した溶射施工により形成した施工体を評価した。各溶射材料で使用した耐火性粉末は珪石である。各溶射材料で使用した金属シリコン粉末のＳｉ純度は９７％である。各溶射材料で使用したウォラストナイトは組成がＣａＯ４５質量％、ＳｉＯ２５２質量％であり、粒子径は１２５μｍ以下である。なお、耐火性粉末の粒子径及び金属シリコン粉末の粒子径は、表１、表２中に示している。表１、表２において、「１０００−２０００」は、１０００μｍより大きく、かつ２０００μｍ以下を意味する。「６００−１０００」は、６００μｍより大きく、かつ１０００μｍ以下を意味する。「２００−６００」は、２００μｍより大きく、かつ６００μｍ以下を意味する。「−２００」は、２００μｍ以下を意味する。また、「７５−」は、７５μｍ以上、を意味する。「２０−７５」は、２０μｍより大きく、かつ７５μｍ未満を意味する。「−２０μｍ」は、２０μｍ以下を意味する。 Thermal spray materials were prepared at the blending ratios shown in Table 1 and Table 2, and construction bodies formed by thermal spraying using the respective thermal spray materials were evaluated. The refractory powder used in each spray material is silica. The Si purity of the metal silicon powder used in each thermal spray material is 97%. The wollastonite used in each thermal spray material has a composition of CaO 45 mass%, SiO 2 52 mass%, and a particle diameter of 125 μm or less. The particle diameters of the refractory powder and the metal silicon powder are shown in Tables 1 and 2. In Tables 1 and 2, “1000-2000” means greater than 1000 μm and less than or equal to 2000 μm. “600-1000” means greater than 600 μm and less than 1000 μm. “200-600” means greater than 200 μm and less than or equal to 600 μm. “−200” means 200 μm or less. “75−” means 75 μm or more. “20-75” means greater than 20 μm and less than 75 μm. “−20 μm” means 20 μm or less.
溶射施工は、各溶射材料４ｋｇを、エジェクタ式の溶射装置を用いて、被溶射体に吹き付けることで実施した。搬送ガスは純度１００％の酸素とし、流量は３２Ｎｍ３／ｈとした。材料供給速度は９５〜１０５ｋｇ／ｈである。ランスは２ｍのものを使用し、先端ノズル径はφ１４とした。被溶射体として、２３０×２３０×３０ｍｍのシャモットれんが（耐火度ＳＫ３６）を炉の中に配置し、炉の中の雰囲気温度を約１０００℃に加熱した後、炉を開放し、れんがの表面温度が約７００℃に冷却されたときに、かまぼこ状に溶射施工を行った。 The thermal spraying was carried out by spraying 4 kg of each thermal spray material on the sprayed body using an ejector-type thermal spraying apparatus. The carrier gas was oxygen having a purity of 100%, and the flow rate was 32 Nm 3 / h. The material supply rate is 95 to 105 kg / h. A lance with a length of 2 m was used, and the tip nozzle diameter was φ14. As a sprayed body, a 230 × 230 × 30 mm chamotte brick (fire resistance SK36) was placed in the furnace, the atmospheric temperature in the furnace was heated to about 1000 ° C., the furnace was opened, and the brick surface temperature Was cooled to about 700 ° C., it was sprayed in a kamaboko shape.
評価は、各溶射材料による施工体に関して溶射作業性として、点火性、燃焼継続性、溶融度合い、付着率について行った。また、施工体物性として施工体の熱膨張率を測定し、珪石れんがの熱膨張率との一致に関して評価した。各評価の結果は、表１、表２中に記載している。 Evaluation was performed about the ignitability, the combustion continuity, the melting degree, and the adhesion rate as the thermal spraying workability for the construction body made of each thermal spray material. Moreover, the thermal expansion coefficient of the construction body was measured as the physical properties of the construction body, and the agreement with the thermal expansion coefficient of the silica brick was evaluated. The results of each evaluation are shown in Tables 1 and 2.
点火性は、溶射施工開始時の点火性を、目視観察により評価した。「○」は速やかに点火し材料が付着し始めたことを示し、「△」は点火したものの燃焼が弱かったことを示している。 The ignitability was evaluated by visual observation of the ignitability at the start of thermal spraying. “◯” indicates that the material was ignited promptly and the material started to adhere, and “Δ” indicates that the material was ignited but the combustion was weak.
燃焼継続性は、溶射施工時の燃焼継続性を、目視観察により評価した。「○」は失火の気配がなく燃焼時の光が強いまま燃焼が継続したことを示し、「△」は失火の気配がないものの燃焼時の光が弱かったことを示している。 Combustion continuity was evaluated by visual observation of combustion continuity during thermal spraying. “◯” indicates that there was no sign of misfire and the combustion continued while the light at the time of combustion was strong, and “△” indicates that the light at the time of combustion was weak although there was no sign of misfire.
溶融度合いは、施工中の様子と切断面観察より評価した。「○」は施工中に垂れずに施工体中の溶射層間が緻密となって一体化し層間の判別が不明になっていたことを示し、「△」は施工体中に垂れなかったが施工体中の溶射層間が一体化していたものの層間の判別がついたことを示し、「×」は焼結促進不足に起因して溶射層間が一体化していなかったことを示し、「××」は溶融過多のため施工中に垂れてしまったことを示す。なお、「△」の評価のうち、過溶融気味であったものは「▲」で示している。 The degree of melting was evaluated from the state during construction and observation of the cut surface. "○" indicates that the sprayed layers in the construction body were dense and integrated without sagging during construction, and the distinction between the layers was unknown. "△" did not sag in the construction body, but the construction body The inside of the thermal spraying layer was integrated, but the interlayer was identified, “×” indicates that the thermal spraying layer was not integrated due to insufficient sintering promotion, and “XX” indicates melting. It shows that it has dripped during construction due to excessive. Of the evaluations of “△”, those that seemed to be overmelted are indicated by “▲”.
付着率は、溶射試験後に被施工体に付着した材料を採取して重量を測定し、先端ノズルから吐出した溶射材料の重量に対する当該付着質量の割合を算出している。 The adhesion rate is obtained by collecting the material adhering to the workpiece after the thermal spray test and measuring the weight, and calculating the ratio of the adhering mass to the weight of the thermal spray material discharged from the tip nozzle.
珪石れんがとの熱膨張の一致は、施工体が冷えた状態で、施工体から円柱状の試料を切出して当該試料の熱間線膨張率を測定し、当該熱間線膨張率と珪石れんがの熱間線膨張率とを４００〜１３００℃の範囲で比較し、その乖離具合をもって評価した。「○」は乖離が０．０５％未満で実用上全く問題がないことを示し、「△」は乖離が０．０５％以上０．１０％未満で実用上問題のない程に一致することを示し、「×」は、０．１０％以上乖離し実用上問題が懸念されることを示している。 The coincidence of thermal expansion with silica brick is that when the construction body is cooled, a cylindrical sample is cut out from the construction body and the hot linear expansion coefficient of the sample is measured. The hot linear expansion coefficient was compared in the range of 400 to 1300 ° C., and the degree of deviation was evaluated. “○” indicates that the deviation is less than 0.05% and there is no practical problem at all, and “△” indicates that the deviation is 0.05% or more and less than 0.10% and that there is no practical problem. "X" indicates that there is a concern about practical problems with a deviation of 0.10% or more.
表１に示す各実施例は、珪石からなる耐火性粉末と金属シリコン粉末とウォラストナイトからなる主原料１００質量％において、金属シリコン粉末の含有量が１０〜２０質量％であり、ウォラストナイトの含有量が、０.１〜９.０質量％である配合である。また、添加剤として、結晶化促進剤である粒子径が１．０ｍｍ以下のスポジュメン、点火促進剤である粒子径が１００μｍ以下の鉄粉、燃焼補助剤である粒子径が１００μｍ以下の酸化第二鉄（酸化鉄（III））粉末を、適宜、添加している。なお、スポジュメン、鉄粉、酸化第二鉄粉末の添加量は、主原料全量に対する外掛けで規定している。また、スポジュメンの配合量は、酸化物（Ｌｉ２Ｏ）換算で記載している。以下、各配合について簡単に説明する。 In each example shown in Table 1, the content of metal silicon powder is 10 to 20% by mass in the main raw material 100% by mass composed of refractory powder composed of silica stone, metal silicon powder and wollastonite, and wollastonite The content is 0.1 to 9.0% by mass. Further, as additives, spodumene having a particle size of 1.0 mm or less as a crystallization accelerator, iron powder having a particle size of 100 μm or less as an ignition accelerator, and second oxidized oxide having a particle size of 100 μm or less as a combustion aid. Iron (iron (III) oxide) powder is appropriately added. In addition, the addition amount of spodumene, iron powder, and ferric oxide powder is prescribed | regulated with the outer coating with respect to the main raw material whole quantity. The amount of spodumene is described in oxide (Li 2 O) conversion. Hereinafter, each formulation will be briefly described.
実施例１〜実施例４及び実施例９〜実施例１０は、ウォラストナイトの配合量をそれぞれ変更している。実施例５〜実施例８は、実施例４の配合において、スポジュメンの配合量、酸化第二鉄粉末の配合量、鉄粉の配合量、珪石の粒度配合をそれぞれ変更している。実施例１１〜実施例１２は、実施例１の配合において、耐火性粉末と金属シリコン粉末との配合割合をそれぞれ変更している。実施例１３〜実施例１４は、実施例１０の配合において、耐火性粉末と金属シリコン粉末との配合割合をそれぞれ変更している。 In Examples 1 to 4 and Examples 9 to 10, the amount of wollastonite is changed. In Examples 5 to 8, the amount of spojumen, the amount of ferric oxide powder, the amount of iron powder, and the particle size of quartzite are changed in the formulation of Example 4. In Examples 11 to 12, the mixing ratio of the refractory powder and the metal silicon powder in the formulation of Example 1 is changed. In Examples 13 to 14, the mixing ratio of the refractory powder and the metal silicon powder in the formulation of Example 10 is changed.
表１に示すように、いずれも点火性、燃焼継続性、溶融度合い、付着率、珪石れんがとの熱膨張の一致の各評価項目において、良好な結果が得られていることが理解できる。珪石れんがとの熱膨張の一致を示す一例として、図１に、実施例４として示す溶射材料の熱膨張特性と珪石れんがの熱膨張特性とを示す。図１において、横軸が温度に対応し、縦軸が線膨張率に対応する。また、図１では、本発明に係る溶射材料の熱膨張特性を実線で示すとともに、珪石れんがの熱膨張特性を破線で示している。４００〜１３００℃の範囲において、良好な一致を示していることが理解できる。 As shown in Table 1, it can be understood that good results are obtained in each of the evaluation items of ignitability, combustion continuity, degree of melting, adhesion rate, and coincidence of thermal expansion with silica brick. As an example showing the coincidence of thermal expansion with silica brick, FIG. 1 shows the thermal expansion characteristic of the thermal spray material shown as Example 4 and the thermal expansion characteristic of silica brick. In FIG. 1, the horizontal axis corresponds to temperature, and the vertical axis corresponds to the linear expansion coefficient. Moreover, in FIG. 1, while showing the thermal expansion characteristic of the thermal spray material which concerns on this invention with a continuous line, the thermal expansion characteristic of a silica brick is shown with the broken line. It can be understood that good agreement is shown in the range of 400 to 1300 ° C.
続いて、比較例について説明する。比較例１は、実施例１〜実施例４及び実施例９〜実施例１０の配合との対比において、ウォラストナイトを添加していない（配合量ゼロ）配合である。この配合では、溶融不足になり緻密性が低下し、付着率も低下した。 Subsequently, a comparative example will be described. Comparative Example 1 is a blend in which wollastonite is not added (zero blending amount) in comparison with the blends of Examples 1 to 4 and Examples 9 to 10. In this formulation, the melting was insufficient, the compactness was lowered, and the adhesion rate was also lowered.
比較例２〜比較例５は、実施例１〜実施例４及び実施例９〜実施例１０の配合との対比において、ウォラストナイトに代えてＭｇＯ質粉又はＣａＯ質粉を添加した配合である。なお、ＭｇＯ質粉は純度９７％で粒子径が１５０μｍ以下のものを使用し、ＣａＯ質粉は純度９７％で粒子径が１２５μｍ以下のものを使用している。これらの配合では、珪石れんがとの熱膨張の一致の評価項目において不一致であった。 Comparative Example 2 to Comparative Example 5 are formulations in which MgO powder or CaO powder was added instead of wollastonite in comparison with the blends of Examples 1 to 4 and Examples 9 to 10. . The MgO powder is 97% pure and the particle diameter is 150 μm or less, and the CaO powder is 97% pure and the particle diameter is 125 μm or less. In these formulations, there was a discrepancy in the evaluation items of the thermal expansion agreement with the silica brick.
比較例６〜比較例９は、実施例１〜実施例４及び実施例９〜実施例１０の配合との対比において、ウォラストナイトの配合量を変更している。比較例６及び比較例７はウォラストナイトの配合量が適正量より少ない場合であり、溶融不足になって緻密性が低下し、付着率も低下した。また、比較例８及び比較例９はウォラストナイトの配合量が適正量より多い場合であり、溶融過多となり垂れたような施工体になった。 In Comparative Examples 6 to 9, the amount of wollastonite is changed in comparison with the formulations of Examples 1 to 4 and Examples 9 to 10. Comparative Example 6 and Comparative Example 7 were cases where the blending amount of wollastonite was less than the appropriate amount, and due to insufficient melting, the compactness decreased and the adhesion rate also decreased. Moreover, the comparative example 8 and the comparative example 9 are cases where the compounding quantity of a wollastonite is more than an appropriate quantity, and it became a construction body which dripped excessively and became dripping.
以上のように、溶射材料を、耐火性粉末と、燃焼剤としての金属粉末と、ウォラストナイトの混合物で構成することにより、熱膨張が珪石れんがと一致する緻密な施工体を形成することができる。また、ウォラストナイトは比較的安定であるため炭酸塩や水和物を生じることがなく、点火性や燃焼継続性を低下させることもない。その結果、作業時間が不要に長時間になることを抑制でき、施工コストの上昇を防止することができる。また、施工作業者が高温で粉塵の多い環境に曝される時間が不要に長時間になることもない。さらに、多量の点火促進剤を添加することなく点火性と燃焼継続性が確保できるため、安全性も確保することができる。加えて、溶射層間の一体性を向上させるために多量のＭｇＯやＣａＯを添加する必要がなく、耐用性が低下することもない。 As described above, by forming the thermal spray material from a mixture of refractory powder, metal powder as a combustion agent, and wollastonite, it is possible to form a dense construction body whose thermal expansion matches that of silica brick. it can. Further, since wollastonite is relatively stable, carbonates and hydrates are not generated, and ignition performance and combustion continuity are not reduced. As a result, it is possible to prevent the work time from becoming unnecessarily long, and to prevent an increase in construction cost. Further, the time for the construction worker to be exposed to a high temperature and dusty environment is not unnecessarily long. Furthermore, since ignition performance and combustion continuity can be ensured without adding a large amount of ignition accelerator, safety can be ensured. In addition, it is not necessary to add a large amount of MgO or CaO in order to improve the integrity between the thermal spray layers, and the durability is not lowered.
本発明に係る溶射材料は、熱膨張が珪石れんがと一致する緻密な施工体を形成することができるとともに、作業性、安全性に優れるため、コークス炉炭化室の補修等に使用する溶射材料として有用である。 As the thermal spray material according to the present invention can form a dense construction body whose thermal expansion matches that of silica brick, and is excellent in workability and safety, it is used as a thermal spray material used for repairing the coke oven carbonization chamber, etc. Useful.
Claims (6)
前記耐火性粉末と前記金属粉末とウォラストナイト（ＣａＯ・ＳｉＯ２）とを主原料とし、前記ウォラストナイトを前記主原料の全量に対して内掛けで０.１〜９.０質量％含有することを特徴とする溶射材料。 A thermal spray material that includes a refractory powder and a metal powder that is a combustion agent, and is used in a thermal spraying method that repairs a repaired surface by spraying with oxygen,
The fireproof powder, the metal powder, and wollastonite (CaO.SiO 2 ) are used as main raw materials, and the wollastonite is contained in an amount of 0.1 to 9.0% by mass based on the total amount of the main raw materials. Thermal spray material characterized by
前記金属粉末としての金属シリコン粉末を、前記主原料の全量に対して１０〜２０質量％含有する、請求項１記載の溶射材料。 The refractory powder is 71.0-89.9% by mass with respect to the total amount of the main raw material,
The thermal spray material of Claim 1 which contains 10-20 mass% of metal silicon powder as said metal powder with respect to the whole quantity of the said main raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016027746A JP6263208B2 (en) | 2016-02-17 | 2016-02-17 | Thermal spray material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016027746A JP6263208B2 (en) | 2016-02-17 | 2016-02-17 | Thermal spray material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017145452A true JP2017145452A (en) | 2017-08-24 |
| JP6263208B2 JP6263208B2 (en) | 2018-01-17 |
Family
ID=59680713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016027746A Active JP6263208B2 (en) | 2016-02-17 | 2016-02-17 | Thermal spray material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6263208B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031379A (en) * | 2021-11-05 | 2022-02-11 | 瑞泰科技股份有限公司 | Aluminum-silicon high-temperature spray coating |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4486545A (en) * | 1982-04-02 | 1984-12-04 | Shinagawa Refractories, Co., Ltd. | SIO2 -CaO Based low cubically expansive flame-spraying material |
| JPS6215508B2 (en) * | 1982-04-02 | 1987-04-08 | Shinagawa Shirorenga Kk | |
| JPS6229389B2 (en) * | 1983-02-23 | 1987-06-25 | Shinagawa Shirorenga Kk | |
| JPH05201772A (en) * | 1991-07-03 | 1993-08-10 | Glaverbel Sa | Mixture and method for forming fire-resistant body combined to surface |
| JPH09510685A (en) * | 1994-03-25 | 1997-10-28 | フイブ − サービシズ ソシエテ アノニム | Refractory composition forming chemical mixture |
| JPH1160342A (en) * | 1997-08-05 | 1999-03-02 | Shinagawa Refract Co Ltd | Thermal spraying material |
| JP2005336001A (en) * | 2004-05-26 | 2005-12-08 | Jfe Refractories Corp | Thermal spraying material |
| JP2006151771A (en) * | 2004-11-30 | 2006-06-15 | Kurosaki Harima Corp | Thermal spray material for repairing industrial kiln |
| JP2009120406A (en) * | 2007-11-12 | 2009-06-04 | Jfe Refractories Corp | Thermal spraying material |
| JP2011094191A (en) * | 2009-10-29 | 2011-05-12 | Jfe Steel Corp | Material for repair by thermal spraying |
| JP2012188345A (en) * | 2011-02-25 | 2012-10-04 | Shinagawa Refractories Co Ltd | Thermal spray material |
| JP2015218104A (en) * | 2014-05-21 | 2015-12-07 | 品川リフラクトリーズ株式会社 | Thermal spray material |
| JP2016079418A (en) * | 2014-10-10 | 2016-05-16 | 品川リフラクトリーズ株式会社 | Thermal spray material |
-
2016
- 2016-02-17 JP JP2016027746A patent/JP6263208B2/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4486545A (en) * | 1982-04-02 | 1984-12-04 | Shinagawa Refractories, Co., Ltd. | SIO2 -CaO Based low cubically expansive flame-spraying material |
| JPS6215508B2 (en) * | 1982-04-02 | 1987-04-08 | Shinagawa Shirorenga Kk | |
| JPS6229389B2 (en) * | 1983-02-23 | 1987-06-25 | Shinagawa Shirorenga Kk | |
| JPH05201772A (en) * | 1991-07-03 | 1993-08-10 | Glaverbel Sa | Mixture and method for forming fire-resistant body combined to surface |
| US5942453A (en) * | 1994-03-25 | 1999-08-24 | Fib-Services | Mixture of chemicals for forming a refractory composition |
| JPH09510685A (en) * | 1994-03-25 | 1997-10-28 | フイブ − サービシズ ソシエテ アノニム | Refractory composition forming chemical mixture |
| JPH1160342A (en) * | 1997-08-05 | 1999-03-02 | Shinagawa Refract Co Ltd | Thermal spraying material |
| JP2005336001A (en) * | 2004-05-26 | 2005-12-08 | Jfe Refractories Corp | Thermal spraying material |
| JP2006151771A (en) * | 2004-11-30 | 2006-06-15 | Kurosaki Harima Corp | Thermal spray material for repairing industrial kiln |
| JP2009120406A (en) * | 2007-11-12 | 2009-06-04 | Jfe Refractories Corp | Thermal spraying material |
| JP2011094191A (en) * | 2009-10-29 | 2011-05-12 | Jfe Steel Corp | Material for repair by thermal spraying |
| JP2012188345A (en) * | 2011-02-25 | 2012-10-04 | Shinagawa Refractories Co Ltd | Thermal spray material |
| JP2015218104A (en) * | 2014-05-21 | 2015-12-07 | 品川リフラクトリーズ株式会社 | Thermal spray material |
| JP2016079418A (en) * | 2014-10-10 | 2016-05-16 | 品川リフラクトリーズ株式会社 | Thermal spray material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031379A (en) * | 2021-11-05 | 2022-02-11 | 瑞泰科技股份有限公司 | Aluminum-silicon high-temperature spray coating |
| CN114031379B (en) * | 2021-11-05 | 2024-01-30 | 瑞泰科技股份有限公司 | Aluminum-silicon high-temperature spray paint |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6263208B2 (en) | 2018-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5781452B2 (en) | Thermal spray material | |
| TWI555882B (en) | Thermal spraying materials | |
| JP5456965B2 (en) | Thermal spray material | |
| CN103449831A (en) | Welding repair material for repairing coking furnace and method for repairing coking furnace | |
| JP6092172B2 (en) | Thermal spray material | |
| JP6263208B2 (en) | Thermal spray material | |
| JP5493711B2 (en) | Thermal spray repair material | |
| JPH09132469A (en) | Flame thermal spray material | |
| JP6386792B2 (en) | Thermal spray material | |
| JP4109663B2 (en) | Thermal spraying material for industrial kiln repair | |
| JP6505797B2 (en) | Thermal spray material | |
| JP4464804B2 (en) | Thermal spraying material for industrial kiln repair | |
| JP6147298B2 (en) | Thermal spray material | |
| JP6882587B1 (en) | Dry spray material for firing pots | |
| JP6372533B2 (en) | Coke oven bottom repair material | |
| JP4493404B2 (en) | Thermal spray material | |
| JP2549035B2 (en) | Fireproof powder for thermal spraying | |
| JP3827119B2 (en) | Powder mixture for flame spray repair | |
| JPH05330931A (en) | Thermal spraying repairing material | |
| JPH10182255A (en) | Repairing material for flame spraying for refractory and its repairing method | |
| JPS5879870A (en) | Powder material for flame spray | |
| JPS63267886A (en) | Flame spraying repair method of refractory | |
| JPS6046063B2 (en) | Manufacturing method of powder material for thermal spraying | |
| JPS59203782A (en) | Limy flame spray repairing material | |
| JPH11279740A (en) | Powder mixture for repair of flame thermal spraying |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170706 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170718 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170822 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20171205 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20171215 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6263208 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |