JP2012188345A - Thermal spray material - Google Patents
Thermal spray material Download PDFInfo
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- JP2012188345A JP2012188345A JP2012026791A JP2012026791A JP2012188345A JP 2012188345 A JP2012188345 A JP 2012188345A JP 2012026791 A JP2012026791 A JP 2012026791A JP 2012026791 A JP2012026791 A JP 2012026791A JP 2012188345 A JP2012188345 A JP 2012188345A
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- 239000000463 material Substances 0.000 title claims abstract description 100
- 239000007921 spray Substances 0.000 title claims abstract description 74
- 239000000843 powder Substances 0.000 claims abstract description 133
- 229910052751 metal Inorganic materials 0.000 claims abstract description 105
- 239000002184 metal Substances 0.000 claims abstract description 105
- 238000002485 combustion reaction Methods 0.000 claims abstract description 96
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 66
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 100
- 239000002245 particle Substances 0.000 claims description 49
- 239000000377 silicon dioxide Substances 0.000 claims description 46
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 38
- 239000011449 brick Substances 0.000 claims description 36
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 30
- 239000012752 auxiliary agent Substances 0.000 claims description 26
- 239000000395 magnesium oxide Substances 0.000 claims description 26
- 230000008439 repair process Effects 0.000 claims description 25
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000292 calcium oxide Substances 0.000 claims description 22
- 235000012255 calcium oxide Nutrition 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 11
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 11
- 159000000000 sodium salts Chemical class 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 2
- 238000010276 construction Methods 0.000 description 32
- 238000002425 crystallisation Methods 0.000 description 29
- 230000008025 crystallization Effects 0.000 description 29
- 239000000203 mixture Substances 0.000 description 25
- 238000007751 thermal spraying Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 13
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- -1 alkali metal salt Chemical class 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000001737 promoting effect Effects 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 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 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- RKGLUDFWIKNKMX-UHFFFAOYSA-L dilithium;sulfate;hydrate Chemical compound [Li+].[Li+].O.[O-]S([O-])(=O)=O RKGLUDFWIKNKMX-UHFFFAOYSA-L 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
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000031070 response to heat Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000010959 steel Substances 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
Landscapes
- Ceramic Products (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Abstract
Description
本発明は、例えばコークス炉炭化室のような工業窯炉等の補修に使用する溶射材料に関し、特に、その材料に含まれる金属粉末の酸化反応熱により耐火性粉末を溶融し、補修面に溶着させる溶射材料に関する。 The present invention relates to a thermal spray material used for repair of an industrial kiln such as a coke oven carbonization chamber, and in particular, melts a refractory powder by oxidation reaction heat of a metal powder contained in the material and welds it to a repair surface. It relates to a thermal spray material to be made.
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、レーザー溶射、火炎溶射がある。しかしながら、これらの溶射方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方法も利用されている（例えば、特許文献１〜４参照）。この溶射方法では、金属粉末（燃焼剤）と耐火性粉末の混合物を酸素で搬送し、高熱の補修面に吹き付ける。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 is also used (for example, see Patent Documents 1 to 4). In this thermal spraying method, a mixture of metal powder (combustion agent) and refractory powder is transported with oxygen and sprayed onto a hot 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.
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、酸化マグネシウムなど）の８０％および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、ジルコニウムなど）の８０％および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、信頼性およ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。 For example, Patent Document 1 discloses that the particle size of the particles sprayed as a mixture is 80% and 20% of the particle size of refractory particles (sillimanite, 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。また、特許文献２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種また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、および、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、コーンスターチ粉など）または金属粉末（鉄粉、マンガン粉、バナジウム粉など）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。 Further, Patent Document 2 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) which is an oxidizing powder. Patent Document 2 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. As an example, 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. 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.
さらに、特許文献３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。また、特許文献４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、付着性および接着性が向上するとされている。 Further, Patent Document 3 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. Patent Document 4 discloses a thermal spray material containing refractory raw material powder (2 to 25 mass% of calcia powder with 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.
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間膨張率と補修に使用される溶射施工体の熱間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間膨張率と同等の熱間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。 The coke oven carbonization chamber, which is one of the objects to be repaired by the above-mentioned sprayed material, opens and closes the door when extruding the coke, so that the furnace temperature fluctuates between 900 ° C. and 1300 ° C., for example, near the door. . 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 hot expansion coefficient of the furnace wall, which is the workpiece, and the thermal expansion coefficient of the thermal spraying object used for repair are significantly different, However, it will be worn away from the furnace wall. Therefore, it is necessary to ensure the durability by using a thermal sprayed construction body having a hot expansion coefficient equivalent to the hot 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２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。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。 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 2, an alkali metal salt that is a safe compound without danger of explosion or the like and is 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. 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.
上述した従来の溶射材料は、溶射材料に求められる以上のような特性のすべてを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、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。また、特許文献２が開示する溶射材料は、アルカリ金属塩の分解時の吸熱に起因する着火性や燃焼継続性の低下が発生する。 The above-mentioned conventional thermal spray material does not satisfy all of the above characteristics required for the thermal spray material. 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 and the continuity of combustion may be insufficient. In addition, the thermal spray material disclosed in Patent Document 2 causes a decrease in ignitability and combustion continuity due to heat absorption during decomposition of the alkali metal salt.
また、特許文献３および特許文献４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、被施工体の補修面に溶射した際に生成されるＭｇＯ・ＳｉＯ２やＣａＯ・ＳｉＯ２は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。 In addition, the thermal spray materials disclosed in Patent Document 3 and Patent Document 4 can be expected to improve the integrity between the thermal spray layers, but MgO · SiO 2 and CaO · SiO generated when sprayed on the repair surface of the work piece. No. 2 has a large thermal expansion at 1000 ° C. or higher. 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.
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、多量の着火促進剤を添加することなく着火性および燃焼継続性を確保でき、かつ耐用性、溶射層間の一体性、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 can ensure ignitability and continuity of combustion without adding a large amount of ignition accelerator, and can provide durability, integrity between sprayed layers, safety. It aims at providing the thermal spraying material which is excellent in property.
本願発明者らは耐用性を維持しつつ、着火促進剤を無添加または少量の添加で、着火性および燃焼継続性を確保する方法を鋭意研究し、本発明に至った。本願発明者らは、耐火性粉末と燃焼剤である金属粉末に、高温下において受熱した際に酸素を供給して燃焼材を酸化させることができる燃焼補助剤を使用することにより着火性と燃焼継続性を維持できることを見出した。また、比較的低温で酸化して燃焼材の酸化反応に必要な初期の熱量を補助する着火促進剤と燃焼補助剤とを併用すると、着火性と燃焼継続性をより好ましく維持できることを見出した。 The inventors of the present application have earnestly studied a method for ensuring ignition performance and combustion continuity by adding no ignition accelerator or adding a small amount of ignition accelerator while maintaining durability, and have reached the present invention. The inventors of the present application use flammability and combustion by using a combustion auxiliary agent that can oxidize the combustion material by supplying oxygen to the refractory powder and the metal powder that is the combustion agent at high temperatures. We found that continuity can be maintained. It has also been found that ignitability and combustion continuity can be maintained more favorably when an ignition accelerator and a combustion auxiliary that are oxidized at a relatively low temperature and assist the initial amount of heat required for the oxidation reaction of the combustion material are used in combination.
すなわち、本発明に係る溶射材料は、酸素を搬送ガスとして被施工体に吹付けられ、金属粉末の酸化反応熱により溶融した耐火性粉末を補修面に溶着させることで、珪石れんがからなる被施工体の補修に使用される溶射材料であって、ＳｉＯ２成分の質量割合が９０％（ＳｉＯ２純度９０％）以上である耐火性粉末を８０〜９０質量％、金属シリコン粉末を１０〜２０質量％含む。また、リチウム塩を、耐火性粉末と金属シリコン粉末との全量に対して外掛け、かつ酸化物換算で０．３〜１．０質量％含む。さらに、被施工体に吹き付けられた際の受熱により金属シリコンへの酸素供給源となる金属酸化物の粉末からなる燃焼補助剤を、耐火性粉末と金属シリコン粉末との全量に対して外掛けで０．３〜２．０質量％含む。 That is, the thermal spray material according to the present invention is sprayed on the work piece using oxygen as a carrier gas, and welded to the repair surface with a refractory powder melted by the oxidation reaction heat of the metal powder, thereby making the work made of silica brick. It is a thermal spray material used for body repair, and the refractory powder having a mass ratio of SiO 2 component of 90% (SiO 2 purity 90%) or more is 80 to 90 mass%, and the metal silicon powder is 10 to 20 mass. % Is included. Moreover, lithium salt is externally added with respect to the whole quantity of a refractory powder and a metal silicon powder, and 0.3-1.0 mass% is contained in conversion of an oxide. Furthermore, a combustion auxiliary agent made of a metal oxide powder that becomes a source of oxygen supply to the metal silicon by receiving heat when sprayed on the work piece is externally applied to the total amount of the refractory powder and the metal silicon powder. Including 0.3 to 2.0% by mass.
上記溶射材料には、アルミニウムを主体とする金属を実質的に含まない金属粉末からなる着火促進剤を、耐火性粉末と金属シリコン粉末との全量に対して外掛けで１．５質量％以下の有限量を、必要に応じてさらに添加することができる。ここで、アルミニウムを主体とする金属は、アルミニウム（Ａｌ）やアルミニウム合金等、燃焼によりＡｌ２Ｏ３を
生成する金属を意味する。また、アルミニウムを主体とする金属を実質的に含まない金属粉末とは、アルミニウムの含有量が１５質量％以下、好ましくは４質量％以下の金属粉末である。
The thermal spraying material includes an ignition accelerator composed of a metal powder substantially free of a metal mainly composed of aluminum, with an outer coating of 1.5% by mass or less based on the total amount of the refractory powder and the metal silicon powder. A finite amount can be further added as needed. Here, the metal mainly composed of aluminum means a metal that produces Al 2 O 3 by combustion, such as aluminum (Al) or an aluminum alloy. Moreover, the metal powder substantially free of metal mainly composed of aluminum is a metal powder having an aluminum content of 15% by mass or less, preferably 4% by mass or less.
また、上記溶射材料には、ＣａＯ成分の質量割合が９０％（ＣａＯ純度９０％）以上である酸化カルシウム粉末およびＭｇＯ成分の質量割合が９０％（ＭｇＯ純度９０％）以上である酸化マグネシウム粉末のうち１種以上を、耐火性粉末と金属シリコン粉末との全量に対して外掛けで合計４．０質量％以下の有限量を、さらに添加してもよい。 The thermal spray material includes calcium oxide powder having a CaO component mass ratio of 90% (CaO purity 90%) or more and magnesium oxide powder having a MgO component mass ratio of 90% (MgO purity 90%) or more. One or more of them may be further added in a finite amount of 4.0% by mass or less as a total amount based on the total amount of the refractory powder and the metal silicon powder.
さらに、上記溶射材料には、ナトリウム塩、カリウム塩の１種以上を、リチウム塩、ナトリウム塩およびカリウム塩の総量が耐火性粉末と金属シリコン粉末との全量に対して外掛け、かつ酸化物換算で１．７質量％以下として添加することもできる。 Further, the above-mentioned thermal spray material includes at least one of sodium salt and potassium salt, the total amount of lithium salt, sodium salt and potassium salt being applied to the total amount of refractory powder and metal silicon powder, and in terms of oxide It can also be added at 1.7% by mass or less.
以上の溶射材料において、耐火性粉末の最大粒子径が２０００μｍ以下であることが好ましい。 In the above thermal spray material, the maximum particle size of the refractory powder is preferably 2000 μm or less.
なお、燃焼補助剤は、好ましくは、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、酸化銅からなる群から選択される１種以上の金属酸化物である。また、着火促進剤は、好ましくは、鉄、マンガン、バナジウム、マグネシウム、チタンおよびこれらの合金からなる群から選択される１種以上の金属粉末である。 The combustion aid is preferably one or more metal oxides selected from the group consisting of scandium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, and copper oxide. It is. The ignition accelerator is preferably one or more metal powders selected from the group consisting of iron, manganese, vanadium, magnesium, titanium, and alloys thereof.
本発明によれば、着火促進剤を無添加あるいは少量の添加で着火性および燃焼継続性を確保でき、かつ溶射層間の一体性、耐用性および安全性に優れる溶射材料を得ることができる。 According to the present invention, it is possible to obtain a thermal spray material that can ensure ignitability and combustion continuity with no addition or a small amount of an ignition accelerator, and that is excellent in integrity, durability and safety between thermal spray layers.
本発明に係る溶射材料は、酸素を搬送ガスとして被施工体に吹付けられ、金属粉末の酸化反応熱により溶融した耐火性粉末を補修面に溶着させることで、珪石れんがからなる被施工体の補修に使用される溶射材料であって、ＳｉＯ２成分の質量割合が９０％以上である耐火性粉末（骨材）と、金属シリコン粉末（燃焼剤）とを含む。耐火性粉末と金属シリコン粉末との全量１００質量％に含まれる耐火性粉末の割合は８０〜９０質量％（８０質量％以上かつ９０質量％以下）であり、金属シリコン粉末の割合は１０〜２０質量％（１０質量％以上かつ２０質量％以下）である。なお、以下では、耐火性粉末と金属シリコン粉末との混合物を主材料という。また、以下では、主材料の全量は、耐火性粉末と金属シリコン粉末とからなる１００質量％の混合物を意味する。 The thermal spray material according to the present invention is sprayed onto the work piece using oxygen as a carrier gas, and welded to the repair surface with a refractory powder melted by the heat of oxidation reaction of the metal powder, so that the work piece made of silica brick is used. It is a thermal spray material used for repair, and includes a refractory powder (aggregate) in which the mass ratio of the SiO 2 component is 90% or more and a metal silicon powder (combustion agent). The ratio of the refractory powder contained in 100% by mass of the total amount of the refractory powder and the metal silicon powder is 80 to 90% by mass (80 to 90% by mass), and the ratio of the metal silicon powder is 10 to 20%. It is mass% (10 mass% or more and 20 mass% or less). Hereinafter, a mixture of refractory powder and metal silicon powder is referred to as a main material. In the following, the total amount of the main material means a 100% by mass mixture of refractory powder and metal silicon powder.
また、本発明に係る溶射材料は、リチウム塩および燃焼補助剤を含む。リチウム塩は、溶射材料の溶射により被施工体に表面に生成された、溶融したシリカを速やかに結晶化させる機能を有する。リチウム塩の添加量は、酸化物（Ｌｉ２Ｏ）換算で、主材料の全量に対して外掛けで０．３〜１．０質量％（０．３質量％以上かつ１．０質量％以下）である。燃焼補助剤は、被施工体に吹き付けられた際の受熱に伴って酸素を放出する酸素供給源となる金属酸化物の粉末からなる。燃焼補助剤は、溶射材料の燃焼中に金属シリコン粉末へ酸素を供給して被施工体上で燃焼材である金属シリコン粉末を酸化させる機能を有する。燃焼補助剤の添加量は、主材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。 The thermal spray material according to the present invention includes a lithium salt and a combustion auxiliary agent. The lithium salt has a function of quickly crystallizing the fused silica generated on the surface of the workpiece by thermal spraying of the thermal spray material. The addition amount of the lithium salt is 0.3 to 1.0% by mass (0.3% by mass or more and 1.0% by mass or less) based on the total amount of the main material in terms of oxide (Li 2 O). ). The combustion auxiliary agent is made of a metal oxide powder that serves as an oxygen supply source that releases oxygen in response to heat reception when sprayed on the work. The combustion auxiliary agent has a function of supplying oxygen to the metal silicon powder during combustion of the thermal spray material to oxidize the metal silicon powder as the combustion material on the workpiece. The addition amount of the combustion auxiliary agent 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 material.
この溶射材料は、被施工体に吹き付けられた際の受熱に伴って、金属シリコン粉末への酸素供給源となる燃焼補助剤を使用した結果、被施工体が比較的低温であっても、着火性と燃焼継続性を確保することが可能である。また、燃焼剤である金属シリコン粉末の着火に必要な初期の熱量を補助する着火促進剤を併用すると、溶射層間の一体性、耐用性および安全性により優れる。以下、各成分についてより詳細に説明する。 This thermal spray material is ignited even when the workpiece is at a relatively low temperature as a result of using a combustion auxiliary agent that serves as an oxygen supply source to the metal silicon powder as it receives heat when sprayed on the workpiece. And combustion continuity can be ensured. In addition, when an ignition accelerator that assists the initial amount of heat necessary for ignition of the metal silicon powder as the combustion agent is used in combination, the integrity, durability and safety between the thermal spray layers are excellent. Hereinafter, each component will be described in more detail.
（耐火性粉末）
本発明に係る溶射材料では、ＳｉＯ２成分の質量割合が９０％以上である耐火性粉末を配合する。この溶射材料は、コークス炉炭化室の内壁等の、珪石れんがからなる被施工体の補修に使用されるため、耐火性粉末のＳｉＯ２成分が９０％未満であると、本溶射材料の溶射により形成された補修施工体の熱間膨張率と被施工体の熱間膨張率との差が大きくなり剥離が発生するからである。耐火性粉末として、珪石れんがの粉砕粉、珪石、珪砂等を使用することができる。特に、補修対象である被施工体の鉱物組成である珪石れんがの粉砕粉が好適に使用することができ、熱間膨張率を調整する目的で溶融シリカなどを添加することもできる。
(Fireproof powder)
The spraying material according to the present invention, the mass ratio of SiO 2 component is blended refractory powder is 90% or more. Since this thermal spray material is used for repairing workpieces made of silica brick, such as the inner wall of a coke oven carbonization chamber, if the SiO 2 component of the refractory powder is less than 90%, This is because the difference between the hot expansion coefficient of the formed repair construction body and the hot expansion coefficient of the work body increases, and peeling occurs. As the refractory powder, crushed powder of silica brick, silica stone, silica sand and the like can be used. In particular, pulverized powder of silica brick, which is the mineral composition of the workpiece to be repaired, can be suitably used, and fused silica or the like can be added for the purpose of adjusting the hot expansion coefficient.
耐火性粉末の最大粒子径は２０００μｍであることが好ましく、さらに好ましくは１０００μｍ以下である。最大粒子径が２０００μｍ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。 The maximum particle size of the refractory powder is preferably 2000 μm, more preferably 1000 μm or less. This is because if the maximum particle diameter is larger than 2000 μm, large particles will rebound at the time of construction, making it difficult to adhere to the work piece and lowering the thermal spraying efficiency.
また、耐火性粉末に含まれるＡｌ２Ｏ３成分の質量割合は、５％以下であることが好ましい。Ａｌ２Ｏ３成分は、結晶化の際に異常膨張を引き起こす。そのため、耐火性粉末に含まれるＡｌ２Ｏ３成分の質量割合が５％より大きいと剥離損耗を引き起こすためである。加えて、耐火性粉末に不純物として低融点組成物が含まれていると、溶射時に低融点組成物が溶融してガラス化し、このガラスが施工後の使用中に徐々に結晶化し膨張することで剥離損耗を引き起こしてしまう。そのため、耐火性粉末に不純物として含まれる低融点組成物は極力少ないことが好ましい。 The mass ratio of Al 2 O 3 component contained in the refractory powder is preferably 5% or less. The Al 2 O 3 component causes abnormal expansion during crystallization. Therefore, if the mass ratio of the Al 2 O 3 component contained in the refractory powder is greater than 5%, it causes peeling wear. In addition, if the refractory powder contains a low-melting-point composition as an impurity, the low-melting-point composition melts and becomes vitrified during spraying, and this glass gradually crystallizes and expands during use after construction. It causes peeling wear. Therefore, it is preferable that the low melting point composition contained as an impurity in the refractory powder is as small as possible.
（金属シリコン粉末）
本発明に係る溶射材料では、金属シリコン粉末は燃焼剤として機能する。燃焼剤は、燃焼後に酸化物（結合相）になる。本発明では、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ため、燃焼剤として金属シリコン粉末を配合する。主材料の全量１００質量％に含まれる金属シリコン粉末の添加量は１０〜２０質量％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。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。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。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などの元素が多く含まれることになるため好ましくない。
(Metal silicon powder)
In the thermal spray material according to the present invention, the metal silicon powder functions as a combustion agent. The combustion agent becomes an oxide (binding phase) after combustion. In the present invention, since the work to be repaired is composed of silica brick mainly composed of silica, metal silicon powder is blended as a combustion agent. The addition amount of the metal silicon powder contained in 100% by mass of the main material is 10 to 20% by mass, and preferably 13 to 17% by mass (13 to 17% by mass). When the addition amount is less than 10% by mass, the combustion reaction becomes weak, 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, the viscosity of the sprayed material decreases and the sprayed material flows down from the work piece, making it impossible to obtain a good work piece. 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.
主材料の全量１００質量％に含まれる、７５μｍより大きい金属シリコン粉末粒子は５質量％以下であり、２０μｍ以下の金属シリコン粉末粒子は３〜１４質量％（３質量％以上かつ１４質量％以下）であり、他の径（２０μｍより大きく、かつ７５μｍ以下の粒子）の金属シリコン粉末粒子が残りの量であることが好ましい。より好ましくは、主材料の全量１００質量％に含まれる７５μｍより大きい金属シリコン粉末粒子は３質量％以下であり、２０μｍ以下の金属シリコン粉末粒子は５〜１２質量％（５質量％以上かつ１２質量％以下）である。粒子径が７５μｍ以上の金属シリコン粉末が５質量％より多くなると、燃焼反応が弱まり燃焼継続性が低下する。粒子径が２０μｍ以下の金属シリコン粉末が３質量％未満である場合も、燃焼反応が弱まり燃焼継続性が低下する。さらに、粒子径が２０μｍ以下の金属シリコン粉末が１４質量％を超えると、粉体流動性が低下するため、被施工体までの搬送時に脈動を引き起こして逆火の危険性が大きくなるからである。 The metal silicon powder particles larger than 75 μm included in 100% by mass of the main material are 5% by mass or less, and the metal silicon powder particles of 20 μm or less are 3 to 14% by mass (3 to 14% by mass). It is preferable that the remaining amount of metal silicon powder particles having other diameters (particles larger than 20 μm and 75 μm or less). More preferably, the metal silicon powder particles larger than 75 μm included in 100% by mass of the main material are 3% by mass or less, and the metal silicon powder particles of 20 μm or less are 5 to 12% by mass (5 to 12% by mass). % Or less). When the amount of metal silicon powder having a particle diameter of 75 μm or more is more than 5% by mass, the combustion reaction is weakened and the combustion continuity is lowered. Even when the metal silicon powder having a particle size of 20 μm or less is less than 3% by mass, the combustion reaction is weakened and the combustion continuity is lowered. Furthermore, if the metal silicon powder having a particle size of 20 μm or less exceeds 14% by mass, the powder fluidity is lowered, and therefore, the risk of backfire is increased by causing pulsation during transportation to the workpiece. .
（結晶化促進剤）
続いて、結晶化促進剤であるリチウム塩について説明する。上述したように、被施工体上に溶射された溶射材料中では、金属シリコン粉末が酸化されてシリカが生成される。当該シリカは燃焼による高温で溶融状態にあり、その後冷却されると、通常シリカガラスが形成される。シリカガラスは非晶質であるため、補修が完了した被施工体の使用中に高温にさらされることにより、徐々に結晶化が進行する。シリカガラスは結晶化すると体積が膨張するため、当該膨張に起因して施工体が被施工体から剥離してしまう。本溶射材料では、このような膨張に起因する施工体の剥離を回避すべく、溶射後速やか（補修施工後の被施工体の冷却中）にシリカを結晶化させるための結晶化促進剤を添加する。
(Crystallization accelerator)
Subsequently, a lithium salt that is a crystallization accelerator will be described. As described above, in the thermal spray material sprayed on the workpiece, the metal silicon powder is oxidized to produce silica. The silica is in a molten state at a high temperature due to combustion, and when cooled, usually silica glass is formed. Since silica glass is amorphous, crystallization gradually proceeds by exposure to a high temperature during use of the work to be repaired. When silica glass is crystallized, the volume expands, so that the construction body is peeled off from the work body due to the expansion. In this thermal spray material, a crystallization accelerator is added to crystallize silica immediately after thermal spraying (during cooling of the workpiece after repair) in order to avoid such peeling of the workpiece due to expansion. To do.
背景技術で述べたように、従来、アルカリ金属であれば結晶化促進効果を有するとされていたが、本願発明者らは、アルカリ金属の中でもリチウムが、特に効率よく結晶化を促進できることを見出した。すなわち、上述したように、アルカリ金属塩は分解時に吸熱するため、アルカリ金属塩の添加に伴い、着火性や燃焼継続性が低下し、施工体の付着性を低下させる。そのため、着火性や燃焼継続性が低下することのない範囲でアルカリ金属塩を添加し、結晶化促進効果を得る必要があるが、このような条件下では、リチウム塩を採用した場合に顕著な結晶化促進効果が得られたのである。 As described in the background art, conventionally, an alkali metal was said to have a crystallization promoting effect, but the present inventors found that lithium can promote crystallization particularly efficiently among alkali metals. It was. That is, as described above, the alkali metal salt absorbs heat at the time of decomposition, and therefore, with the addition of the alkali metal salt, the ignitability and the combustion continuity are lowered, and the adhesion of the construction body is lowered. Therefore, it is necessary to add an alkali metal salt within a range where the ignitability and combustion continuity do not decrease, and to obtain a crystallization promoting effect. Under such conditions, it is remarkable when a lithium salt is employed. The effect of promoting crystallization was obtained.
そこで、本発明では、結晶化促進剤としてリチウム塩を配合している。リチウム塩の添加量は、酸化物（Ｌｉ２Ｏ）換算で、主材料の全量に対して外掛けで０．３〜１．０質量％であり、より好ましくは、０．４〜０．７質量％（０．４質量％以上かつ０．７質量％以下）である。添加量が０．３質量％未満であると結晶化促進効果が得られず、添加量が１．０質量％を超えると、分解時の吸熱の作用により、着火性や燃焼継続性が顕著に低下するからである。なお、リチウム塩としては炭酸リチウム、硫酸リチウムなどを好適に使用することができる。 Therefore, in the present invention, a lithium salt is blended as a crystallization accelerator. The addition amount of the lithium salt is 0.3 to 1.0% by mass on the basis of the total amount of the main material in terms of oxide (Li 2 O), and more preferably 0.4 to 0.7%. Mass% (0.4 mass% or more and 0.7 mass% or less). If the addition amount is less than 0.3% by mass, the effect of promoting crystallization cannot be obtained. If the addition amount exceeds 1.0% by mass, the ignitability and combustion continuity are notable due to the endothermic action during decomposition. It is because it falls. In addition, lithium carbonate, lithium sulfate, etc. can be used suitably as lithium salt.
（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、燃焼材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配合する。燃焼補助剤は、被施工体に付着した際の受熱に伴い酸素を放出する酸素供給源となる金属酸化物の粉末からなる。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）を好適に使用することができる。これらの金属酸化物は、被施工体に吹き付けられ燃焼する際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では、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。
(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 material is blended on the workpiece. The combustion auxiliary agent is made of a metal oxide powder that serves as an oxygen supply source that releases oxygen with heat received when attached to the work. 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. These metal oxides oxidize metal silicon by reducing the oxidation number of the metal oxides when they are sprayed on the work piece and burned. 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 ) is particularly suitable because it has an effect of increasing the oxygen permeation rate when it is dissolved in silica glass formed by oxidation of metal silicon powder. Can be used for
燃焼補助剤の添加量は、主材料の全量に対して外掛けで０．３〜２．０質量％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、２．０質量％より多いとシリカ結晶化を阻害する不純物として作用す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。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。 The addition amount of the combustion auxiliary agent is 0.3 to 2.0% by mass on the basis of the total amount of the main material. If the addition amount is less than 0.3% by mass, the combustion continuation effect of the combustor is small, and if it is more than 2.0% by mass, it acts as an impurity inhibiting silica crystallization, which is not preferable. Moreover, it is preferable that the particle diameter of metal oxide powder is 100 micrometers or less. When it is larger than 100 μm, the reactivity becomes poor, and the effect of improving the continuity of combustion cannot be obtained.
（着火促進剤）
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着火促進剤を必要に応じて配合する。着火促進剤の添加量は、主材料の全量に対して外掛けで１．５質量％以下である。着火促進剤は、アルミニウムを主体とする金属を実質的に含まない金属粉末からなる。ここでは、着火促進剤は、当該着火促進剤に含まれるアルミニウム（Ａｌ）の質量割合が１５％以下、好ましくは４％以下の金属粉末からなる。従来、着火促進剤としてアルミニウム粉末やアルミニウム合金粉末が使用されているが、上述したように、アルミニウムを主体とする金属の燃焼によりＡｌ２Ｏ３が生成されると、施工体の剥離損耗を引き起こす可能性があり、また、シリカの結晶化も阻害される。本実施形態ではアルミニウムの含有量が１５質量％以下の着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、溶射開始時の着火を促進しつつ、施工体の特性を改善することができる。なお、当該着火促進剤は、アルカリ金属、アルカリ土類金属を実質的に含まないことがより好ましい。
(Ignition accelerator)
In the thermal spray material according to the present invention, an ignition accelerator having a function of assisting the initial amount of heat necessary for the oxidation reaction of the metal silicon powder is blended as necessary. The addition amount of the ignition accelerator is 1.5% by mass or less as an outer shell with respect to the total amount of the main material. The ignition accelerator is made of a metal powder that does not substantially contain a metal mainly composed of aluminum. Here, the ignition accelerator is made of a metal powder having a mass ratio of aluminum (Al) contained in the ignition accelerator of 15% or less, preferably 4% or less. Conventionally, aluminum powder or aluminum alloy powder has been used as an ignition accelerator, but as described above, when Al 2 O 3 is generated by the combustion of a metal mainly composed of aluminum, it causes peeling wear of the construction body. There is also a possibility that silica crystallization is also inhibited. In the present embodiment, by blending an ignition accelerator having an aluminum content of 15% by mass or less, even when the temperature of the workpiece is a relatively low temperature of 800 ° C. or less, promoting ignition at the start of thermal spraying, The characteristics of the construction body can be improved. In addition, it is more preferable that the ignition accelerator does not substantially contain an alkali metal or an alkaline earth metal.
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。 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 added alone or in combination of two or more.
着火促進剤の添加量は、主材料の全量に対して外掛けで１．５質量％以下である。１．５質量％より多いとシリカの結晶化を阻害する上、爆発や逆火などの作業上の危険性が高まってしまうため好ましくない。また、金属粉末の粒子径は１００μｍ以下であることが好ましい。１００μｍより大きいと反応性が乏しくなり、着火促進効果が得られなくなるからである。 The addition amount of the ignition accelerator is 1.5% by mass or less as an outer shell with respect to the total amount of the main material. If the amount is more than 1.5% by mass, the crystallization of silica is hindered, and the danger of work such as explosion or flashback increases, which is not preferable. Moreover, it is preferable that the particle diameter of a metal powder is 100 micrometers or less. This is because if it is larger than 100 μm, the reactivity becomes poor, and the ignition promoting effect cannot be obtained.
（その他の添加物）
上述の各成分に加えて、ＣａＯ純度が９０％以上である酸化カルシウム粉末、ＭｇＯ純度が９０％以上である酸化マグネシウム粉末の１種以上を、主材料の全量に対して外掛けで４．０質量％以下の有限量を添加してもよい。
(Other additives)
In addition to the above-described components, one or more of calcium oxide powder having a CaO purity of 90% or more and magnesium oxide powder having an MgO purity of 90% or more is 4.0% on the basis of the total amount of the main material. A finite amount of mass% or less may be added.
溶射施工は、被施工体に溶射材料を吐出するノズルを、被施工面に対して移動（往復動）させながら実施される。そのため、施工体は複数の層が重なったものとして被施工体上に形成される。この場合、各層の一体性が乏しいと、施工体が層間で剥離する等の不具合が発生しやすくなる。ＣａＯ純度９０％以上の酸化カルシウム粉末、ＭｇＯ純度９０％以上の酸化マグネシウム粉末の１種以上を添加すると、被施工体上で溶融したＳｉＯ２の粘性を低下させることができ、層間の一体性を向上させることができる。 Thermal spraying is performed while moving (reciprocating) a nozzle that discharges a thermal spray material onto the workpiece. Therefore, the construction body is formed on the construction body as a plurality of layers overlapped. In this case, if the integrity of each layer is poor, problems such as separation of the construction body between layers tend to occur. When one or more of calcium oxide powder having a CaO purity of 90% or more and magnesium oxide powder having an MgO purity of 90% or more are added, the viscosity of the SiO 2 melted on the workpiece can be reduced, and the interlaminar integrity can be improved. Can be improved.
なお、添加量が４．０質量％を超えると、添加した酸化カルシウム粉末や酸化マグネシウム粉末に起因する結合相の組成変化が大きくなり、珪石れんがとの熱間膨張率の一致が図れなくなるため好ましくない。また、酸化カルシウム粉末、酸化マグネシウム粉末の、粒子径は２００μｍ以下であることが好ましい。粒子径が２００μｍを超えると結合相となるシリカと反応し難くなり、粘性が低下せず層間の一体性を向上させる効果が期待できなくなるからである。 In addition, when the addition amount exceeds 4.0% by mass, the compositional change of the binder phase due to the added calcium oxide powder or magnesium oxide powder becomes large, and it is not possible to match the hot expansion coefficient with the silica brick, which is preferable. Absent. Moreover, it is preferable that the particle diameter of a calcium oxide powder and a magnesium oxide powder is 200 micrometers or less. This is because when the particle diameter exceeds 200 μm, it becomes difficult to react with the silica as the binder phase, and the effect of improving the integrity between layers cannot be expected without lowering the viscosity.
また、層間の一体性を向上させる観点では、ナトリウム塩、カリウム塩の１種以上を添加してもよい。上述したように、本発明において、ナトリウム塩、カリウム塩の少量の添加による結晶化促進効果は期待できないが、当該添加により、層間の一体性を高めることは可能であった。ただし、上述のように、ナトリウム塩やカリウム塩は、着火性や燃焼継続性の低下を招くため、その添加量は、リチウム塩、ナトリウム塩およびカリウム塩の総量が、主材料の全量に対して外掛け、かつ酸化物（Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ）換算で１．７質量％以下であることが好ましい。より好ましくは、１．３質量％以下である。なお、ナトリウム塩、カリウム塩としては炭酸ナトリウム、炭酸カリウム、硫酸ナトリウム、硫酸カリウムなどを好適に使用することができる。 Further, from the viewpoint of improving interlaminar integrity, one or more of a sodium salt and a potassium salt may be added. As described above, in the present invention, the effect of promoting crystallization due to the addition of a small amount of sodium salt or potassium salt cannot be expected, but it was possible to enhance the integrity between the layers. However, as described above, sodium salt and potassium salt cause a decrease in ignitability and combustion continuity. Therefore, the total amount of lithium salt, sodium salt, and potassium salt is based on the total amount of the main material. It is preferable that it is not more than 1.7% by mass in terms of the outer cover and oxide (Li 2 O, Na 2 O, K 2 O). More preferably, it is 1.3 mass% or less. In addition, as a sodium salt and potassium salt, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, etc. can be used conveniently.
上記の他、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、窒化物などを添加することもできる。 In addition to the above, within the range not inhibiting the effect of the present invention, fumed silica, oxides of elements selected from magnesium, calcium, iron, carbides, nitrides, etc. for the purpose of improving fluidity and adjusting mineral composition Can also be added.
以下に実施例およ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、ＳｉＯ２純度９５％の珪石れんが粉である。当該耐火性粉末に含まれるＡｌ２Ｏ３成分の質量割合は２％であった。また、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。なお、耐火性粉末の粒子径および金属シリコン粉末の粒子径も、表１、表２中に示している。表１、表２において、「１０００〜２０００μｍ」は、１０００μｍより大きく、かつ２０００μｍ以下を意味する。「６００〜１０００μｍ」は、６００μｍより大きく、かつ１０００μｍ以下を意味する。「２００〜６００μｍ」は、２００μｍより大きく、かつ６００μｍ以下を意味する。「〜２００μｍ」は、２００μｍ以下を意味する。また、「７５μｍ〜」は、７５μｍより大きい、を意味する。「２０〜７５μｍ」は、２０μｍより大きく、かつ７５μｍ以下を意味する。「〜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 thermal spray material is a silica brick with a SiO 2 purity of 95%. The mass proportion of the Al 2 O 3 component contained in the refractory powder was 2%. Further, the Si purity of the metal silicon powder used in each thermal spray material is 97%. The particle diameter of the refractory powder and the particle diameter of the metal silicon powder are also shown in Tables 1 and 2. In Tables 1 and 2, “1000 to 2000 μm” means larger than 1000 μm and not larger than 2000 μm. “600 to 1000 μm” means larger than 600 μm and 1000 μm or less. “200 to 600 μm” means larger than 200 μm and 600 μm or less. “˜200 μm” means 200 μm or less. Further, “75 μm˜” means larger than 75 μm. “20 to 75 μm” means larger than 20 μm and 75 μm or less. “˜20 μm” means 20 μm or less.
また、結晶化促進剤として、硫酸リチウム一水和物を使用し、着火促進剤として、粒子径が１００μｍ以下の鉄粉を使用した。燃焼補助剤は、粒子径が１００μｍ以下である酸化第二鉄（酸化鉄（III））粉末である。酸化カルシウム粉末のＣａＯ純度は９５％であり、粒子径は７５μｍ以下である。また、酸化マグネシウム粉末のＭｇＯ純度は９７％であり、粒子径は１５０μｍ以下である。ナトリウム塩、カリウム塩としては、それぞれ、硫酸ナトリウム、硫酸カリウムを使用した。 Further, lithium sulfate monohydrate was used as the crystallization accelerator, and iron powder having a particle size of 100 μm or less was used as the ignition accelerator. The combustion auxiliary agent is ferric oxide (iron (III) oxide) powder having a particle size of 100 μm or less. The calcium oxide powder has a CaO purity of 95% and a particle size of 75 μm or less. Further, the MgO purity of the magnesium oxide powder is 97%, and the particle diameter is 150 μm or less. As the sodium salt and potassium salt, sodium sulfate and potassium sulfate were used, respectively.
溶射施工は、各溶射材２ｋｇを、溶射装置のスクリューフィーダーで切り出し、被施工体に吹き付けることで実施した。搬送ガスは純度１００％の酸素とした。材料供給速度は７０ｋｇ／ｈである。被施工体とノズル先端との間の距離は１５０ｍｍとし、被施工体に対するノズル走査速度は３０ｍｍ／ｓとした。ここでは、各溶射材料による施工体の形成のみを目的としているため、表面温度が５００〜６００℃のシャモットれんが（耐火度ＳＫ３６）を被施工体にしている。 The thermal spraying was carried out by cutting out 2 kg of each thermal spray material with a screw feeder of a thermal spraying apparatus and spraying it on the workpiece. The carrier gas was oxygen having a purity of 100%. The material supply rate is 70 kg / h. The distance between the workpiece and the nozzle tip was 150 mm, and the nozzle scanning speed for the workpiece was 30 mm / s. Here, since it aims only at formation of the construction body by each thermal spray material, the chamotte brick (fire resistance SK36) whose surface temperature is 500-600 degreeC is made into the to-be-executed body.
各溶射材料による施工体について、溶射作業性（着火性、燃焼継続性、付着率）、施工体物性（珪石れんがとの熱間膨張率の一致、溶射層間の一体性）の試験を実施して、表１、表２中に記載した。表中の「◎」、「○」、「×」、「−」の記号は、各項目についての評価結果を示している。以下、各試験項目について簡単に説明する。 Tests of the thermal spray workability (ignition, combustion continuity, adhesion rate) and physical properties of the construction body (matching of the thermal expansion coefficient with silica bricks, integrity between the thermal spray layers) are performed on construction bodies made of each thermal spray material. These are shown in Tables 1 and 2. The symbols “「 ”,“ ◯ ”,“ × ”, and“ − ”in the table indicate the evaluation results for each item. Hereinafter, each test item will be briefly described.
着火性は、溶射施工開始時の着火性を、目視観察により評価した。「◎」は、速やかに着火し材料が付着し始めたことを示し、「○」は、数秒で着火し材料が付着し始めたことを示し、「×」は、着火しないことを示している。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、失火の気配がなく強い光を発しながら燃焼が継続したことを示し、「○」は、失火の気配がないもののやや弱い光を発しながら燃焼が継続したことを示し、「−」は着火しなかったために評価できなかったことを示している。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、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。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り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、実用上問題のない程度に一致することを示し、「×」は、乖離することを示し、「−」は着火しなかったために施工体が得られずに評価できなかったことを示している。溶射層間の一体性は、溶射施工後に、施工体が付着した被施工体を切断し、その切断面を目視観察することにより溶射層間の一体性を評価した。「○」は、溶射層間が不明確で一体性があることを示し、「−」は着火しなかったために施工体が得られずに評価できな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 ignited promptly and the material began to adhere, “○” indicates that the material ignited in a few seconds and the material began to adhere, and “×” indicates that the material did not ignite. . Combustion continuity was evaluated by visual observation of combustion continuity during thermal spraying. “◎” indicates that there was no misfiring sign and combustion continued while emitting strong light, “○” indicates that although there was no misfire sign, burning continued while emitting slightly weak light. "Indicates that it was not possible to evaluate because it did not ignite. The adhesion rate is obtained by collecting the material adhering to the workpiece after the thermal spray test, measuring the weight, and calculating the ratio of the adhering mass to the weight of the thermal spray material discharged from the nozzle. 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 there is no problem in practical use, “×” indicates that there is a divergence, and “−” indicates that the construction body was not obtained and could not be evaluated because it did not ignite. Is shown. The integrity between the thermal sprayed layers was evaluated by cutting the workpiece to which the construction body adhered after the thermal spraying and visually observing the cut surface. “◯” indicates that the thermal sprayed layers are unclear and integrated, and “−” indicates that the construction body could not be obtained and evaluation could not be performed because ignition did not occur.
表１に示す各実施例は、耐火性粉末、金属シリコン粉末、結晶化促進剤、燃焼補助剤、さらに適宜、着火促進剤、酸化マグネシウム粉末、酸化カルシウム粉末を使用し、燃焼補助剤である酸化第二鉄を外掛けで０．３〜２．０質量％添加した配合である。 Each example shown in Table 1 uses a refractory powder, a metal silicon powder, a crystallization accelerator, a combustion auxiliary, and further, an ignition accelerator, a magnesium oxide powder, and a calcium oxide powder as appropriate. It is a blend in which ferric iron is added in an amount of 0.3 to 2.0% by mass.
表１において、実施例１、２および１２〜１７は、耐火性粉末を、「６００〜１０００μｍ」の粒子径を有する珪石れんが粉を０．５質量％、「２００〜６００μｍ」の粒子径を有する珪石れんが粉を５６．５質量％、「〜２００μｍ」の粒子径を有する珪石れんが粉を２８．０質量％の配合としている。また、金属シリコン粉末を、「７５μｍ〜」の粒子径を０．２質量％、「２０〜７５μｍ」の粒子径を２．８質量％、「〜２０μｍ」の粒子径を１２．０質量％の配合としている。 In Table 1, Examples 1, 2, and 12-17 have refractory powder, 0.5% by mass of silica brick powder having a particle size of “600 to 1000 μm”, and a particle size of “200 to 600 μm”. Silica brick powder is 56.5% by mass, and silica stone brick having a particle size of “˜200 μm” is 28.0% by mass. Further, the metal silicon powder has a particle diameter of “75 μm˜” of 0.2 mass%, a particle diameter of “20-75 μm” of 2.8 mass%, and a particle diameter of “˜20 μm” of 12.0 mass%. It is formulated.
実施例１は、耐火性粉末、金属シリコン粉末、結晶化促進剤、燃焼補助剤および酸化マグネシウム粉末を使用し、燃焼補助剤である酸化第二鉄を外掛けで２．００質量％添加した配合である。実施例１３、１４は、実施例１の配合において燃焼補助剤である酸化第二鉄の配合を外掛けで１．００質量％に減量するとともに、酸化マグネシウム粉末に代えて酸化カルシウムを使用している。また、実施例２は、実施例１の配合において燃焼補助剤である酸化第二鉄の配合を外掛けで１．５０質量％に減量するとともに、着火促進剤である鉄粉を外掛けで０．２０質量％添加している。実施例１２、１５は、実施例２の配合において酸化第二鉄の配合を外掛けで１．００質量％に減量するとともに、酸化マグネシウム粉末に代えて酸化カルシウムを使用している。実施例１６、１７は、実施例１２の配合からさらに着火促進剤である鉄粉を増量するとともに、燃焼補助剤である酸化第二鉄の配合を減量している。表１に示すように、これらの各実施例では、着火性、燃焼継続性、付着率、珪石れんがとの熱膨張の一致、溶射層間の一体性の全評価項目において、良好な結果が得られた。特に、燃焼補助剤と着火促進剤を併用する実施例２、１２、１５〜１７では、着火性、燃焼継続性において、より良好な結果が得られた。 Example 1 uses a refractory powder, a metal silicon powder, a crystallization accelerator, a combustion auxiliary agent and a magnesium oxide powder, and a ferrous oxide which is a combustion auxiliary agent is added as an outer coating to 2.00% by mass. It is. In Examples 13 and 14, the amount of ferric oxide as a combustion auxiliary agent was reduced to 1.00% by mass in the formulation of Example 1, and calcium oxide was used instead of magnesium oxide powder. Yes. In Example 2, the amount of ferric oxide as a combustion auxiliary agent in the formulation of Example 1 was reduced to 1.50% by mass, and the iron powder as an ignition accelerator was reduced to 0 by outer coating. 20% by mass is added. In Examples 12 and 15, the amount of ferric oxide was reduced to 1.00% by mass in the formulation of Example 2 and calcium oxide was used instead of magnesium oxide powder. In Examples 16 and 17, the amount of iron powder, which is an ignition accelerator, is further increased from the formulation of Example 12, and the amount of ferric oxide, which is a combustion auxiliary agent, is decreased. As shown in Table 1, in each of these examples, good results were obtained in all the evaluation items of ignitability, combustion continuity, adhesion rate, coincidence of thermal expansion with silica brick, and integrity between sprayed layers. It was. In particular, in Examples 2, 12, and 15 to 17 in which the combustion auxiliary agent and the ignition accelerator were used in combination, better results were obtained in terms of ignitability and combustion continuity.
このように、施工体上で酸素を供給し金属シリコン粉末を酸化させることができる燃焼補助剤を適量添加することにより、着火性と燃焼継続性に優れた溶射材料を実現できる。また、比較的低温で酸化し、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着火促進剤を併用することで、より効果が得られる。 Thus, the thermal spray material excellent in ignition property and combustion continuity is realizable by adding a suitable quantity of the combustion adjuvant which can supply oxygen on a construction body and can oxidize metal silicon powder. Further, the effect can be further improved by using together with an ignition accelerator that oxidizes at a relatively low temperature and assists the initial amount of heat necessary for the oxidation reaction of the metal silicon powder.
表１において、実施例３〜１１は、実施例１、２および１２〜１７に比べて粒子径の大きな珪石れんが粉の配合比率を高めるとともに、着火促進剤を併用した実施例である。実施例３は、耐火性粉末、金属シリコン粉末、結晶化促進剤、着火促進剤、燃焼補助剤および酸化マグネシウム粉末を使用し、着火促進剤である鉄粉を外掛けで０．２０質量％、燃焼補助剤である酸化第二鉄を外掛けで０．６０質量％添加している。上述のように、燃焼補助剤と着火促進剤とを併用すると、着火性、燃焼継続性が向上する。そのため、この実施例では、燃焼補助剤である酸化第二鉄を実施例２の配合に比べて、より減量している。表１に示すように、着火性、燃焼継続性、付着率、珪石れんがとの熱膨張の一致、溶射層間の一体性の全評価項目において、良好な結果が得られた。なお、実施例３では、実施例２に比べて粒子径の大きな金属シリコン粉末の配合比率を高めているため、燃焼継続性の評価において実施例２に比べて発する光が弱くなっているが、結果としては良好である。 In Table 1, Examples 3 to 11 are examples in which the mixing ratio of the silica brick having a larger particle diameter than that of Examples 1, 2, and 12 to 17 is increased, and an ignition accelerator is used in combination. Example 3 uses a refractory powder, a metal silicon powder, a crystallization accelerator, an ignition accelerator, a combustion auxiliary agent and a magnesium oxide powder, and 0.20% by mass of iron powder as an ignition accelerator, 0.60% by mass of ferric oxide as a combustion auxiliary agent is added as an outer shell. As described above, when the combustion auxiliary agent and the ignition accelerator are used in combination, the ignitability and the combustion continuity are improved. Therefore, in this example, the amount of ferric oxide, which is a combustion auxiliary agent, is further reduced compared to the formulation of Example 2. As shown in Table 1, good results were obtained in all evaluation items of ignitability, combustion continuity, adhesion rate, coincidence of thermal expansion with silica brick, and integrity of the sprayed layers. In Example 3, since the blending ratio of the metal silicon powder having a large particle diameter is increased as compared with Example 2, the light emitted in the evaluation of combustion continuity is weaker than that in Example 2, The result is good.
実施例４および実施例５は、実施例３の配合において、耐火性粉末である珪石れんが粉と、燃焼剤である金属シリコン粉末との配合比率を変更している。実施例４は、珪石れんが粉を９０質量％にし、金属シリコン粉末を１０質量％にしている。また、金属シリコン粉末比率の減少に起因する燃焼性の低下を補うため、実施例４では、鉄粉および酸化第二鉄の添加量を、それぞれ０．５０質量％、１．５０質量％に増量している。一方、実施例５は、珪石れんが粉を８０質量％にし、金属シリコン粉末を２０質量％にしている。また、金属シリコン粉末比率の増大に起因して燃焼が不要に激しくなることを避けるため、実施例５では、鉄粉および酸化第二鉄の添加量を、それぞれ０．１０質量％、０．３０質量％に減量している。これらの配合においても、全評価項目において、良好な結果が得られた。 In Example 4 and Example 5, in the formulation of Example 3, the blending ratio of silica brick powder, which is a refractory powder, and metal silicon powder, which is a combustion agent, is changed. In Example 4, the silica brick powder is 90% by mass and the metal silicon powder is 10% by mass. Further, in order to compensate for the decrease in combustibility due to the decrease in the metal silicon powder ratio, in Example 4, the addition amounts of iron powder and ferric oxide were increased to 0.50 mass% and 1.50 mass%, respectively. is doing. On the other hand, in Example 5, the silica brick powder is 80% by mass and the metal silicon powder is 20% by mass. Further, in order to avoid unnecessarily intense combustion due to the increase in the metal silicon powder ratio, in Example 5, the addition amounts of iron powder and ferric oxide were 0.10 mass% and 0.30, respectively. Reduced to mass%. Even in these formulations, good results were obtained in all evaluation items.
実施例６および実施例７は、実施例３の配合において、珪石れんが粉の粒子径の配合比率を変更している。実施例６は、「１０００〜２０００μｍ」の粒子径を有する珪石れんが粉を１５．０質量％、「６００〜１０００μｍ」の粒子径を有する珪石れんが粉を３５．０質量％、「２００〜６００μｍ」の粒子径を有する珪石れんが粉を３５．０質量％とした配合である。また、実施例７は、「６００〜１０００μｍ」の粒子径を有する珪石れんが粉を４７．５質量％、「２００〜６００μｍ」の粒子径を有する珪石れんが粉を３７．０質量％、「〜２００μｍ」の粒子径を有する珪石れんが粉を０．５質量％とした配合である。実施例７では、結晶化促進剤であるリチウム塩の添加量を酸化物換算かつ外掛けで０．８９質量％に増量している。また、リチウム塩の増量に起因する着火性の低下を補うため、実施例７では、鉄粉および酸化第二鉄の添加量を増量している。これらの配合においても、全評価項目において、良好な結果が得られた。 In Example 6 and Example 7, the mixing ratio of the particle size of the silica brick powder is changed in the formulation of Example 3. In Example 6, 15.0% by mass of silica brick powder having a particle size of “1000 to 2000 μm”, 35.0% by mass of silica brick powder having a particle size of “600 to 1000 μm”, “200 to 600 μm” Silica brick powder having a particle size of 35.0% by mass. In addition, in Example 7, 47.5% by mass of silica brick powder having a particle size of “600 to 1000 μm”, 37.0% by mass of silica brick powder having a particle size of “200 to 600 μm”, and “˜200 μm”. The silica brick having a particle size of "" is blended with 0.5% by mass. In Example 7, the addition amount of the lithium salt, which is a crystallization accelerator, is increased to 0.89% by mass in terms of oxide and externally added. In addition, in Example 7, the addition amounts of iron powder and ferric oxide are increased in order to compensate for the decrease in ignitability caused by the increase in the lithium salt. Even in these formulations, good results were obtained in all evaluation items.
実施例８〜実施例１１は、その他の添加剤である、酸化カルシウム粉末、酸化マグネシウム粉末、硫酸ナトリウム、硫酸カリウムの配合比率を変更している。これらの配合においても、全評価項目において良好な結果が得られた。これらの添加物の配合比率を変更することで、耐火性粉末、金属シリコン粉末、結晶化促進剤、着火促進剤および燃焼補助剤の配合比率を変更した結果、溶射層間の一体性が乏しい状況が仮に発生したとしても、一体性を向上させることができる。 In Examples 8 to 11, the mixing ratio of calcium oxide powder, magnesium oxide powder, sodium sulfate, and potassium sulfate, which are other additives, is changed. Even in these formulations, good results were obtained in all evaluation items. By changing the blending ratio of these additives, as a result of changing the blending ratio of refractory powder, metal silicon powder, crystallization accelerator, ignition accelerator and combustion aid, there is a situation where the integrity between the thermal spray layers is poor. Even if it occurs, the integrity can be improved.
以上のように、本発明では、耐火性粉末、金属シリコン粉末、結晶化促進剤、着火促進剤、燃焼補助剤、およびその他の添加剤の純度、粒子径、添加量などを最適に調整したことにより、各原料の特性を活かしつつ欠点を補うことができる。その結果、多量の着火促進剤を添加することなく着火性および燃焼継続性を確保し、かつ溶射層間の一体性、耐用性および安全性に優れる溶射材料を得ることができる。 As described above, in the present invention, the purity, particle size, addition amount, etc. of the refractory powder, metal silicon powder, crystallization accelerator, ignition accelerator, combustion auxiliary agent, and other additives are optimally adjusted. This makes it possible to compensate for the drawbacks while utilizing the characteristics of each raw material. As a result, it is possible to obtain a thermal spray material that ensures ignitability and combustion continuity without adding a large amount of an ignition accelerator and is excellent in integrity, durability and safety between thermal spray layers.
比較例１および比較例２は、実施例３の配合について、珪石れんが粉と金属シリコン粉末との配合比率を変更している。比較例１は、珪石れんが粉を９５質量％にし、金属シリコン粉末を５質量％にしている。また、金属シリコン粉末比率の減少に起因する燃焼性の低下を補うため、鉄粉および酸化第二鉄の添加量を、それぞれ０．５０質量％、１．５０質量％に増量している。また、比較例２は、珪石れんが粉を７５質量％にし、金属シリコン粉末を２５質量％にしている。比較例１では、着火性と燃焼継続性が著しく損なわれて施工することができなかった。また、比較例２では、燃焼が激しく、施工体が被施工体から流れ落ちる結果、付着率が著しく低下した。 In Comparative Example 1 and Comparative Example 2, the blending ratio of the silica brick powder and the metal silicon powder is changed for the blending of Example 3. In Comparative Example 1, the silica brick powder is 95% by mass and the metal silicon powder is 5% by mass. Moreover, in order to compensate the combustibility fall resulting from the reduction | decrease of a metal silicon powder ratio, the addition amount of iron powder and ferric oxide is increased to 0.50 mass% and 1.50 mass%, respectively. In Comparative Example 2, the silica brick powder is 75% by mass and the metal silicon powder is 25% by mass. In Comparative Example 1, the ignitability and combustion continuity were remarkably impaired and construction could not be performed. Moreover, in the comparative example 2, combustion was intense and as a result of a construction body flowing down from a to-be-constructed body, the adhesion rate fell remarkably.
比較例３〜５は、実施例３の配合について、鉄粉を添加しない配合にするとともに、酸化第二鉄の添加量をそれぞれ０質量％、０．１０質量％、３．００質量％にしている。比較例３および４では、着火促進剤である鉄粉が添加されておらず、また、燃焼補助剤の添加量も適量より少ないため、着火性が悪く施工することができなかった。比較例５では、燃焼補助剤を多量に添加することで着火性を改善し施工ができたもの、結晶化不足に起因する珪石れんがとの熱膨張の一致の評価項目について満足できる結果は得られなかった。 In Comparative Examples 3 to 5, the composition of Example 3 was made not to add iron powder, and the addition amounts of ferric oxide were 0% by mass, 0.10% by mass, and 3.00% by mass, respectively. Yes. In Comparative Examples 3 and 4, iron powder as an ignition accelerator was not added, and the addition amount of the combustion auxiliary agent was less than an appropriate amount, so that the ignitability was poor and construction could not be performed. In Comparative Example 5, a satisfactory result was obtained with respect to an evaluation item of coincidence of thermal expansion with silica brick due to improvement in ignitability by adding a large amount of combustion auxiliary agent and construction. There wasn't.
比較例６では、比較例２〜５の配合について、鉄粉および酸化第二鉄の添加量を、それぞれ０．５０質量％、２．００質量％にするとともに、結晶化不足を解消するために硫酸リチウムを２．０質量％に増量している。しかしながら、着火性が悪く施工することができなかった。また、比較例７では、比較例６の配合について、着火性改善のため、ＭｇＯを減量するとともに着火を阻害する硫酸リチウムを１．５質量％まで減量している。しかしながら、着火性が悪く施工することができなかった。 In Comparative Example 6, for the blends of Comparative Examples 2 to 5, the addition amounts of iron powder and ferric oxide were 0.50 mass% and 2.00 mass%, respectively, and in order to eliminate insufficient crystallization The amount of lithium sulfate is increased to 2.0% by mass. However, construction was not possible due to poor ignitability. Moreover, in the comparative example 7, about the mixing | blending of the comparative example 6, in order to improve ignitability, while reducing MgO, the lithium sulfate which inhibits ignition is reduced to 1.5 mass%. However, construction was not possible due to poor ignitability.
以上の結果より、耐火性粉末（シリカ系）と金属シリコン粉末に、被施工体に吹き付けられた際の受熱により酸素供給源となる燃焼補助剤を使用することにより、着火性と燃焼継続性に優れ、耐用性と安全性に優れる溶射材料を実現できる。さらに、燃焼補助剤に加えて、比較的低温で酸化し、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着火促進剤を使用すると、より着火性と燃焼継続性に優れ、耐用性と安全性に優れる溶射材料を実現できる。 From the above results, ignitability and continuity of combustion can be achieved by using a combustion auxiliary agent that becomes an oxygen supply source by receiving heat when sprayed on the work piece to the refractory powder (silica) and metal silicon powder. Excellent thermal spray material with excellent durability and safety can be realized. Furthermore, in addition to combustion aids, use of an ignition accelerator that oxidizes at a relatively low temperature and assists the initial amount of heat required for the oxidation reaction of the metal silicon powder results in better ignitability and combustion continuity and durability. Thermally sprayed material with excellent safety can be realized.
本発明に係る溶射材料は、着火性および燃焼継続性に優れるとともに、耐用性と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部材として有用である。 Since the thermal spray material according to the present invention is excellent in ignitability and combustion continuity, and is excellent in durability and safety, it is useful as a thermal spray member used for repairing a coke oven carbonization chamber or the like.
Claims (7)
ＳｉＯ２成分の質量割合が９０％以上である耐火性粉末を、８０〜９０質量％、
金属シリコン粉末を、１０〜２０質量％、
リチウム塩を、前記耐火性粉末と前記金属シリコン粉末との全量に対して外掛け、かつ酸化物換算で０．３〜１．０質量％、
金属酸化物の粉末からなり、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を、前記耐火性粉末と前記金属シリコン粉末との全量に対して外掛けで０．３〜２．０質量％、
を含む溶射材料。 Thermal spray material used to repair the work piece made of silica brick by spraying oxygen onto the work piece as carrier gas and welding the refractory powder melted by the oxidation reaction heat of the metal powder to the repair surface Because
80 to 90% by mass of a refractory powder having a SiO 2 component mass ratio of 90% or more,
10-20% by mass of metal silicon powder,
Lithium salt is externally applied to the total amount of the refractory powder and the metal silicon powder, and 0.3 to 1.0% by mass in terms of oxide,
Combustion aid made of metal oxide powder, which becomes an oxygen supply source to metal silicon when receiving heat, is externally applied to the total amount of the refractory powder and metal silicon powder by 0.3-2. 0% by mass,
Including thermal spray material.
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