JP6662346B2 - Refractory and manufacturing method thereof - Google Patents
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- JP6662346B2 JP6662346B2 JP2017082762A JP2017082762A JP6662346B2 JP 6662346 B2 JP6662346 B2 JP 6662346B2 JP 2017082762 A JP2017082762 A JP 2017082762A JP 2017082762 A JP2017082762 A JP 2017082762A JP 6662346 B2 JP6662346 B2 JP 6662346B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000000463 material Substances 0.000 claims description 77
- 239000002994 raw material Substances 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 51
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 28
- 238000005470 impregnation Methods 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000011819 refractory material Substances 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052716 thallium Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 description 83
- 230000000694 effects Effects 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 22
- 230000007547 defect Effects 0.000 description 16
- 238000010304 firing Methods 0.000 description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000011029 spinel Substances 0.000 description 10
- 229910052596 spinel Inorganic materials 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910052580 B4C Inorganic materials 0.000 description 5
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- -1 for example Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920000142 Sodium polycarboxylate Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical compound [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 description 1
- 229910052849 andalusite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 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
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000010443 kyanite Substances 0.000 description 1
- 229910052850 kyanite Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
本発明は耐火物及びその製造方法に関する。 The present invention relates to a refractory and a method for producing the same.
耐火物は高温で使用されるので熱膨張や組織の変質による割れが発生することが多い。特に高温溶融物を扱う設備においては、割れから高温溶融物が侵入し熱膨張や組織の変質を更に加速せしめる。このような現象は損耗に繋がるため、問題である。 Since the refractory is used at a high temperature, cracking often occurs due to thermal expansion or structural deterioration. In particular, in a facility that handles a high-temperature melt, the high-temperature melt penetrates from cracks to further accelerate thermal expansion and structural deterioration. Such a phenomenon is a problem because it leads to wear.
このようななか、割れの予防と欠陥（割れ等）の拡大抑制が検討されている。
欠陥の拡大抑制のためには、割れによって生じた空隙を埋め、高温溶融物などの侵入を抑制することが望まれる。そのためには割れの発生に応じて体積膨張を伴う反応を示し、欠陥を充填する物質が有効である。この例としては金属シリコンや金属アルミニウムを添加し、後に酸化して酸化アルミニウムや酸化ケイ素となって体積が２倍前後に増加することを利用した欠陥の充填方法が提案されている。
Under such circumstances, prevention of cracks and suppression of expansion of defects (cracks, etc.) are being studied.
In order to suppress the expansion of defects, it is desired to fill voids generated by cracks and to suppress intrusion of a high-temperature melt or the like. For this purpose, a substance that exhibits a reaction accompanied by volume expansion in response to the occurrence of cracks and fills defects is effective. As an example of this, a defect filling method utilizing the fact that the volume is increased by about twice by adding metal silicon or metal aluminum and then oxidizing to aluminum oxide or silicon oxide has been proposed.
また、割れの予防には高強度化の他に低弾性率化、高熱伝導率化による温度勾配の低減などの対策が執られるが、高強度化と低弾性率の両立は難しく、高熱伝導材料は酸素などとの反応性が高く用途が限られるといった課題があった。炭素（カーボン）は高温に耐え、かつ熱伝導率の高い代表的な物質であり、マグネシア−カーボン質、ドロマイト−カーボン質、アルミナ−マグネシア−カーボン質、アルミナ−カーボン質、アルミナ−炭化珪素−カーボン質など、多くの耐火物材料で利用されている。ところが、炭素は数百℃以上の高温では、酸素や二酸化炭素や水蒸気を含む酸化性の気体や、酸化鉄や酸化マンガンを含む酸化性の溶融物により容易に酸化され消失する。炭素の酸化消失を抑制するためには、自らが酸化して炭素の酸化を阻害する物質、たとえば特開平５−１４８０１１号公報（特許文献１）では金属アルミニウムを、たとえば特許第５２０５７１２号公報（特許文献２）では金属シリコンを、たとえば特許第５４６２６０１号公報（特許文献３）では炭化ホウ素を、添加することが提案されている。 To prevent cracking, measures such as lowering the elastic modulus and reducing the temperature gradient by increasing the thermal conductivity are taken in addition to increasing the strength.However, it is difficult to achieve both high strength and low elastic modulus. Has a problem that its reactivity with oxygen or the like is high and its use is limited. Carbon (carbon) is a typical substance that withstands high temperatures and has high thermal conductivity, and includes magnesia-carbon, dolomite-carbon, alumina-magnesia-carbon, alumina-carbon, alumina-silicon carbide-carbon. Used in many refractory materials, such as quality. However, carbon is easily oxidized and lost by oxidizing gas containing oxygen, carbon dioxide and water vapor, or oxidizing melt containing iron oxide and manganese oxide at a high temperature of several hundred degrees Celsius or more. In order to suppress the disappearance of oxidation of carbon, a substance that oxidizes itself and inhibits oxidation of carbon, for example, metal aluminum in Japanese Patent Application Laid-Open No. 5-148011 (Patent Document 1), for example, Japanese Patent No. 5205712 (Patent Reference 2) proposes adding metal silicon, for example, Japanese Patent No. 5462601 (Patent Document 3), adding boron carbide.
割れの発生に応じて体積膨張を伴う反応を起こし欠陥を充填するために、金属シリコンや金属アルミニウムを添加し、後に酸化して酸化アルミニウムや酸化ケイ素となって体積が２倍前後に増加することを利用した欠陥の充填方法については、これらの酸化し易い金属の多くは低融点であり、たとえば溶鋼用途のように１５００℃以上の温度での使用においては耐火物の割れの発生よりも先に金属アルミニウムや金属シリコンが溶融酸化してしまい、膨張応力が割れを助長して耐損耗性が不十分となる（本明細書の比較例１−２及び１−３に相当）。
また、カーボンを含有する耐火物の、使用開始前の予熱時や使用開始直後のカーボンの酸化防止方法は多く提案されているが、金属アルミニウムや金属シリコンや炭化ホウ素を添加する方法では、添加物自体の硬さにより耐火物の圧縮成型時の欠陥の原因となり、結果として耐損耗性が低下する（本明細書の比較例２−２に相当）こと、これらの添加物は微粉とする事が製造上または取扱上高コストであるので一般に耐火物原料の微紛に比べて大粒径であるので反応生成物が局部的な高弾性化や低融点化といった耐火物性能の低下を招くこと、という弊害がある。また、ケイ酸ソーダ等の水溶液と固体の混合物を塗布する方法では、室温〜数百℃でのケイ酸ソーダの脱水収縮時に固体との界面に亀裂や欠陥が発生し酸素を遮断する性能が低下するという課題がある。また、界面の亀裂を抑制するためにアルカリ金属酸化物などの比較的融点の低い固体をケイ酸ソーダと混合することが提案されているが、摺動面に沿ってのエアリークや多孔質耐火物外周側面の通気を抑制するには十分であるものの、カーボンの酸化は微小な亀裂や欠陥を通しての少量の酸素でも進行するので効果が不十分である。また、ケイ酸ソーダを塗布する対象としてはＡｌ２Ｏ３−ＳｉＯ２系などの、耐火性能の低いＳｉＯ２を多く含む耐火物を対象としており、たとえば融点が２３２℃と低い溶融錫などには有効であるが、融点が５００℃以上のアルミ・銅・ガラス・鉄鋼などには適用できない。耐火物面への金属板の接着は酸素の遮断効果が高くカーボンの酸化が良好に防止できるが、そのコストの高さから適用範囲が限られる。
In order to cause a reaction accompanied by volume expansion in response to the occurrence of cracks and to fill defects, metal silicon or metal aluminum is added, and later oxidized to aluminum oxide or silicon oxide, and the volume increases about twice. With regard to the method of filling defects using, many of these easily oxidizable metals have a low melting point, and when used at a temperature of 1500 ° C. or more, for example, in molten steel, cracking of the refractory occurs earlier than cracking. Metallic aluminum and metallic silicon are melt-oxidized, and expansion stress promotes cracking, resulting in insufficient wear resistance (corresponding to Comparative Examples 1-2 and 1-3 in this specification).
Also, many methods for preventing carbon oxidation during reheating of carbon-containing refractories during preheating before use or immediately after use have been proposed.However, in the method of adding metallic aluminum, metallic silicon, or boron carbide, the additive is not used. The hardness of the refractory causes a defect at the time of compression molding of the refractory, resulting in a decrease in wear resistance (corresponding to Comparative Example 2-2 of the present specification). These additives may be fine powder. Since it is expensive in production or handling, it generally has a large particle size compared to fine powder of refractory raw material, so that the reaction product causes a decrease in refractory performance such as local high elasticity and low melting point, There is a negative effect. Further, in the method of applying a mixture of an aqueous solution such as sodium silicate and a solid, cracks and defects occur at the interface with the solid during dehydration shrinkage of the sodium silicate at room temperature to several hundreds degrees Celsius, and the performance of blocking oxygen is reduced. There is a problem to do. In addition, it has been proposed to mix a relatively low melting point solid such as an alkali metal oxide with sodium silicate in order to suppress interface cracking. However, air leaks along the sliding surface and porous refractories have been proposed. Although sufficient to suppress ventilation on the outer peripheral side surface, the effect of carbon oxidation is insufficient because even a small amount of oxygen passes through minute cracks and defects. In addition, as a target to which sodium silicate is applied, a refractory containing a large amount of SiO 2 having low fire resistance, such as an Al 2 O 3 —SiO 2 system, is targeted. For example, molten tin having a melting point as low as 232 ° C. is used. Although effective, it cannot be applied to aluminum, copper, glass, steel, etc. having a melting point of 500 ° C. or more. Adhesion of a metal plate to a refractory surface has a high effect of blocking oxygen and can prevent oxidation of carbon satisfactorily, but its high cost limits its application range.
そこで、本発明は、上記実情を鑑みて、耐損耗性に優れる耐火物及びその製造方法を提供することを目的とする。 In view of the above circumstances, an object of the present invention is to provide a refractory having excellent wear resistance and a method for producing the same.
本発明者は、上記課題について鋭意検討した結果、特定の量のＭＡＸ相物質を添加することで上記課題が解決できることを見出し、本発明に至った。
すなわち、本発明者は、以下の構成により上記課題が解決できることを見出した。
The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by adding a specific amount of the MAX phase substance, and have accomplished the present invention.
That is, the present inventor has found that the above problem can be solved by the following configuration.
（１） 耐火物原料と、下記式（１）で表されるＭＡＸ相物質とを含有し、
上記ＭＡＸ相物質の含有量が、上記耐火物原料に対して、０．２〜８．０質量％である、耐火物。
Ｍｎ＋１ＡＸｎ （１）
式（１）中、
Ｍは、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、又は、Ｔａを表し、
Ａは、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ｇａ、Ｇｅ、Ａｓ、Ｃｄ、Ｉｎ、Ｓｎ、Ｔｌ、又は、Ｐｂを表し、
Ｘは、Ｃ、又は、Ｎを表し、
ｎは、１、２、又は、３を表す。
（２） 上記耐火物原料が、炭素を１質量％以上含有する、上記（１）に記載の耐火物。
（３） 上記（１）又は（２）に記載の耐火物を製造する耐火物の製造方法であって、
耐火物原料を含有する耐火物前駆体を成形することで、成形体を得る、成形工程と、
上記成形体を下記式（１）で表されるＭＡＸ相物質を含有する液に浸漬させ、上記成形体に上記ＭＡＸ相物質を含浸させることで、上記（１）又は（２）に記載の耐火物を得る、含浸工程とを備える、耐火物の製造方法。
Ｍｎ＋１ＡＸｎ （１）
式（１）中、
Ｍは、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、又は、Ｔａを表し、
Ａは、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ｇａ、Ｇｅ、Ａｓ、Ｃｄ、Ｉｎ、Ｓｎ、Ｔｌ、又は、Ｐｂを表し、
Ｘは、Ｃ、又は、Ｎを表し、
ｎは、１、２、又は、３を表す。
（４） 上記成形工程の前に、さらに、
耐火物原料と、上記式（１）で表されるＭＡＸ相物質とを混合し、上記耐火物原料と、上記式（１）で表されるＭＡＸ相物質とを含有する耐火物前駆体を得る、混合工程を備え、
上記耐火物に含有される上記式（１）で表されるＭＡＸ相物質のうち、２０質量％以上のＭＡＸ相物質が、上記含浸工程により添加された、上記（３）に記載の耐火物の製造方法。
(1) It contains a refractory raw material and a MAX phase material represented by the following formula (1),
A refractory, wherein the content of the MAX phase substance is 0.2 to 8.0% by mass based on the refractory raw material.
M n + 1 AX n (1)
In equation (1),
M represents Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, or Ta;
A represents Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, Tl, or Pb;
X represents C or N;
n represents 1, 2, or 3.
(2) The refractory according to (1), wherein the refractory raw material contains 1% by mass or more of carbon.
(3) A method for producing a refractory according to the above (1) or (2),
By molding a refractory precursor containing a refractory raw material, to obtain a molded body, a molding step,
The molded article is immersed in a liquid containing a MAX phase substance represented by the following formula (1), and the molded article is impregnated with the MAX phase substance, whereby the refractory material according to the above (1) or (2) is obtained. A method for producing a refractory, comprising: obtaining an object; and an impregnation step.
M n + 1 AX n (1)
In equation (1),
M represents Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, or Ta;
A represents Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, Tl, or Pb;
X represents C or N;
n represents 1, 2, or 3.
(4) Before the molding step,
The refractory raw material and the MAX phase material represented by the above formula (1) are mixed to obtain a refractory precursor containing the refractory raw material and the MAX phase material represented by the above formula (1). , With a mixing step,
20% by mass or more of the MAX phase material represented by the formula (1) contained in the refractory is added to the refractory by the impregnation step. Production method.
以下に示すように、本発明によれば、耐損耗性に優れる耐火物及びその製造方法を提供することができる。 As described below, according to the present invention, a refractory excellent in wear resistance and a method for producing the same can be provided.
以下に、本発明の耐火物及びその製造方法について説明する。
なお、本明細書において、「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
また、本明細書において、耐火物とは、焼成前の耐火物（以下、「耐火物（焼成前）」とも言う）と、焼成後の耐火物（以下、「耐火物（焼成後）」の両方を含むものとする。
Hereinafter, the refractory of the present invention and the method for producing the refractory will be described.
In addition, in this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In this specification, the term “refractory” refers to a refractory before firing (hereinafter, also referred to as “refractory (before firing)”) and a refractory after firing (hereinafter, “refractory (after firing)”). It shall include both.
［耐火物］
本発明の耐火物は、耐火物原料と、下記式（１）で表されるＭＡＸ相物質とを含有する。ここで、上記ＭＡＸ相物質の含有量は、上記耐火物原料に対して、０．２〜８．０質量％である。
Ｍｎ＋１ＡＸｎ （１）
式（１）中、
Ｍは、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、又は、Ｔａを表し、
Ａは、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ｇａ、Ｇｅ、Ａｓ、Ｃｄ、Ｉｎ、Ｓｎ、Ｔｌ、又は、Ｐｂを表し、
Ｘは、Ｃ、又は、Ｎを表し、
ｎは、１、２、又は、３を表す。
[Refractory]
The refractory of the present invention contains a refractory raw material and a MAX phase material represented by the following formula (1). Here, the content of the MAX phase material is 0.2 to 8.0% by mass based on the refractory raw material.
M n + 1 AX n (1)
In equation (1),
M represents Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, or Ta;
A represents Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, Tl, or Pb;
X represents C or N;
n represents 1, 2, or 3.
本発明の耐火物は、このような構成をとるため、所望の効果が得られるものと考えられる。その理由は明らかではないが、およそ以下のとおりと推測される。
本発明の耐火物に含有されるＭＡＸ相物質は、遷移金属である「Ｍ」の炭化物又は窒化物の結晶格子が、「Ａ」の原子層を挟んで積み重なった結晶構造をしていることが知られている。そのため「Ａ」の原子層内で転位が可能であり常温で塑性変形できる特徴を持っている。結果として、常温での可塑性に富み、成形時に欠陥の原因となり難い。また、局部的な高弾性化や低融点化といった耐火物性能の低下にも繋がり難い。
また、仮に耐火物の使用中に割れ等の欠陥が生じたとしても、ＭＡＸ相物質が高温において酸素と反応し膨張（例えば、体積で２倍）するため、欠陥にＭＡＸ相物質が充填され、欠陥へのスラグ等の侵入が抑制されるものと考えられる。
さらには、上述のとおり、本発明の耐火物に含有されるＭＡＸ相物質は酸素と反応するため、本発明の耐火物に含有される耐火物原料が炭素を含有する場合には、炭素の酸化消失も抑制される。
これらの理由により、本発明の耐火物は極めて優れた耐損耗性を示すものと考えられる。
なお、本発明ではＭＡＸ相物質の含有量を特定の量に限定しているが、これは、ＭＡＸ相物質の含有量が多すぎると、ＭＡＸ相物質の酸化反応生成物が液相を生成し、損耗が進むという、本発明者の知見に基づくものである。
これらのことは、ＭＡＸ相物質を含有しない場合（比較例１−１及び２−１）、ＭＡＸ相物質の代わりに硬い金属アルミニウム、金属シリコン又は炭化ホウ素を添加した場合（比較例１−２、１−３及び２−２）、並びに、ＭＡＸ相物質を含有するがＭＡＸ相物質の含有量が耐火物原料に対して８．０質量％を超える場合（比較例１−４、１−５及び２−３）には耐損耗性が不十分となることからも推測される。
Since the refractory of the present invention has such a configuration, it is considered that a desired effect can be obtained. The reason is not clear, but is presumed to be as follows.
The MAX phase material contained in the refractory material of the present invention may have a crystal structure in which a crystal lattice of a carbide or nitride of “M” as a transition metal is stacked with an atomic layer of “A” interposed therebetween. Are known. Therefore, it has the characteristic that dislocation is possible in the atomic layer of “A” and that it can be plastically deformed at room temperature. As a result, it is highly plastic at room temperature and hardly causes defects during molding. Further, it is hard to lead to a decrease in refractory performance such as a local increase in elasticity and a decrease in melting point.
Further, even if a defect such as a crack occurs during use of the refractory, the MAX phase material reacts with oxygen at a high temperature and expands (for example, double in volume), so that the defect is filled with the MAX phase material, It is considered that slag and the like are prevented from entering the defect.
Further, as described above, since the MAX phase material contained in the refractory of the present invention reacts with oxygen, when the refractory raw material contained in the refractory of the present invention contains carbon, the oxidation of carbon may occur. Disappearance is also suppressed.
For these reasons, it is believed that the refractories of the present invention exhibit extremely good wear resistance.
In the present invention, the content of the MAX phase substance is limited to a specific amount. However, if the content of the MAX phase substance is too large, the oxidation reaction product of the MAX phase substance generates a liquid phase. This is based on the knowledge of the inventor that the wear proceeds.
These facts indicate that when no MAX phase material is contained (Comparative Examples 1-1 and 2-1), hard metal aluminum, metallic silicon or boron carbide is added instead of the MAX phase material (Comparative Examples 1-2, 1-3 and 2-2), and the case where the content of the MAX phase material exceeds 8.0% by mass with respect to the refractory raw material (Comparative Examples 1-4, 1-5 and Inferred from 2-3) is that the wear resistance is insufficient.
以下、本発明の耐火物に含有される各成分について詳述する。 Hereinafter, each component contained in the refractory of the present invention will be described in detail.
〔耐火物原料〕
本発明の耐火物に含有される耐火物原料は、耐火物の原料であって、後述するＭＡＸ相物質以外のものである。
耐火物原料としては、従来公知の原料を用いることができるが、例えば、耐火性粉体、結合剤、分散剤、添加剤（例えば、繊維類、硬化時間調整剤、増粘剤など）などが挙げられる。
なお、以下、複数の耐火物原料からなる組成物を「耐火物原料組成物」とも言う。
(Refractory raw materials)
The refractory raw material contained in the refractory of the present invention is a refractory raw material other than the MAX phase material described below.
As the refractory raw material, conventionally known raw materials can be used. For example, refractory powders, binders, dispersants, additives (eg, fibers, curing time regulators, thickeners, etc.) and the like can be used. No.
Hereinafter, a composition comprising a plurality of refractory raw materials is also referred to as a “refractory raw material composition”.
＜耐火性粉体＞
耐火性粉体としては、従来公知の原料を用いることができ、例えば、ブラウンアルミナ、電融アルミナ、焼結アルミナ、ボーキサイト、ダイアスポア、ばん土頁岩、仮焼アルミナなどのアルミナ質原料；珪石、珪砂、無定形シリカ（例えば、マイクロシリカ、シリカフラワー、ヒュームドシリカ、ホワイトカーボン）などのシリカ質原料；蝋石、シャモット、粘土、焦宝石、アンダリュサイト、シリマナイト、カイヤナイト、ムライトなどのアルミナシリカ質原料；石炭、コークス、ピッチ、人造黒鉛、天然黒鉛（例えば、鱗状黒鉛、土状黒鉛）、カーボンブラックなどの炭素質原料；電融スピネル、焼結スピネルなどのスピネル質原料；マグネシアクリンカーなどのマグネシア質原料；ドロマイトクリンカーなどのドロマイト質原料；電融ジルコニアなどのジルコニア質原料；ジルコンサンドなどのジルコン質原料；窒化珪素質原料；窒化アルミニウム質原料；炭化珪素質原料；炭化硼素質原料；硼化チタン質原料；硼化ジルコニウム質原料；等が挙げられる。
なかでも、本発明の効果がより優れる理由から、アルミナ質原料、スピネル質原料、マグネシア質原料及び炭素質原料（カーボン質原料）からなる群から選ばれる少なくとも１種であることが好ましく、アルミナ−スピネル質原料又はマグネシア−炭素質原料（カーボン質原料）であることがより好ましい。
<Refractory powder>
As the refractory powder, conventionally known raw materials can be used, for example, alumina raw materials such as brown alumina, fused alumina, sintered alumina, bauxite, diaspore, sand shale, and calcined alumina; silica, silica sand , Amorphous silica (eg, microsilica, silica flour, fumed silica, white carbon); siliceous raw materials such as limestone, chamotte, clay, gems, andalusite, sillimanite, kyanite, mullite, etc. Raw materials; carbonaceous materials such as coal, coke, pitch, artificial graphite, natural graphite (for example, flake graphite, earthy graphite), and carbon black; spinel materials such as electrofused spinel and sintered spinel; magnesia such as magnesia clinker Raw material; dolomite raw material such as dolomite clinker; Zirconia raw materials such as luconia; zircon raw materials such as zircon sand; silicon nitride raw materials; aluminum nitride raw materials; silicon carbide raw materials; boron carbide raw materials; titanium boride raw materials; zirconium boride raw materials; Can be
Among them, at least one selected from the group consisting of alumina-based materials, spinel-based materials, magnesia-based materials, and carbon-based materials (carbon-based materials) is preferable because the effects of the present invention are more excellent. More preferably, it is a spinel material or magnesia-carbon material (carbon material).
耐火性粉体の各含有量は特に限定されないが、本発明の効果がより優れる理由から、化学成分として、アルミナ（Ａｌ２Ｏ３）が９０質量％以上、マグネシア（ＭｇＯ）が５質量％以上となる組成が好ましい。このような化学成分は、例えば、蛍光Ｘ線分析装置などを用いて測定できる。また、理論化学成分が目的の数値となるように各耐火性粉体を配合してもよい。 Each content of the refractory powder is not particularly limited, but alumina (Al 2 O 3 ) is 90% by mass or more and magnesia (MgO) is 5% by mass or more as chemical components because the effect of the present invention is more excellent. Is preferable. Such a chemical component can be measured using, for example, an X-ray fluorescence analyzer. Further, each refractory powder may be blended so that the theoretical chemical component has a target value.
耐火性粉体の粒径は特に限定されないが、本発明の効果がより優れる理由から、粒径が７５μｍ未満の微粒の含有量が３５質量％以下であるのが好ましく、粒径１ｍｍ以上の粗粒の含有量が５０質量％以上であるのが好ましい。 Although the particle size of the refractory powder is not particularly limited, the content of fine particles having a particle size of less than 75 μm is preferably 35% by mass or less, and the coarse particles having a particle size of 1 mm or more are preferred because the effects of the present invention are more excellent. The content of the particles is preferably 50% by mass or more.
＜結合剤＞
結合剤としては、特に限定されないが、例えば、アルミナセメント、水硬性遷移アルミナ、ケイ酸塩、リン酸塩などが挙げられ、本発明の効果がより優れる理由から、アルミナセメントが好ましい。
結合剤の添加量は、特に限定されないが、本発明の効果がより優れる理由から、耐火性粉体１００質量％に対する外掛けで、０．５〜２５質量％であることが好ましい。
<Binder>
Examples of the binder include, but are not particularly limited to, alumina cement, hydraulic transition alumina, silicate, phosphate, and the like. Alumina cement is preferred because the effects of the present invention are more excellent.
The amount of the binder to be added is not particularly limited, but is preferably 0.5 to 25% by mass based on 100% by mass of the refractory powder because the effect of the present invention is more excellent.
＜分散剤＞
分散剤としては、特に限定されないが、例えば、トリポリリン酸ソーダ、ヘキサメタリン酸ソーダ、ウルトラポリリン酸ソーダ、酸性ヘキサメタリン酸ソーダなどのアルカリ金属リン酸塩；ポリカルボン酸ソーダなどのポリカルボン酸塩；アルキルスルホン酸塩；芳香族スルホン酸塩；ポリアクリル酸ソーダなどのポリアクリル酸塩；スルホン酸ソーダなどのスルホン酸塩；等が挙げられる。
分散剤の添加量は、特に限定されないが、本発明の効果がより優れる理由から、耐火性粉体１００質量％に対する外掛けで、０．０１〜１質量％であることが好ましい。
<Dispersant>
Examples of the dispersant include, but are not particularly limited to, alkali metal phosphates such as sodium tripolyphosphate, sodium hexametaphosphate, sodium ultrapolyphosphate, and sodium hexametaphosphate; polycarboxylates such as sodium polycarboxylate; alkyl sulfones Acid salts; aromatic sulfonates; polyacrylates such as sodium polyacrylate; sulfonates such as sodium sulfonate;
The addition amount of the dispersant is not particularly limited, but is preferably 0.01 to 1% by mass based on 100% by mass of the refractory powder because the effect of the present invention is more excellent.
〔ＭＡＸ相物質〕
上述のとおり、本発明の耐火物は下記式（１）で表されるＭＡＸ相物質（以下、「式（１）で表されるＭＡＸ相物質」を単に「ＭＡＸ相物質」とも言う）を含有する。
Ｍｎ＋１ＡＸｎ （１）
式（１）中、
Ｍは、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、又は、Ｔａを表し、
Ａは、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ｇａ、Ｇｅ、Ａｓ、Ｃｄ、Ｉｎ、Ｓｎ、Ｔｌ、又は、Ｐｂを表し、
Ｘは、Ｃ、又は、Ｎを表し、
ｎは、１、２、又は、３を表す。
[MAX phase substance]
As described above, the refractory of the present invention contains a MAX phase material represented by the following formula (1) (hereinafter, the “MAX phase material represented by the formula (1)” is also simply referred to as a “MAX phase material”). I do.
M n + 1 AX n (1)
In equation (1),
M represents Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, or Ta;
A represents Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, Tl, or Pb;
X represents C or N;
n represents 1, 2, or 3.
式（１）中、Ｍは、本発明の効果がより優れる理由から、Ｔｉ、Ｃｒ、Ｚｒ、又は、Ｎｂであることが好ましい。
式（１）中、Ａは、本発明の効果がより優れる理由から、Ａｌ、Ｓｉ、又は、Ｇａであることが好ましい。
式（１）中、Ｘは、本発明の効果がより優れる理由から、Ｃであることが好ましい。
In the formula (1), M is preferably Ti, Cr, Zr, or Nb because the effect of the present invention is more excellent.
In the formula (1), A is preferably Al, Si, or Ga because the effect of the present invention is more excellent.
In the formula (1), X is preferably C because the effect of the present invention is more excellent.
ＭＡＸ相物質は、本発明の効果がより優れる理由から、高温での安定性に優れた、
式（１）中のＭがＴｉ、Ｃｒ、Ｚｒ、又は、Ｎｂであり、
ＡがＡｌ、Ｓｉ、又は、Ｇａであり、
ＸがＣであることが好ましく、
なかでも、Ｃｒ２ＡｌＣ、Ｔｉ２ＡｌＣ又はＺｒ２ＧａＣであることがより好ましく、Ｃｒ２ＡｌＣであることがさらに好ましい。
The MAX phase material has excellent stability at high temperatures for the reason that the effect of the present invention is more excellent.
M in the formula (1) is Ti, Cr, Zr, or Nb;
A is Al, Si, or Ga;
X is preferably C,
Among them, Cr 2 AlC, Ti 2 AlC or Zr 2 GaC is more preferable, and Cr 2 AlC is more preferable.
＜ＭＡＸ相物質の製造方法＞
ＭＡＸ相物質を製造する方法は特に制限されないが、ＭＡＸ相物質がＣｒ２ＡｌＣである場合、本発明の効果がより優れる理由から、下記方法であることが好ましい。
<Method for producing MAX phase material>
The method for producing the MAX phase material is not particularly limited, but when the MAX phase material is Cr 2 AlC, the following method is preferred because the effect of the present invention is more excellent.
（ＭＡＸ相物質の製造方法の好適な態様）
まず、Ｃｒ、Ａｌ、Ｃの粉末をＣｒ：Ａｌ：Ｃ＝１０４：２７：１２の質量比で混合する。粉末は粒径１５０μｍ以下、望ましくは７５μｍ以下とすればより均質なＭＡＸ相物質が得られ、結果として、本発明の効果がより優れる。ここで、粒径は、例えば、ＪＩＳ Ｚ８８０１に規定される篩の公称目開きの数値を用いることができる。
(Preferred Embodiment of Method for Producing MAX Phase Material)
First, powders of Cr, Al, and C are mixed at a mass ratio of Cr: Al: C = 104: 27: 12. If the powder has a particle size of 150 μm or less, preferably 75 μm or less, a more uniform MAX phase material can be obtained, and as a result, the effects of the present invention are more excellent. Here, as the particle size, for example, a numerical value of a nominal opening of a sieve specified in JIS Z8801 can be used.
次に、得られた混合物を加圧成型する。
加圧成型の圧力は、得られる成形体が崩れ難く作業性が向上する理由から、１０ＭＰａ以上であることが好ましい。加圧成型の圧力が高い程空隙が減り、得られるＭＡＸ相物質が均質になるが、１００ＭＰａを超えると空隙はほぼ一定になると考えられる。そのため、加圧成型の圧力は１０〜１００ＭＰａが好適である。
次に、得られた成形体を非酸化雰囲気で焼成する。焼成の温度が高温であるほど焼成が速く、焼成の温度は１０００℃以上であることが好ましい。一方で、高温過ぎると液相が生成するので注意が必要である。Ｃｒ２ＡｌＣの場合、１２００℃４８時間、１５００℃で６時間焼成するとＭＡＸ相が十分に生成する。
Next, the obtained mixture is molded under pressure.
The pressure for the pressure molding is preferably 10 MPa or more, because the obtained molded body is less likely to collapse and the workability is improved. It is considered that the higher the pressure of the pressure molding, the smaller the voids and the obtained MAX phase material becomes homogeneous, but if the pressure exceeds 100 MPa, the voids become almost constant. Therefore, the pressure for the pressure molding is preferably from 10 to 100 MPa.
Next, the obtained molded body is fired in a non-oxidizing atmosphere. The higher the firing temperature, the faster the firing, and the firing temperature is preferably 1000 ° C. or higher. On the other hand, if the temperature is too high, a liquid phase is generated, so care must be taken. In the case of Cr 2 AlC, the MAX phase is sufficiently formed when calcined at 1200 ° C. for 48 hours and 1500 ° C. for 6 hours.
＜ＭＡＸ相物質の含有量＞
ＭＡＸ相物質の含有量は、上述した耐火物原料に対して、０．２〜８．０質量％である。ここで、ＭＡＸ相物質の含有量の基準となる耐火物原料は、全ての耐火物原料の合計を意図する。すなわち、ＭＡＸ相物質の含有量は、全ての耐火物原料の合計に対して、外掛けで、０．２〜８．０質量％である。
ＭＡＸ相物質の含有量は、本発明の効果がより優れる理由から、０．４〜８．０質量％であることが好ましい。
<Content of MAX phase substance>
The content of the MAX phase material is 0.2 to 8.0% by mass based on the refractory raw material described above. Here, the refractory raw material serving as a reference for the content of the MAX phase material is intended to be the sum of all refractory raw materials. That is, the content of the MAX phase material is 0.2 to 8.0% by mass on the basis of the sum of all the refractory raw materials.
The content of the MAX phase material is preferably 0.4 to 8.0% by mass because the effect of the present invention is more excellent.
ＭＡＸ相物質の添加量は、空隙を充填する目的からは多いことが望ましいが、微細な割れによる欠陥を充填する目的では０．２質量％の添加量でも効果を発揮する。その一方、ＭＡＸ相物質が酸化して生成する物質はＴｉＯ２やＳｉＯ２など比較的高融点の耐火性物質であるものの、耐火物の主成分であるＭｇＯやＡｌ２Ｏ３などの異種の耐火性物質と化合し融点を若干なりとも下げるので過多の添加は耐火性能を損なう。一般に耐火物の空隙率は１０〜２０％のものが多いが、大サイズの空隙ほどスラグや酸素の侵入が多くなるので、大サイズの空隙を選択的に充填すれば、空隙を半減することで侵入を１０分の１以下とすることができる。ＭＡＸ相物質は、その可塑性により耐火物粒子の間隙に選択的に存在させる事が可能であり、８質量％添加すれば酸化物生成にともなう体積膨張によって大サイズの空隙を８％低減することが出来、十分な効果を得られる。 The addition amount of the MAX phase material is desirably large for the purpose of filling voids, but the effect is exhibited even with the addition amount of 0.2% by mass for the purpose of filling defects due to fine cracks. On the other hand, the material generated by oxidizing the MAX phase material is a refractory material having a relatively high melting point such as TiO 2 or SiO 2, but a different type of refractory material such as MgO or Al 2 O 3 which is a main component of the refractory. Excessive addition impairs the refractory performance, since it is combined with a toxic substance and lowers the melting point at all. In general, the porosity of refractories is often 10 to 20%, but the larger the size of the void, the more the slag and oxygen infiltrate. Intrusion can be reduced to 1/10 or less. The MAX phase material can be selectively present in the interstices of the refractory particles due to its plasticity, and when added in an amount of 8% by mass, the large-sized voids can be reduced by 8% by volume expansion accompanying oxide formation. It is possible to obtain a sufficient effect.
［耐火物の製造方法］
本発明の耐火物を製造する方法は特に制限されないが、例えば、耐火物原料とＭＡＸ相物質とを混合する方法（混合法）、耐火物原料を成形してから成形後の空隙にＭＡＸ相物質を含浸させる方法（含浸法）などが挙げられる。
[Method of manufacturing refractories]
The method for producing the refractory of the present invention is not particularly limited. For example, a method of mixing a refractory raw material and a MAX phase material (mixing method), a method in which the refractory raw material is molded, and the MAX phase material (Impregnation method).
〔混合法〕
耐火物原料とＭＡＸ相物質とを混合する方法は特に制限されず、従来公知の方法を用いることができる。
(Mixing method)
The method of mixing the refractory raw material and the MAX phase material is not particularly limited, and a conventionally known method can be used.
〔含浸法〕
耐火物原料を成形してから成形後の空隙にＭＡＸ相物質を含浸させる方法は特に制限されないが、本発明の効果がより優れる理由から、下記態様であることが好ましい。
(Impregnation method)
The method of impregnating the voids after molding with the MAX phase material after molding the refractory raw material is not particularly limited, but the following embodiment is preferable because the effect of the present invention is more excellent.
＜含浸法の好適な態様＞
含浸法の好適な態様としては、例えば、
耐火物原料を含有する耐火物前駆体を成形することで、成形体を得る、成形工程と、
得られた成形体を、ＭＡＸ相物質を含有する液（例えば、ＭＡＸ相物質を水に懸濁させたスラリー）に浸漬させ（好ましくは、３０分以上分）、成形体にＭＡＸ相物質を含浸させることで、本発明の耐火物を得る、含浸工程とを備える方法が挙げられる。
上記好適な態様において、含浸深さがより深くなり、結果として本発明の効果がより優れる理由から、ＭＡＸ相物質は粒径４０μｍ以下であることが好ましい。ここで、粒径は、例えば、ＪＩＳ Ｚ８８０１に規定される篩の公称目開きの数値を用いることができる。
<Preferred embodiment of impregnation method>
As a preferred embodiment of the impregnation method, for example,
By molding a refractory precursor containing a refractory raw material, to obtain a molded body, a molding step,
The obtained molded body is immersed (preferably for 30 minutes or more) in a liquid containing the MAX phase substance (for example, a slurry in which the MAX phase substance is suspended in water), and the molded body is impregnated with the MAX phase substance. The method includes an impregnation step of obtaining the refractory of the present invention.
In the above preferred embodiment, the MAX phase material preferably has a particle size of 40 μm or less because the impregnation depth becomes deeper, and as a result, the effect of the present invention is more excellent. Here, as the particle size, for example, a numerical value of a nominal opening of a sieve specified in JIS Z8801 can be used.
〔混合法＋含浸法〕
また、本発明の効果がより優れる理由から、混合法と含浸法とを組み合わせた方法（混合法＋含浸法）も好ましい。
混合法＋含浸法は、本発明の効果がより優れる理由から、下記態様であることが好ましい。
[Mixing method + impregnation method]
Further, a method (mixing method + impregnation method) in which the mixing method and the impregnation method are combined is also preferable because the effect of the present invention is more excellent.
The mixing method and the impregnation method are preferably the following embodiments because the effect of the present invention is more excellent.
＜混合法＋含浸法の好適な態様＞
混合法＋含浸法の好適な態様としては、上述した含浸法の好適な態様において、上述した成形工程の前に、さらに、耐火物原料と、ＭＡＸ相物質とを混合し、耐火物原料と、ＭＡＸ相物質を含有する耐火物前駆体を得る、混合工程を備える方法が挙げられる。
ここで、本発明の効果がより優れる理由から、得られる耐火物に含有されるＭＡＸ相物質のうち、２０質量％以上のＭＡＸ相物質が、上述した含浸工程により添加されたものであることが好ましい。耐火物に含有されるＭＡＸ相物質のうち含浸工程により添加される割合の上限は特に制限されないが、本発明の効果がより優れる理由から、９０質量％以下であることが好ましい。
<Preferred embodiment of mixing method + impregnation method>
As a preferred embodiment of the mixing method and the impregnation method, in the preferred embodiment of the impregnation method described above, before the molding step described above, further, a refractory raw material and a MAX phase material are mixed, A method including a mixing step for obtaining a refractory precursor containing a MAX phase material may be used.
Here, from the reason that the effect of the present invention is more excellent, the MAX phase material contained in the obtained refractory may be one in which 20% by mass or more of the MAX phase material is added by the above-described impregnation step. preferable. The upper limit of the proportion added in the impregnation step in the MAX phase substance contained in the refractory is not particularly limited, but is preferably 90% by mass or less from the viewpoint that the effect of the present invention is more excellent.
［用途］
本発明の耐火物の用途は特に制限されないが、溶鋼容器（溶鋼鍋）又は転炉用の耐火物に特に好適である。
[Use]
Although the use of the refractory of the present invention is not particularly limited, it is particularly suitable for a refractory for a molten steel vessel (a molten steel pot) or a converter.
以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
〔耐火物の製造〕
以下のとおり、各耐火物を製造した。
[Manufacture of refractories]
Each refractory was manufactured as follows.
＜比較例１−１〜１−５及び２−１〜２−３、並びに、実施例１−１〜１−２及び２−１〜２−３＞（混合法）
表１に示される耐火物原料組成物１００質量％に対して、同表に示されるＭＡＸ相物質又は比較物質を同表に示される割合（質量％）で混合することで各耐火物（焼成前）を得た。なお、比較例１−１及び２−１ではＭＡＸ相物質も比較物質も混合しなかった。
得られた耐火物（焼成前）を用いて成形体（厚み：比較例１−１〜１−５及び実施例１−１〜１−２は１４０ｍｍ、比較例２−１〜２−３及び実施例２−１〜２−３は５４０ｍｍ）を作製し、これをコークスブリーズ中にて１４００℃×３時間の還元焼成を行った。このようにして、各耐火物（焼成後）を得た。
<Comparative Examples 1-1 to 1-5 and 2-1 to 2-3, and Examples 1-1 to 1-2 and 2-1 to 2-3> (mixing method)
Each refractory (before firing) was mixed with 100% by mass of the refractory raw material composition shown in Table 1 at a ratio (% by mass) shown in the table with the MAX phase material or the comparative material shown in the table. ) Got. In Comparative Examples 1-1 and 2-1, neither the MAX phase substance nor the comparative substance was mixed.
Using the obtained refractory (before firing), a molded article (thickness: 140 mm for Comparative Examples 1-1 to 1-5 and Examples 1-1 to 1-2, Comparative Examples 2-1 to 2-3 and Examples) (Examples 2-1 to 2-3 were 540 mm), and this was subjected to reduction firing at 1400 ° C. × 3 hours in a coke breathe. Thus, each refractory (after firing) was obtained.
＜実施例１−３＞（混合法＋含浸法）
表１に示されるアルミナ−スピネル質耐火物原料組成物１００質量％に対して、同表に示されるＣｒ２ＡｌＣを６質量％の割合で混合することで耐火物前駆体を得た。（混合工程）
得られた耐火物前駆体を用いて成形体（厚み：１４０ｍｍ）を作製した。（成形工程）
次いで、表１に示されるＣｒ２ＡｌＣを水に懸濁させたスラリーを調製した。そして、上述のとおり得られた成形体を真空容器内に装入し、さらに上記スラリーを注入して成形体（焼成前）を浸漬させた。その後、大気圧まで復圧させ、アルミナ−スピネル質耐火物原料組成物に対するＣｒ２ＡｌＣの含有量が７．５質量％になるまで含浸させた。（含浸工程）
このようにしてＭＡＸ相物質であるＣｒ２ＡｌＣ含有する耐火物（焼成前）を得た。得られた耐火物（焼成前）において、耐火物に含有されるＣｒ２ＡｌＣのうち、２０質量％（＝１．５／７．５×１００）のＣｒ２ＡｌＣは、含浸工程により添加されたものである。
さらに、得られた耐火物（焼成前）をコークスブリーズ中にて１４００℃×３時間の還元焼成を行った。このようにして、耐火物（焼成後）を得た。
<Example 1-3> (mixing method + impregnation method)
Cr 2 AlC shown in Table 1 was mixed at a ratio of 6% by mass with respect to 100% by mass of the alumina-spinel refractory raw material composition shown in Table 1 to obtain a refractory precursor. (Mixing process)
A molded article (thickness: 140 mm) was produced using the obtained refractory precursor. (Molding process)
Next, a slurry in which Cr 2 AlC shown in Table 1 was suspended in water was prepared. Then, the molded body obtained as described above was charged into a vacuum vessel, and the slurry was further injected to immerse the molded body (before firing). Thereafter, the pressure was restored to the atmospheric pressure, and impregnation was performed until the content of Cr 2 AlC with respect to the alumina-spinel refractory raw material composition became 7.5% by mass. (Impregnation step)
Thus, a refractory (before firing) containing Cr 2 AlC as a MAX phase material was obtained. In the obtained refractory (before firing), of the Cr 2 AlC contained in the refractory, 20% by mass (= 1.5 / 7.5 × 100) of Cr 2 AlC was added by the impregnation step. Things.
Further, the obtained refractory (before firing) was reduced and fired at 1400 ° C. for 3 hours in a coke breather. Thus, a refractory (after firing) was obtained.
〔耐損耗性の評価〕
実施例１−１、１−２及び１−３並びに比較例１−１、１−２、１−３、１−４及び１−５については、それぞれの耐火物を用いた溶鋼容器に、炭素含有量が０．１質量％の溶鋼を装入し、ＬＦ処理４０％、ＲＨ処理６０％の割合で二次精錬の処理を行った後に、連続鋳造工程に供するまでを１チャージとして、耐火物の残厚が４０ｍｍになるまで（つまり、元厚１４０ｍｍから１００ｍｍ減るまで）のチャージ数を測定した。測定結果を表１の「耐用」の欄に示す。チャージ数の値が大きいほど、溶鋼による溶損が抑制され、耐損耗性に優れるものとして評価できる。
実施例２−１、２−２及び２−３並びに比較例２−１、２−２及び２−３については、それぞれの耐火物を用いた転炉に、炭素含有量が４質量％の溶鋼を装入し、炭素含有量が０．１重量％となるまで脱炭処理を行った後に、二次精錬工程に供するまでを１チャージとして、耐火物の残厚が１５０ｍｍになるまで（つまり、元厚５４０ｍｍから３９０ｍｍ減るまで）のチャージ数を測定した。測定結果を表１の「耐用」の欄に示す。チャージ数の値が大きいほど、溶鋼による溶損が抑制され、耐損耗性に優れるものとして評価できる。
[Evaluation of wear resistance]
For Examples 1-1, 1-2 and 1-3 and Comparative Examples 1-1, 1-2, 1-3, 1-4 and 1-5, carbon steel was added to a molten steel container using each refractory. After charging molten steel having a content of 0.1% by mass and performing secondary refining at a ratio of LF treatment of 40% and RH treatment of 60%, the refractory is treated as one charge until it is subjected to a continuous casting process. The number of charges was measured until the remaining thickness became 40 mm (that is, 100 mm from the original thickness of 140 mm). The measurement results are shown in the column of “Durable” in Table 1. The larger the value of the charge number, the more the erosion due to molten steel is suppressed, and it can be evaluated as having excellent wear resistance.
In Examples 2-1, 2-2, and 2-3 and Comparative Examples 2-1, 2-2, and 2-3, the converter using each refractory was prepared by adding molten steel having a carbon content of 4% by mass to the converter. , And after performing a decarburization treatment until the carbon content becomes 0.1% by weight, and then subjecting it to the secondary refining process as one charge, until the residual thickness of the refractory becomes 150 mm (that is, The number of charges (from the original thickness of 540 mm to a reduction of 390 mm) was measured. The measurement results are shown in the column of “Durable” in Table 1. The larger the value of the charge number, the more the erosion due to molten steel is suppressed, and it can be evaluated as having excellent wear resistance.
上記表１に示される耐火物原料組成物及びＭＡＸ相物質の詳細は以下のとおりである。
・アルミナ−スピネル質：ＭｇＯ：Ａｌ２Ｏ３のモル比が１：１．２〜１：２．２の範囲であり且つ粒径が５ｍｍ以下であるアルミナ・スピネルクリンカーと、アルミナ原料と、アルミナセメントとから構成されるアルミナ−スピネル質耐火物原料組成物
・マグネシア−１０％カーボン質：ＭｇＯ純度が９５％以上であり且つ粒径が５ｍｍ以下である電融ＭｇＯ原料と、鱗状黒鉛１０％とから構成されるマグネシア−１０％カーボン質耐火物原料組成物（炭素の含有量：１０質量％）
・Ｃｒ２ＡｌＣ：以下のとおり製造したＭＡＸ相物質であるＣｒ２ＡｌＣ
Ｃｒ、Ａｌ、Ｃの粉末（粒径７５μｍ以下）をＣｒ：Ａｌ：Ｃ＝１０４：２７：１２の質量比で混合した。次にこの混合物を１０〜１００ＭＰａの圧力で加圧成型した。次にこの成形体を１０００℃以上の非酸化雰囲気で焼成した（１２００℃で４８時間、１５００℃で６時間）。このようにしてＭＡＸ相物質であるＣｒ２ＡｌＣを得た。
・Ｔｉ２ＡｌＣ：以下のとおり製造したＭＡＸ相物質であるＴｉ２ＡｌＣ
Ｔｉ、Ａｌ、Ｃの粉末（粒径７５μｍ以下）をＴｉ：Ａｌ：Ｃ＝１０４：２７：１２の質量比で混合した。次にこの混合物を１０〜１００ＭＰａの圧力で加圧成型した。次にこの成形体を１０００℃以上の非酸化雰囲気で焼成した（１２００℃で４８時間、１５００℃で６時間）。このようにしてＭＡＸ相物質であるＴｉ２ＡｌＣを得た。
・Ｚｒ２ＧａＣ：以下のとおり製造したＭＡＸ相物質であるＺｒ２ＧａＣ
Ｚｒ、Ｇａ、Ｃの粉末（粒径７５μｍ以下）をＺｒ：Ｇａ：Ｃ＝１０４：２７：１２の質量比で混合した。次にこの混合物を１０〜１００ＭＰａの圧力で加圧成型した。次にこの成形体を１０００℃以上の非酸化雰囲気で焼成した（１２００℃で４８時間、１５００℃で６時間）。このようにしてＭＡＸ相物質であるＺｒ２ＧａＣを得た。
The details of the refractory raw material composition and the MAX phase material shown in Table 1 above are as follows.
Alumina - spinel: MgO: molar ratio of Al 2 O 3 is 1: 1.2 to 1: and alumina spinel clinker 2.2 in the range of and particle size is 5mm or less, and alumina raw material, alumina Alumina-spinel refractory raw material composition composed of cement and magnesia-10% carbonaceous material: electrofused MgO raw material having a MgO purity of 95% or more and a particle size of 5 mm or less, and 10% of flaky graphite -Magnesia-10% carbonaceous refractory raw material composition (carbon content: 10% by mass)
· Cr 2 AlC: Cr 2 AlC a MAX phase material prepared as follows
Cr, Al, and C powders (particle diameter of 75 μm or less) were mixed at a mass ratio of Cr: Al: C = 104: 27: 12. Next, this mixture was molded under pressure at a pressure of 10 to 100 MPa. Next, this molded body was fired in a non-oxidizing atmosphere at 1000 ° C. or higher (48 hours at 1200 ° C., 6 hours at 1500 ° C.). Thus, Cr 2 AlC as a MAX phase material was obtained.
· Ti 2 AlC: Ti 2 AlC a MAX phase material prepared as follows
Powders of Ti, Al, and C (particle diameter of 75 μm or less) were mixed at a mass ratio of Ti: Al: C = 104: 27: 12. Next, this mixture was molded under pressure at a pressure of 10 to 100 MPa. Next, this molded body was fired in a non-oxidizing atmosphere at 1000 ° C. or higher (48 hours at 1200 ° C., 6 hours at 1500 ° C.). Thus, Ti 2 AlC as a MAX phase material was obtained.
· Zr 2 GaC: Zr 2 GaC a MAX phase material prepared as follows
Powders of Zr, Ga, and C (particle size: 75 μm or less) were mixed at a mass ratio of Zr: Ga: C = 104: 27: 12. Next, this mixture was molded under pressure at a pressure of 10 to 100 MPa. Next, this molded body was fired in a non-oxidizing atmosphere at 1000 ° C. or higher (48 hours at 1200 ° C., 6 hours at 1500 ° C.). In this way, Zr 2 GaC as a MAX phase material was obtained.
表１中、「製造方法」に記載の「混合法」及び「混合法＋含浸法」は、上述した「混合法」及び「混合法＋含浸法」を表す。 In Table 1, “mixing method” and “mixing method + impregnation method” described in “production method” represent the “mixing method” and “mixing method + impregnation method” described above.
表１から分かるように、ＭＡＸ相物質を添加しなかった比較例１−１と比較して、ＭＡＸ相物質を添加した実施例１−１〜１−３は、優れた耐損耗性を示した。 As can be seen from Table 1, Examples 1-1 to 1-3 in which the MAX phase material was added exhibited excellent wear resistance as compared with Comparative Example 1-1 in which the MAX phase material was not added. .
ここで、ＭＡＸ相物質を添加しなかった比較例１−１は残厚４０ｍｍ程度となった時点で２０ｍｍ以上の剥離が生じていた。これは、内部の欠陥にスラグが侵入して変質し、膨張率、強度、ヤング率などの物性が変化することで表層から約２０ｍｍの深さの部位に大きな亀裂が入ることが原因であった。
これに対して、ＭＡＸ相物質を添加した実施例１−１〜３では、内部の欠陥をＭＡＸ相物質の酸化反応性生物であるところのＣｒ２Ｏ３又はＴｉ２Ｏ３とＡｌ２Ｏ３とが充填し、スラグの侵入が大幅に軽減されていることが確認された。
Here, in Comparative Example 1-1 in which the MAX phase material was not added, peeling of 20 mm or more occurred when the remaining thickness was about 40 mm. This was due to the fact that the slag penetrated into the internal defect and deteriorated, and the physical properties such as the expansion rate, strength, and Young's modulus changed, resulting in a large crack at a depth of about 20 mm from the surface layer. .
On the other hand, in Examples 1-1 to 1-3 in which the MAX phase material was added, the internal defects were changed to Cr 2 O 3 or Ti 2 O 3 and Al 2 O 3 which are oxidation reaction products of the MAX phase material. It was confirmed that infiltration of slag was significantly reduced.
また、ＭＡＸ相物質を添加しなかった比較例２−１と比較して、ＭＡＸ相物質を添加した実施例２−１〜２−３は、優れた耐損耗性を示した。 Further, as compared with Comparative Example 2-1 in which the MAX phase material was not added, Examples 2-1 to 2-3 in which the MAX phase material was added exhibited excellent wear resistance.
ＭＡＸ相物質を添加しなかった比較例２−１は、使用中にカーボンの酸化消失が進み、割れが発生していた。
これに対して、ＭＡＸ相物質を添加した実施例２−１〜２−３はカーボンが良好に保持されていた。
In Comparative Example 2-1 in which the MAX phase material was not added, the carbon was oxidized and disappeared during use, and cracks occurred.
On the other hand, in Examples 2-1 to 2-3 to which the MAX phase material was added, carbon was favorably retained.
また、実施例１−１と１−２との対比（混合法を用いて製造した態様同士の対比）から、上述した式（１）中のＭがＣｒである実施例１−１は、より優れた耐損耗性を示した。
また、実施例１−１と１−３との対比（ＭＡＸ相物質としてＣｒ２ＡｌＣを用いた態様同士の対比）から、含浸法（混合法＋含浸法）を用いて製造した実施例１−３は、より優れた耐損耗性を示した。
また、実施例２−１と２−３との対比（ＭＡＸ相物質の含有量が７．５質量％である態様同士の対比）から、上述した式（１）中のＭがＺｒである実施例２−３は、より優れた耐損耗性を示した。
Also, from the comparison between Examples 1-1 and 1-2 (comparison between embodiments manufactured using the mixing method), Example 1-1 in which M in the above formula (1) is Cr is more It showed excellent wear resistance.
In addition, from the comparison between Examples 1-1 and 1-3 (comparison between embodiments using Cr 2 AlC as the MAX phase material), Example 1 manufactured using the impregnation method (mixing method + impregnation method). No. 3 showed better wear resistance.
Further, from the comparison between Examples 2-1 and 2-3 (comparison between the embodiments in which the content of the MAX phase substance is 7.5% by mass), the case where M in the above formula (1) is Zr. Example 2-3 showed better wear resistance.
ＭＡＸ相物質の代わりに金属アルミニウムを添加した比較例１−２、及び、ＭＡＸ相物質の代わりに金属シリコンを添加した比較例１−３は、耐損耗性が不十分であった。同様に、ＭＡＸ相物質の代わりに炭化ホウ素を添加した比較例２−２も、耐損耗性が不十分であった。 Comparative Example 1-2 in which metallic aluminum was added instead of the MAX phase material and Comparative Example 1-3 in which metallic silicon was added instead of the MAX phase material had insufficient wear resistance. Similarly, Comparative Example 2-2 in which boron carbide was added instead of the MAX phase material also had insufficient wear resistance.
また、ＭＡＸ相物質を含有するが、ＭＡＸ相物質の含有量が耐火物原料に対して８．０質量％を超える比較例１−４及び１−５は、耐損耗性が不十分であった。同様に、ＭＡＸ相物質を含有するが、ＭＡＸ相物質の含有量が耐火物原料に対して８．０質量％を超える比較例２−３も、耐損耗性が不十分であった。ＭＡＸ相物質の酸化反応生成物が液相を生成したためと推測される。 Comparative Examples 1-4 and 1-5, which contain a MAX phase substance but have a MAX phase substance content of more than 8.0% by mass with respect to the refractory raw material, had insufficient wear resistance. . Similarly, Comparative Example 2-3, which contains a MAX phase substance but has a MAX phase substance content of more than 8.0% by mass based on the refractory raw material, also had insufficient wear resistance. It is presumed that the oxidation reaction product of the MAX phase material formed a liquid phase.
Claims (4)
前記ＭＡＸ相物質の含有量が、前記耐火物原料に対して、０．２〜８．０質量％である、耐火物。
Ｍｎ＋１ＡＸｎ （１）
式（１）中、
Ｍは、Ｃｒを表し、
Ａは、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ｇａ、Ｇｅ、Ａｓ、Ｃｄ、Ｉｎ、Ｓｎ、Ｔｌ、又は、Ｐｂを表し、
Ｘは、Ｃ、又は、Ｎを表し、
ｎは、１、２、又は、３を表す。 It contains a refractory raw material and a MAX phase material represented by the following formula (1),
A refractory, wherein the content of the MAX phase substance is 0.2 to 8.0% by mass based on the refractory raw material.
M n + 1 AX n (1)
In equation (1),
M represents Cr ,
A represents Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, Tl, or Pb;
X represents C or N;
n represents 1, 2, or 3.
前記ＭＡＸ相物質の含有量が、前記耐火物原料に対して、０．２〜８．０質量％である、耐火物を製造する耐火物の製造方法であって、
耐火物原料を含有する耐火物前駆体を成形することで、成形体を得る、成形工程と、
前記成形体を下記式（１）で表されるＭＡＸ相物質を含有する液に浸漬させ、前記成形体に前記ＭＡＸ相物質を含浸させることで、前記耐火物を得る、含浸工程とを備える、耐火物の製造方法。
Ｍｎ＋１ＡＸｎ （１）
式（１）中、
Ｍは、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、又は、Ｔａを表し、
Ａは、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ｇａ、Ｇｅ、Ａｓ、Ｃｄ、Ｉｎ、Ｓｎ、Ｔｌ、又は、Ｐｂを表し、
Ｘは、Ｃ、又は、Ｎを表し、
ｎは、１、２、又は、３を表す。 It contains a refractory raw material and a MAX phase material represented by the following formula (1),
A method for producing a refractory for producing a refractory , wherein the content of the MAX phase substance is 0.2 to 8.0% by mass based on the refractory raw material ,
By molding a refractory precursor containing a refractory raw material, to obtain a molded body, a molding step,
The molded body is immersed in a liquid containing the MAX phase material represented by the following formula (1), by impregnating the MAX phase material to the molded body to obtain said refractory, and a impregnating step, How to make refractories.
M n + 1 AX n (1)
In equation (1),
M represents Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, or Ta;
A represents Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, Tl, or Pb;
X represents C or N;
n represents 1, 2, or 3.
耐火物原料と、前記式（１）で表されるＭＡＸ相物質とを混合し、前記耐火物原料と、前記式（１）で表されるＭＡＸ相物質とを含有する耐火物前駆体を得る、混合工程を備え、
前記耐火物に含有される前記式（１）で表されるＭＡＸ相物質のうち、２０質量％以上のＭＡＸ相物質が、前記含浸工程により添加された、請求項３に記載の耐火物の製造方法。 Before the molding step,
The refractory raw material and the MAX phase material represented by the formula (1) are mixed to obtain a refractory precursor containing the refractory raw material and the MAX phase material represented by the formula (1). , With a mixing step,
4. The refractory according to claim 3, wherein 20% by mass or more of the MAX phase material represented by the formula (1) contained in the refractory is added in the impregnation step. Method.
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