WO2024029363A1 - Matériau de base revêtu - Google Patents
Matériau de base revêtu Download PDFInfo
- Publication number
- WO2024029363A1 WO2024029363A1 PCT/JP2023/026615 JP2023026615W WO2024029363A1 WO 2024029363 A1 WO2024029363 A1 WO 2024029363A1 JP 2023026615 W JP2023026615 W JP 2023026615W WO 2024029363 A1 WO2024029363 A1 WO 2024029363A1
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- WO
- WIPO (PCT)
- Prior art keywords
- film
- base material
- thickness
- region
- coating
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 134
- 239000011248 coating agent Substances 0.000 claims abstract description 69
- 238000000576 coating method Methods 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- 230000007423 decrease Effects 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 description 111
- 239000007788 liquid Substances 0.000 description 66
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 45
- 239000002904 solvent Substances 0.000 description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 28
- 239000002184 metal Substances 0.000 description 28
- 229910052736 halogen Inorganic materials 0.000 description 25
- 150000002367 halogens Chemical class 0.000 description 25
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 22
- 229910052740 iodine Inorganic materials 0.000 description 22
- 239000011630 iodine Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 17
- 238000003917 TEM image Methods 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 10
- 150000004703 alkoxides Chemical class 0.000 description 9
- -1 aluminum alkoxide Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 229910000889 permalloy Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 2
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 2
- QQLIGMASAVJVON-UHFFFAOYSA-N 1-naphthalen-1-ylethanone Chemical compound C1=CC=C2C(C(=O)C)=CC=CC2=C1 QQLIGMASAVJVON-UHFFFAOYSA-N 0.000 description 1
- SNOJPWLNAMAYSX-UHFFFAOYSA-N 2-methylpropan-1-ol;titanium Chemical compound [Ti].CC(C)CO.CC(C)CO.CC(C)CO.CC(C)CO SNOJPWLNAMAYSX-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910017082 Fe-Si Inorganic materials 0.000 description 1
- 229910017133 Fe—Si Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000702 sendust Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910000815 supermalloy Inorganic materials 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
Definitions
- the present disclosure relates to coated substrates.
- Patent Documents 1 to 4 disclose coated substrates provided with metal oxide films.
- a wet film forming method is adopted.
- a dry film forming method (dry process) is employed to control the thickness in accordance with the complex shape of the base material.
- conventional coated base materials are not necessarily sufficient, and there has been a strong desire for the development of new coated base materials.
- JP2011-32521A Japanese Patent Application Publication No. 2009-147192 JP2015-93821A Japanese Patent Application Publication No. 9-202606
- the present disclosure has been made in view of the above circumstances, and aims to provide a novel coated base material that is applicable to various fields and can be mass-produced.
- the present disclosure can be realized as the following forms.
- the base material is covered with a film,
- the thickness of the film is 1 nm or more and less than 800 nm,
- the total elemental percentage of metal elements and O (oxygen) is 70 atm% or more,
- the relative density of the film is 90% or more,
- a coated base material that satisfies at least one of the following conditions (1) and (2).
- Condition (1) The maximum thickness of the film formed on the edge region of the surface of the base material is greater than the thickness of the film formed on the inner region of the surface, which is inside the edge region. big.
- Condition (2) The maximum thickness of the film formed on the region where the convex portion is present on the surface of the base material is greater than the thickness of the film formed on the region where the convex portion is not present on the surface. .
- the maximum thickness of the coating formed on the edge region is 10% or more greater than the thickness of the coating formed on the inner region, [1] or [2] Coated substrate as described.
- the maximum thickness of the film formed on the region where the convex portion is present is 10% or more greater than the thickness of the film formed on the region where the convex portion is not present, [1 ] or the coated base material according to [2].
- the thickness of the coating decreases from the maximum thickness portion of the coating formed on the edge region toward the inner region. coated base material.
- the thickness of the coating decreases from the maximum thickness portion of the coating formed on the region where the convex portion exists toward the region where the convex portion does not exist, [1] Or the coated base material according to [2].
- the metal elements include Al (aluminum), Ti (titanium), Mo (molybdenum), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Zr (zirconium),
- the coating according to [1] or [2] which is at least one member selected from the group consisting of V (vanadium), W (tungsten), Ta (tantalum), Nb (niobium), and Sn (tin). Base material.
- a novel coated base material that is applicable to various fields and can be mass-produced is provided.
- FIG. 3 is a schematic diagram of a cross section of a coated base material.
- FIG. 3 is a schematic diagram of a cross section of a coated base material. It is a schematic diagram of a film-forming apparatus. It is a graph showing the relationship between electrodeposition time and deposited weight (deposited mass). It is a graph showing the relationship between the number of sample samples and the concentration of aluminum element in the bath liquid.
- the coated base material 1 is formed by covering a base material 5 with a film 3.
- the thickness T of the film 3 is 1 nm or more and less than 800 nm.
- the total elemental percentage of metal elements and O (oxygen) is 70 atm % or more.
- the relative density of the film 3 is 90% or more.
- the coated base material 1 satisfies at least one of the following conditions (1) and (2). By satisfying at least one of condition (1) and condition (2), the functionality of the coated substrate 1 is enhanced.
- Condition (1) The maximum thickness T1max of the coating 3 formed on the edge region S1 of the surface S of the base material 5 is the maximum thickness T1max of the coating 3 formed on the inner region S2 inside the edge region S1 of the surface S. is larger than the thickness T2.
- Condition (2) The maximum thickness T3max of the coating 3 formed on the convexity existing region S3 on the surface S of the base material 5 is the thickness of the coating 3 formed on the convexity non-existence region S4 on the surface S. Larger than T4.
- FIG. 1 shows a schematic cross-sectional view of an example of the coated base material 1. As shown in FIG. Although FIG. 1 shows an example in which the film 3 is formed on one side of the base material 5, the film 3 may be formed on both sides.
- FIG. 2 shows a schematic cross-sectional view of another example of the coating base material 1. Although FIG. 2 shows an example in which the film 3 is formed on one side of the base material 5, the film 3 may be formed on both sides.
- the base material 5 is not particularly limited. In order to improve the adhesion of the film 3 to the base material 5, at least the portion (area) of the base material 5 covered by the film 3 is made of a material that has conductivity and can serve as the negative electrode 7 (cathode). It is preferable. Since the part of the base material 5 covered by the film 3 has conductivity and becomes the negative electrode 7 (cathode), the film 3 can be easily formed on this part by the manufacturing method described below.
- the surface portion of the base material 5 may be made of a material that has conductivity and can serve as the negative electrode 7.
- the entire base material 5 may be made of a material that can serve as the negative electrode 7.
- iron-based alloys and carbon are preferably used as the material that can become the negative electrode 7, for example.
- iron alloys include Fe-Ni-Cr alloy (stainless steel), Fe-Ni alloy (permalloy), Fe-Si alloy (silicon iron), Fe-Si-Al alloy (sendust), and Fe- Preferred examples include one or more selected from Ni-Mo (supermalloy), Fe-Co alloy (permendur), and Fe-C-B alloy (amorphous).
- the thickness T of the film 3 is the shortest distance from a point on the surface of the film 3 to the surface S of the base material 5.
- the thickness T of the film 3 is 1 nm or more, preferably 10 nm or more, and more preferably 50 nm or more, from the viewpoint of developing a function depending on the material of the film 3.
- the thickness is less than 800 nm, preferably 500 nm or less, and more preferably 200 nm or less.
- the thickness T of the film 3 is 1 nm or more and less than 800 nm, preferably 10 nm or more and 500 nm or less, and more preferably 50 nm or more and 200 nm or less.
- the thickness T of the coating 3 is not constant, the requirements for the thickness T are satisfied as long as the thickness T of at least a portion of the coating 3 is within the above-mentioned range.
- the thickness of the film 3 can be determined by FIB-SEM observation.
- Condition (1) is such that the maximum thickness T1max of the film 3 formed on the edge region S1 of the surface S of the base material 5 is such that the maximum thickness T1max of the film 3 formed on the inner region S2 inside the edge region S1 of the surface S is The condition is that the thickness is larger than the thickness T2 of No. 3.
- the maximum thickness T1max of the coating 3 formed on the edge region S1 is the maximum value of the thickness T1 of the coating 3 formed on the edge region S1.
- the edge area S1 is not particularly limited as long as it is an edge of the surface S.
- the edge region S1 is, for example, a region within a radius of 5 mm centered on the end SE of the surface S of the base material 5 in the cross-sectional view.
- the edge area S1 is an area surrounded by a dashed line.
- the maximum thickness T1max is the thickness T1 at the end SE.
- the maximum thickness T1max is not particularly limited.
- the maximum thickness T1max is, for example, preferably 10 nm or more and 1000 nm or less, more preferably 50 nm or more and 800 nm or less, and even more preferably 100 nm or more and 500 nm or less.
- the thickness T2 is not particularly limited as long as it is smaller than the maximum thickness T1max.
- the thickness T2 is, for example, preferably 1 nm or more and 800 nm or less, more preferably 10 nm or more and 500 nm or less, and even more preferably 50 nm or more and 200 nm or less.
- the maximum thickness T1max of the coating 3 formed on the edge region S1 is greater than the thickness T2 of the coating 3 formed on the inner region S2 from the viewpoint of increasing the functionality of the coating base material 1. It is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more.
- the thickness T2 is not uniform, this relationship is satisfied if the maximum thickness T1max is larger than the thickness T2 by a predetermined percentage or more using the value of the thickness T2 in at least a part of the inner region S2. It turns out.
- the upper limit of the ratio of the maximum thickness T1max to the thickness T2 is not limited, in condition (1), the maximum thickness T1max is preferably 400% or less of the thickness T2.
- the thickness T of the coating 3 decreases from the region of the maximum thickness T1max of the coating 3 formed on the edge region S1 toward the inner region S2. Incidentally, irregularities of 10% or less of the maximum thickness T1max are not considered.
- the influence of residual stress generated at the interface of the base material 5 can be alleviated over a wide area.
- the condition (1) regarding the thickness T of the coating 3 is determined by FIB-SEM observation of a cross section of the coated substrate 1 in a direction perpendicular to the surface S of the substrate 5.
- Condition (2) is that the maximum thickness T3max of the coating 3 formed on the convexity existing region S3 of the surface S of the base material 5 is equal to the maximum thickness T3max of the coating 3 formed on the convexity non-existence region S4 of the surface S.
- the condition is that the thickness is greater than the thickness T4.
- the maximum thickness T3max of the coating 3 formed on the convex portion existing region S3 is the maximum value of the thickness T3 of the coating 3 formed on the convex portion existing region S3.
- the shape, size, and number of the convex portions 12 are not particularly limited.
- the film 3 formed on the convex portion existing region S3 related to one convex portion 12 and the adjacent convex portion non-existent region S4 are If condition (2) is satisfied in the formed film 3, condition (2) regarding the thickness T of the film 3 is satisfied.
- the convex portion 12 may be, for example, chevron-shaped, protruding, needle-shaped, or columnar.
- the maximum height h of the convex portion 12 is not particularly limited, but is preferably, for example, 100 nm or more and 10 mm or less, more preferably 500 nm or more and 5 mm or less, and even more preferably 1000 nm or more and 2 mm or less.
- the maximum height h of the convex portion 12 means the height based on the surface S of the base material 5 in the convex portion non-existing region S4.
- the area occupied by the convex portion 12 when viewed from vertically above the base material 5 is not particularly limited, but is preferably, for example, 10 ⁇ m 2 or more and 100 mm 2 or less, more preferably 100 ⁇ m 2 or more and 10 mm 2 or less, and 500 ⁇ m 2 or more and 1 mm 2 or less. The following are more preferable.
- the maximum thickness T3max is not particularly limited.
- the maximum thickness T3max is, for example, preferably 10 nm or more and 1000 nm or less, more preferably 50 nm or more and 800 nm or less, and even more preferably 100 nm or more and 500 nm or less.
- the thickness T4 is not particularly limited as long as it is smaller than the maximum thickness T3max.
- the thickness T4 is, for example, preferably 1 nm or more and 800 nm or less, more preferably 10 nm or more and 500 nm or less, and even more preferably 50 nm or more and 200 nm or less.
- the maximum thickness T3max of the coating 3 formed on the convex portion existing region S3 is the maximum thickness T3max of the coating formed on the convex portion non-existing region S4 from the viewpoint of increasing the functionality of the coating base material 1. It is preferably 10% or more larger than the thickness T4 of No. 3, more preferably 20% or more, and even more preferably 30% or more. If the thickness T4 is not uniform, using the value of the thickness T4 in at least a part of the convex portion non-existing region S4, if the maximum thickness T3max is larger than the thickness T4 by a predetermined percentage or more, this relationship is established. This means that it satisfies the following.
- the maximum thickness T3max is preferably 400% or less of the thickness T4.
- the thickness T of the film 3 decreases from the maximum thickness T3max of the film 3 formed on the convex part existing region S3 toward the convex part non-existent region S4. .
- irregularities of 10% or less of the maximum thickness T3max are not considered. With this structure, the influence of residual stress generated at the interface of the base material 5 can be alleviated over a wide area.
- condition (2) regarding the thickness T of the coating 3 is determined by FIB-SEM observation of a cross section of the coated substrate 1 in a direction perpendicular to the surface S of the substrate 5.
- Elemental percentage of C (carbon) The elemental percentage of C (carbon) when the film 3 is measured by X-ray photoelectron spectroscopy (XPS method) suppresses crystal grain growth in the film 3, and From the viewpoint of stabilizing the properties, the content is 0.1 atm% or more, preferably 0.5 atm% or more, and more preferably 1 atm% or more. On the other hand, from the viewpoint of making the film 3 function sufficiently as an inorganic film, the content is less than 20 atm%, preferably 15 atm% or less, and more preferably 10 atm% or less.
- the elemental percentage of C (carbon) is 0.1 atm% or more and less than 20 atm%, preferably 0.5 atm% or more and 15 atm% or less, and more preferably 1 atm% or more and 10 atm% or less.
- the composition of the film 3 is not constant, if the composition of at least a part of the film 3 is within the above-mentioned range, the requirements for the element percentage of C (carbon) are satisfied.
- Composition analysis by X-ray photoelectron spectroscopy can be performed using an X-ray photoelectron spectrometer. The measurement conditions are that the X-ray source is K alpha rays of aluminum metal, the beam diameter is 100 ⁇ m, and the X-ray incident angle to the surface to be analyzed is 45°, and the measurement can be performed by scanning the cross section.
- the total element percentage of metal elements and O (oxygen) is From the viewpoint of fully functioning as an inorganic film, the content is 70 atm% or more, preferably 80 atm% or more, and more preferably 90 atm% or more.
- the upper limit of the total element percentage of metal elements and O (oxygen) is a value obtained by subtracting the element percentage (atm %) of C (carbon) from 100 atm %. In the case where the composition of the coating 3 is not constant, if the composition of at least a portion of the coating 3 is within the above-mentioned range, the requirements for the total element percentage of the metal element and O (oxygen) are satisfied.
- the relative density of film 3 is 90% or more, preferably 95% or more, and more preferably 98% or more, from the viewpoint of fully exhibiting the function of film 3.
- the relative density of the coating 3 may be 100%.
- the relative density of the film 3 is determined by the following method. A cross-sectional TEM image of the film 3 cut in the film thickness direction is obtained. The area of the pores is measured in a field of view of 300 nm in length and 1000 nm in width.
- the relative density (%) is determined from the following equation (1).
- the average value of the relative densities of the 10 visual fields is the relative density of the film 3.
- Relative density (%) ⁇ (S1-S2)/S1 ⁇ 100 (1)
- S1 is the area (nm 2 ) of a visual field of 300 nm long x 1000 nm wide
- S2 is the total area (nm 2 ) of pores in the visual field of 300 nm long x 1000 nm wide.
- the film 3 is preferably amorphous. Confirmation that it is amorphous can be performed using a TEM image. Since the film 3 is amorphous, it can be expected to exhibit unique functionality such as no crystal grains falling off and smoothing of the outermost surface due to uniform film growth.
- the element percentage of the halogen element is preferably 0.1 atm% or more, more preferably 0.3 atm% or more, More preferably, it is 0.5 atm% or more.
- the upper limit of the element percentage of the halogen element is 3 atm % or less. Since the halogen element is contained in a small amount in the film 3, the oxide film existing on the surface S of the base material 5 is removed by the action of the halogen element, resulting in a structure in which the film 3 and the base material 5 are in direct contact with each other. It is considered that the adhesion between the base material 5 and the film 3 is ensured.
- the metal element is not particularly limited. From the viewpoint of making the film 3 function as a high-quality protective film for the base material 5, the metal elements include Al (aluminum), Ti (titanium), Mo (molybdenum), Cr (chromium), Mn (manganese), and Fe (iron). , Co (cobalt), Ni (nickel), Zr (zirconium), V (vanadium), W (tungsten), Ta (tantalum), Nb (niobium), and Sn (tin). It is preferable that there be more than one species.
- a preferred manufacturing method is a method for manufacturing the coated substrate 1 using a bath liquid 2 using an organic solvent as a solvent.
- the bath liquid 2 has a water content of less than 1% by mass, contains at least one metal element, and contains at least one halogen element.
- the film 3 is formed on the base material 5 on the negative electrode 7 side (cathode side) by applying a voltage while the base material 5 is immersed in the bath liquid 2.
- oxidation of the base material 5 can be suppressed more than by electrodepositing on the positive electrode 6 side (anode side).
- the bath liquid 2 uses an organic solvent as a solvent.
- (1.1) Moisture Content From the viewpoint of ensuring the homogeneity of the film 3 and suppressing oxidation of the base material 5, the water content of the bath liquid 2 is set to be less than 1% by mass. The moisture content is preferably less than 0.5% by mass, more preferably less than 0.1% by mass. The moisture content may be 0% by mass. The water content of the bath liquid 2 can be determined by GC-MS analysis.
- the bath liquid 2 contains at least one metal element.
- the metal element is not particularly limited. From the viewpoint of making the film 3 function as a high-quality protective film for the base material 5, the metal elements include Al (aluminum), Ti (titanium), Mo (molybdenum), Cr (chromium), Mn (manganese), and Fe (iron). , Co (cobalt), Ni (nickel), Zr (zirconium), V (vanadium), W (tungsten), Ta (tantalum), Nb (niobium), and Sn (tin). It is preferable that there be more than one species. In the manufacturing method of the present disclosure, an oxide film, which is the film 3, is formed depending on the metal element in the bath liquid 2.
- the metal elements contained in the bath liquid 2 may be supplied into the bath liquid 2 by elution from the positive electrode 6 (anode).
- the positive electrode 6 anode
- the positive electrode 6 is at least one electrode selected from an Al electrode, a Ti electrode, and a Mo electrode.
- the metal element in the bath liquid 2 may be supplied from a metal alkoxide and/or an inorganic metal compound.
- the metal element When the metal element is supplied by dissolving a metal alkoxide and/or an inorganic metal compound, it is possible to handle elements that are difficult to elute and supply from the positive electrode 6 (anode). Moreover, in this case, it becomes possible to form a film in which a plurality of metal elements are combined and the composition ratio is controlled.
- the metal alkoxide include aluminum alkoxide, titanium alkoxide, and molybdenum alkoxide.
- aluminum alkoxide include aluminum trialkoxide.
- Examples of aluminum trialkoxides include aluminum tripropoxide (e.g., aluminum triisopropoxide, aluminum tri-n-propoxide), aluminum triethoxide, aluminum tributoxide (e.g., aluminum trisec-butoxide, aluminum tri-n- butoxide), etc.
- Examples of the titanium alkoxide include titanium trialkoxide and titanium tetraalkoxide, with titanium tetraalkoxide being preferred.
- titanium tetraalkoxide examples include titanium tetrapropoxide (e.g., titanium tetraisopropoxide, titanium tetra n-propoxide, etc.), titanium tetramethoxide, titanium tetraethoxide, titanium tetrabutoxide (e.g., titanium tetraisobutoxide). , titanium tetra n-butoxide, etc.), titanium tetrapentoxide, titanium tetrahexoxide, titanium tetra(2-ethylhexoxide), and the like.
- the inorganic metal compound examples include aluminum chloride, aluminum bromide, aluminum iodide, and titanium iodide.
- the concentration of the metal element in the bath liquid 2 is not particularly limited.
- the concentration of the metal element in the bath liquid 2 is preferably 1 ppm or more and 100 ppm or less, more preferably 3 ppm or more and 10 ppm or less, and even more preferably 4 ppm or more and 6 ppm or less, from the viewpoint of forming a good film 3.
- ppm is "parts per million” and "mg/L”.
- the concentration of the metal elements mentioned above means the total concentration of the plurality of metal elements.
- the concentration of metal elements in the bath liquid 2 can be measured by ICP-MS analysis.
- the bath liquid 2 contains at least one type of halogen element.
- a halogen element By containing a halogen element in the bath liquid 2, film formation is performed at a practical speed, and the film 3 tends to be homogeneous.
- the halogen element is not particularly limited. From the viewpoint of causing the organic electrochemical reaction to proceed rapidly and allowing the film 3 to function as a high-quality protective film for the base material 5, the halogen element is selected from the group consisting of Cl (chlorine), Br (bromine), and I (iodine). It is preferable that at least one kind is selected.
- the concentration of the halogen element in the bath liquid 2 is not particularly limited.
- the concentration of the halogen element is preferably 1 ppm or more and 20,000 ppm or less, and 5 ppm or more, from the viewpoint of controlling the reaction rate appropriately, controlling the homogeneity and thickness T of the film 3, and suppressing peeling of the film 3. It is more preferably 2000 ppm or more, and even more preferably 10 ppm or more and 100 ppm or less. Note that "ppm” is "parts per million” and "mg/L".
- the concentration of the halogen element in the bath liquid 2 can be determined by the amount of halogen element added at the time of bath preparation or by ICP-MS analysis of the bath liquid.
- the solvent contains at least one selected from the group consisting of ketones and nitriles. It is presumed that by containing a ketone or a nitrile in the solvent, a condensation reaction occurs on the electrode surface (cathode surface), making electrodeposition possible. Furthermore, it is thought that by including a ketone in the solvent, ketoenol tautomerism occurs in the presence of a halogen, thereby improving the reactivity of the bath liquid 2.
- the ketone include acetone, methyl ethyl ketone (MEK), 1-hexanone, 2-hexanone, 4-heptanone, 2-heptanone (methyl amyl ketone), 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, Examples include diisobutyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, phenylacetone, acetophenone, methyl naphthyl ketone, cyclohexanone (CHN), methylcyclohexanone, and the like.
- acetone and methyl ethyl ketone are preferable as the ketone from the viewpoint that the film 3 is formed particularly well.
- Nitrile Nitrile is an organic solvent containing a nitrile group (-CN) in its structure.
- the nitrile include acetonitrile, propionitrile, valeronitrile, butyronitrile, and the like. Among these, acetonitrile is preferable as the nitrile from the viewpoint that the film 3 is formed particularly well.
- Base material 5 Regarding the “base material 5", the explanation in the column “(1) Base material 5" in the above “1. Covered base material 1" is applied as is.
- the positive electrode 6 and the negative electrode 7 are immersed in the bath liquid 2, and a potential gradient is generated between the two electrodes.
- the positive electrode 6 any known conductive substrate can be used.
- the positive electrode 6 is preferably at least one electrode selected from an Al electrode, a Ti electrode, and a Mo electrode.
- the shape, thickness, size, etc. of the positive electrode 6 are not particularly limited.
- the positive electrode 6 may have a foil shape, a plate shape, a foam shape, a nonwoven fabric shape, a mesh shape, a felt shape, or an expanded shape, for example. It is preferable that the positive electrode 6 and the negative electrode 7 are arranged facing each other.
- the positive electrode 6 and the negative electrode 7 are connected to a DC power source, and a potential gradient can be generated between the positive electrode 6 and the negative electrode 7 by the DC power source.
- a voltage For example, a constant voltage
- the potential gradient generated between the two electrodes is preferably 10 V or more and 300 V or less, more preferably 20 V or more and 100 V or less, and even more preferably 60 V or more and 80 V or less, from the viewpoint of forming a film at a practical speed.
- the voltage application time is not particularly limited.
- the application time is, for example, preferably 10 seconds or more and 300 seconds or less, more preferably 30 seconds or more and 240 seconds or less, and even more preferably 60 seconds or more and 180 seconds or less. Note that the voltage may not be a constant voltage but may vary in magnitude.
- the amount of carbon in the film 3 may be reduced by heat treatment and/or light irradiation.
- the treatment temperature of the heat treatment is not particularly limited. From the viewpoint of efficiently reducing the amount of carbon, the temperature is preferably 100°C or more and 1000°C or less, more preferably 300°C or more and 800°C or less, and even more preferably 500°C or more and 600°C or less.
- the treatment time of the heat treatment is not particularly limited.
- the time is preferably 1 minute or more and 60 minutes or less, more preferably 5 minutes or more and 45 minutes or less, and even more preferably 10 minutes or more and 30 minutes or less.
- the wavelength of light in light irradiation is not particularly limited. From the viewpoint of efficiently reducing the amount of carbon, the wavelength of the light is preferably 250 nm or more and 1100 nm or less, more preferably 300 nm or more and 800 nm or less, and even more preferably 400 nm or more and 500 nm or less.
- the light irradiation time is not particularly limited.
- the time is preferably 3 seconds or more and 120 seconds or less, more preferably 5 seconds or more and 60 seconds or less, and even more preferably 10 seconds or more and 30 seconds or less. Note that the decrease in the amount of carbon in the film 3 can be confirmed by XPS analysis.
- the coating of the edge region S1 and the convex portion existing region S3 that are particularly likely to come into contact with the surrounding environment is By selectively forming a thick film of No. 3, excellent functionality and/or durability can be achieved.
- a novel coated base material 1 that is applicable to various fields and can be mass-produced is provided.
- the coated base material 1 of this embodiment can be formed without using expensive raw materials or with a very small amount of expensive raw materials, so it is advantageous in terms of cost.
- the coated base material 1 of this embodiment forms the coating 3 without necessarily performing post-treatment such as heat treatment or light irradiation, the options for the material of the base material 5 and the shape of the base material 5 can be expanded. I can do it.
- Example 1 solvent: MEK, positive electrode 6: aluminum
- a film forming apparatus 11 shown in FIG. 3 was used.
- An aluminum wire was used as the positive electrode 6.
- a stainless steel plate was used as the negative electrode 7.
- the negative electrode 7 is a base material 5 on which a film 3 is formed.
- Methyl ethyl ketone (MEK) was used as the solvent for bath liquid 2.
- 600 ppm of iodine as a halogen was dissolved.
- 80 V was applied between the positive electrode 6 and the negative electrode 7 for 3 minutes.
- the relative density of the film 3 was determined by the following method, the relative density was 100%.
- the relative density of film 3 was determined by the following method. A cross-sectional TEM image of the film 3 cut in the film thickness direction was obtained. The area of the pores was measured in a field of view of 300 nm in length and 1000 nm in width. The relative density (%) was determined from the following equation (1). The average value of the relative densities of the 10 visual fields is the relative density of the film 3.
- the thickness of the film 3 is smaller than 300 nm vertically, the measurement shall be performed with a field of view that matches the thickness of the film 3.
- Relative density (%) ⁇ (S1-S2)/S1 ⁇ 100(1) (In the formula, S1 is the area (nm 2 ) of a visual field of 300 nm long x 1000 nm wide, and S2 is the total area (nm 2 ) of pores in the visual field of 300 nm long x 1000 nm wide.)
- Example 2 (solvent: acetone, positive electrode 6: aluminum) Acetone was used as a solvent for bath liquid 2. In the bath liquid 2, 14 ppm of iodine as a halogen was dissolved. The experiment was carried out in the same manner as in Example 1 in other respects.
- the cross section of the negative electrode 7 was observed using FIB-SEM, it was found that a 130 nm thick film 3 was formed on the surface of the base material 5. Analysis by XPS revealed that this film 3 was aluminum oxide. Further, the elemental percentage of carbon element in the film 3 was 6.5 atm%, and the total elemental percentage of aluminum element and oxygen element was 93.3 atm%. Further, the elemental percentage of iodine in this film 3 was 0.1 atm%.
- Example 3 (solvent: MEK, positive electrode 6: titanium) A titanium wire was used as the positive electrode 6. The experiment was carried out in the same manner as in Example 1 in other respects.
- the cross section of the negative electrode 7 was observed using FIB-SEM, it was found that a 90 nm thick film 3 was formed on the surface of the base material 5.
- Analysis by XPS revealed that this film 3 was a titanium oxide. Further, the elemental percentage of carbon element in the film 3 was 24.6 atm%, and the total elemental percentage of titanium element and oxygen element was 78.7 atm%. Further, the elemental percentage of iodine in this film 3 was 0.3 atm%.
- Example 4 (solvent: acetone, positive electrode 6: titanium) Acetone was used as a solvent for bath liquid 2. In the bath liquid 2, 2400 ppm of iodine as a halogen was dissolved. The experiment was conducted in the same manner as in Example 3 in other respects. When the cross section of the negative electrode 7 was observed using FIB-SEM, it was found that a 500 nm thick film 3 was formed on the surface of the base material 5. Analysis by XPS revealed that this film 3 was a titanium oxide. Further, the elemental percentage of carbon element in the film 3 was 9.2 atm%, and the total elemental percentage of titanium element and oxygen element was 83.7 atm%.
- the elemental percentage of iodine in this film 3 was 0.4 atm %. Further, in a cross-sectional TEM image taken in the film thickness direction of the film 3, no crystal grains were observed, so it was confirmed that the film 3 was amorphous. Further, when the relative density of the film 3 was determined by the above-mentioned method, the relative density was 100%.
- Example 5 (solvent: MEK, positive electrode 6: molybdenum) A molybdenum wire was used as the positive electrode 6. The experiment was carried out in the same manner as in Example 1 in other respects.
- the cross section of the negative electrode 7 was observed using FIB-SEM, it was found that a 160 nm thick film 3 was formed on the surface of the base material 5.
- Analysis by XPS revealed that this film 3 was molybdenum oxide.
- the elemental percentage of carbon element in the film 3 was 14.8 atm%, and the total elemental percentage of molybdenum element and oxygen element was 78.7 atm%. Further, the elemental percentage of iodine in this film 3 was less than 0.1 atm % (below the detection limit).
- Example 6 (solvent: acetone, positive electrode 6: molybdenum) Acetone was used as a solvent for bath liquid 2. In the bath liquid 2, 2400 ppm of iodine as a halogen was dissolved. The experiment was conducted in the same manner as in Example 5 except for the above. When the cross section of the negative electrode 7 was observed using FIB-SEM, it was found that a 480 nm thick film 3 was formed on the surface of the base material 5. Analysis by XPS revealed that this film 3 was molybdenum oxide. Further, the elemental percentage of carbon element in the film 3 was 12.7 atm%, and the total elemental percentage of molybdenum element and oxygen element was 78.0 atm%.
- the elemental percentage of iodine in this film 3 was less than 0.1 atm % (below the detection limit). Further, in a cross-sectional TEM image taken in the film thickness direction of the film 3, no crystal grains were observed, so it was confirmed that the film 3 was amorphous. Further, when the relative density of the film 3 was determined by the above-mentioned method, the relative density was 100%.
- Example 7 (solvent: acetonitrile, positive electrode 6: aluminum) Acetonitrile was used as the solvent for bath liquid 2.
- 2400 ppm of iodine as a halogen was dissolved.
- the experiment was carried out in the same manner as in Example 1 in other respects.
- FIB-SEM When the cross section of the negative electrode 7 was observed using FIB-SEM, it was found that a 140 nm thick film 3 was formed on the surface of the base material 5. Analysis by XPS revealed that this film 3 was aluminum oxide. Oxygen, which was not present in the bath liquid 2, was present in the film 3. This is presumed to be oxygen derived from water contained in the bath liquid 2 or water absorbed from the atmosphere.
- the elemental percentage of carbon element in the film 3 was 9.8 atm%, and the total elemental percentage of aluminum element and oxygen element was 90.1 atm%. Further, the elemental percentage of iodine in this film 3 was 0.1 atm%. Further, in a cross-sectional TEM image taken in the film thickness direction of the film 3, no crystal grains were observed, so it was confirmed that the film 3 was amorphous. Further, when the relative density of the film 3 was determined by the above-mentioned method, the relative density was 100%.
- Example 1-7 A cross section of film 3 in Example 1-7 was observed by FIB-SEM.
- the maximum thickness T1max of the film 3 formed on the edge region S1 of the surface S of the base material 5 is the maximum thickness T1max of the film 3 formed on the inner region S2 inside the edge region S1 of the surface S. It was larger than the thickness T2 of the formed film 3.
- the maximum thickness T1max of the coating 3 formed on the edge region S1 was 10% or more larger than the thickness T2 of the coating 3 formed on the inner region S2.
- the thickness T of the film 3 decreased from the region of the maximum thickness T1max of the film 3 formed on the edge region S1 toward the inner region S2.
- Example 1 where the metal element is supplied from the metal alkoxide into the bath liquid (solvent: acetone, metal alkoxide: aluminum triisopropoxide)
- a film forming apparatus 11 shown in FIG. 3 was used.
- a carbon electrode was used as the positive electrode 6.
- a stainless steel plate was used as the negative electrode 7.
- the negative electrode 7 is a base material 5 on which a film 3 is formed on the surface S thereof.
- Acetone was used as the solvent for bath liquid 2.
- 16 mg/L (16 ppm) of aluminum triisopropoxide was dissolved, and 2400 mg/L (2400 ppm) of iodine as a halogen was dissolved.
- Example 9 (solvent: MEK, metal alkoxide: aluminum triisopropoxide) Methyl ethyl ketone (MEK) was used as a solvent for bath liquid 2.
- MEK Methyl ethyl ketone
- Example 10 (solvent: acetone, metal alkoxide: titanium tetraisopropoxide) Titanium tetraisopropoxide was used in place of aluminum triisopropoxide. The experiment was conducted in the same manner as in Example 8 except for the above. When the cross section of the negative electrode 7 was observed using FIB-SEM, it was found that a film 3 was formed on the surface S of the base material 5. Analysis by XPS revealed that this film 3 was a titanium oxide. Further, the elemental percentage of carbon element in the film 3 was 8.8 atm%, and the total elemental percentage of titanium element and oxygen element was 86.1 atm%. Moreover, the elemental percentage of iodine in this film 3 was 1.3 atm %.
- Example 11 (solvent: acetone, metal alkoxide: titanium tetra n-propoxide) Titanium tetra-n-propoxide was used in place of aluminum triisopropoxide.
- the experiment was conducted in the same manner as in Example 8 except for the above.
- FIB-SEM cross section of the negative electrode 7 was observed using FIB-SEM, it was found that a film 3 was formed on the surface S of the base material 5.
- Analysis by XPS revealed that this film 3 was a titanium oxide.
- the elemental percentage of carbon element in the film 3 was 9.5 atm%, and the total elemental percentage of titanium element and oxygen element was 85.9 atm%.
- the elemental percentage of iodine in this film 3 was 0.9 atm%.
- Example 8-11 A cross section of film 3 in Example 8-11 was observed by FIB-SEM.
- the maximum thickness T1max of the coating 3 formed on the edge region S1 of the surface S of the base material 5 is the same as that of the film 3 formed on the inner region S2 inside the edge region S1 of the surface S. It was larger than the thickness T2 of the formed film 3.
- the maximum thickness T1max of the coating 3 formed on the edge region S1 was 10% or more larger than the thickness T2 of the coating 3 formed on the inner region S2.
- the thickness T of the coating 3 decreased from the portion of the coating 3 formed on the edge region S1 where the maximum thickness T1max was toward the inner region S2.
- a film forming apparatus 11 shown in FIG. 1 was used.
- An aluminum wire was used as the positive electrode 6.
- a stainless steel plate was used as the negative electrode 7.
- the negative electrode 7 is a base material 5 on which a film 3 is formed on the surface S thereof.
- Various solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and diisobutyl ketone were used as the solvent for bath liquid 2.
- MEK methyl ethyl ketone
- diisobutyl ketone were used as the solvent for bath liquid 2.
- 2100 mg/L (2100 ppm) of iodine as a halogen was dissolved.
- the graph of FIG. 4 shows the relationship between the application time (electrodeposition time) and the deposited weight (deposited mass) for each solvent.
- the deposited weight is the weight of the film formed. From the graph of FIG. 4, it was confirmed that the deposited weight tended to increase as the electrodeposition time increased. Moreover, from the graph of FIG. 4, it was confirmed that the smaller the number of carbon atoms in the hydrocarbon group of the solvent, the faster the precipitation rate.
- the first sample was pulled out of the bath liquid 2, a new stainless steel plate was placed in the bath liquid 2, and the voltage was applied in the same manner as the first sample to prepare a second sample. In the same manner, the third and subsequent samples were successively produced.
- the results are shown in Table 1.
- the evaluation in Table 1 is as follows. A: Film 3 was formed. The adhesion between the film 3 and the base material 5 was good. B: Film 3 was formed. The adhesion between the film 3 and the base material 5 was slightly poor, and the film 3 tended to peel off.
- Example 8 Examination of the types of base materials 5 Formation of the film 3 was attempted using various base materials 5. In place of the stainless steel plate as the negative electrode 7 in Example 1, a permalloy plate, a titanium plate, a copper plate, and a carbon plate were used, respectively. The experiment was carried out in the same manner as in Example 1 in other respects. A stable film 3 was formed on any of the base materials 5. Therefore, it was confirmed that stable film 3 could be formed regardless of the type of base material 5.
- the base material is covered with a film,
- the thickness of the film is 1 nm or more and less than 800 nm,
- the total elemental percentage of metal elements and O (oxygen) is 70 atm% or more,
- the relative density of the film is 90% or more,
- a coated base material that satisfies at least one of the following conditions (1) and (2).
- Condition (1) The maximum thickness of the film formed on the edge region of the surface of the base material is greater than the thickness of the film formed on the inner region of the surface, which is inside the edge region. big.
- Condition (2) The maximum thickness of the film formed on the region where the convex portion is present on the surface of the base material is greater than the thickness of the film formed on the region where the convex portion is not present on the surface. .
- the maximum thickness of the coating formed on the edge region is 10% or more greater than the thickness of the coating formed on the inner region.
- the coated base material according to any one of the items.
- the maximum thickness of the film formed on the region where the convex portion is present is 10% or more greater than the thickness of the film formed on the region where the convex portion is not present, [1 ] to [5].
- the thickness of the coating decreases from the maximum thickness portion of the coating formed on the edge region toward the inner region.
- the thickness of the coating decreases from the maximum thickness portion of the coating formed on the region where the convex portion exists toward the region where the convex portion does not exist, [1] The coated base material according to any one of [7].
- the metal elements include Al (aluminum), Ti (titanium), Mo (molybdenum), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Zr (zirconium), Any one of [1] to [8], which is at least one member selected from the group consisting of V (vanadium), W (tungsten), Ta (tantalum), Nb (niobium), and Sn (tin).
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Abstract
La présente invention concerne un nouveau matériau de base revêtu qui est applicable à divers domaines, tout en étant capable d'être produit en masse. Un matériau de base revêtu (1) selon la présente invention est obtenu en recouvrant un matériau de base (5) avec un film de revêtement (3). L'épaisseur du film de revêtement (3) est comprise entre 1nm et 800 nm. Le pourcentage élémentaire total d'éléments métalliques et d'oxygène (O) dans le film de revêtement (3) est supérieur ou égal à 70% en pourcentage atomique tel que déterminé par spectroscopie photoélectronique à rayons X. Le film de revêtement (3) a une densité relative de 90% ou plus. Ce matériau de base revêtu (1) satisfait la condition (1) et/ou la condition (2) décrites ci-dessous. Condition (1): L'épaisseur maximale du film de revêtement (3) formé sur une région de bord de la surface du matériau de base (5) est supérieure à l'épaisseur du film de revêtement (3) formé sur une région interne de la surface, la région interne étant à l'intérieur de la région de bord. Condition (2): L'épaisseur maximale du film de revêtement (3) formé sur une région de la surface du matériau de base (5), la région ayant une saillie, est supérieure à l'épaisseur du film de revêtement (3) formé sur une autre région de la surface, l'autre région n'ayant pas de saillie.
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JPH0248103A (ja) * | 1989-06-20 | 1990-02-16 | Sumitomo Electric Ind Ltd | 被覆超硬合金工具及びその製造法 |
JPH11264066A (ja) * | 1998-03-16 | 1999-09-28 | Hitachi Tool Eng Ltd | 被覆硬質工具 |
JP2000117509A (ja) * | 1998-10-14 | 2000-04-25 | Mitsubishi Materials Corp | 耐摩耗性の優れた表面被覆超硬合金製スローアウエイ切削チップ |
JP2010105979A (ja) * | 2008-10-31 | 2010-05-13 | General Electric Co <Ge> | 金属酸化物コーティング |
JP2012233223A (ja) * | 2011-04-28 | 2012-11-29 | Waseda Univ | 電気めっき組成物、および、電気めっき液 |
US20140178659A1 (en) * | 2012-12-26 | 2014-06-26 | Shanghua Wu | Al2o3 or al2o3-contained multilayer coatings for silicon nitride cutting tools by physical vapor deposition and methods of making the same |
JP2020006487A (ja) * | 2018-07-10 | 2020-01-16 | 三菱マテリアル株式会社 | 硬質被覆層が優れた耐チッピング性を発揮する表面切削工具 |
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2023
- 2023-07-20 WO PCT/JP2023/026615 patent/WO2024029363A1/fr active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0248103A (ja) * | 1989-06-20 | 1990-02-16 | Sumitomo Electric Ind Ltd | 被覆超硬合金工具及びその製造法 |
JPH11264066A (ja) * | 1998-03-16 | 1999-09-28 | Hitachi Tool Eng Ltd | 被覆硬質工具 |
JP2000117509A (ja) * | 1998-10-14 | 2000-04-25 | Mitsubishi Materials Corp | 耐摩耗性の優れた表面被覆超硬合金製スローアウエイ切削チップ |
JP2010105979A (ja) * | 2008-10-31 | 2010-05-13 | General Electric Co <Ge> | 金属酸化物コーティング |
JP2012233223A (ja) * | 2011-04-28 | 2012-11-29 | Waseda Univ | 電気めっき組成物、および、電気めっき液 |
US20140178659A1 (en) * | 2012-12-26 | 2014-06-26 | Shanghua Wu | Al2o3 or al2o3-contained multilayer coatings for silicon nitride cutting tools by physical vapor deposition and methods of making the same |
JP2020006487A (ja) * | 2018-07-10 | 2020-01-16 | 三菱マテリアル株式会社 | 硬質被覆層が優れた耐チッピング性を発揮する表面切削工具 |
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