JP5890394B2 - 三価クロムめっき液 - Google Patents
三価クロムめっき液 Download PDFInfo
- Publication number
- JP5890394B2 JP5890394B2 JP2013507708A JP2013507708A JP5890394B2 JP 5890394 B2 JP5890394 B2 JP 5890394B2 JP 2013507708 A JP2013507708 A JP 2013507708A JP 2013507708 A JP2013507708 A JP 2013507708A JP 5890394 B2 JP5890394 B2 JP 5890394B2
- Authority
- JP
- Japan
- Prior art keywords
- plating solution
- trivalent chromium
- chromium plating
- compound
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000007747 plating Methods 0.000 title claims description 171
- 239000011651 chromium Substances 0.000 title claims description 97
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 95
- 229910052804 chromium Inorganic materials 0.000 title claims description 95
- 239000000243 solution Substances 0.000 claims description 98
- 239000002245 particle Substances 0.000 claims description 47
- -1 sulfamate compound Chemical class 0.000 claims description 47
- 239000000919 ceramic Substances 0.000 claims description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000001845 chromium compounds Chemical class 0.000 claims description 6
- 239000006174 pH buffer Substances 0.000 claims description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000006179 pH buffering agent Substances 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 claims description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 2
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 claims description 2
- 230000035939 shock Effects 0.000 claims description 2
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 claims description 2
- 230000002744 anti-aggregatory effect Effects 0.000 claims 1
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000009471 action Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229940063656 aluminum chloride Drugs 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000013011 mating Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003086 Ti–Pt Inorganic materials 0.000 description 1
- XFJRTXJMYXFAEE-UHFFFAOYSA-K [Cr+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O Chemical compound [Cr+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O XFJRTXJMYXFAEE-UHFFFAOYSA-K 0.000 description 1
- NCNKLTFZTZEYLK-AHUNZLEGSA-H [Cr+3].[Cr+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O Chemical compound [Cr+3].[Cr+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O NCNKLTFZTZEYLK-AHUNZLEGSA-H 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- 229960001040 ammonium chloride Drugs 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229940064958 chromium citrate Drugs 0.000 description 1
- 229940076130 chromium gluconate Drugs 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- ANPGUZATXCGJJH-OPDGVEILSA-K chromium(3+);(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Cr+3].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O ANPGUZATXCGJJH-OPDGVEILSA-K 0.000 description 1
- BLSQUKMVYMBIIK-UHFFFAOYSA-H chromium(3+);2,3-dihydroxybutanedioate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O BLSQUKMVYMBIIK-UHFFFAOYSA-H 0.000 description 1
- QYHKPQCMTYXLIA-UHFFFAOYSA-K chromium(3+);2-hydroxyacetate Chemical compound [Cr+3].OCC([O-])=O.OCC([O-])=O.OCC([O-])=O QYHKPQCMTYXLIA-UHFFFAOYSA-K 0.000 description 1
- SWXXYWDHQDTFSU-UHFFFAOYSA-K chromium(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cr+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SWXXYWDHQDTFSU-UHFFFAOYSA-K 0.000 description 1
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- YPHMISFOHDHNIV-FSZOTQKASA-N cycloheximide Chemical compound C1[C@@H](C)C[C@H](C)C(=O)[C@@H]1[C@H](O)CC1CC(=O)NC(=O)C1 YPHMISFOHDHNIV-FSZOTQKASA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- AFAXGSQYZLGZPG-UHFFFAOYSA-N ethanedisulfonic acid Chemical compound OS(=O)(=O)CCS(O)(=O)=O AFAXGSQYZLGZPG-UHFFFAOYSA-N 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical compound OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 102200082816 rs34868397 Human genes 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Pistons, Piston Rings, And Cylinders (AREA)
- Fluid-Damping Devices (AREA)
- Electroplating Methods And Accessories (AREA)
Description
スルホン酸基含有化合物又はその塩の濃度はスルホン酸基基準で0.02〜0.1mol/Lが好ましく、0.04〜0.07mol/Lがより好ましい。
以下の表1に示す成分を水に添加して、同表に示す組成を有する三価のクロムのめっき液を調製した。得られためっき液を用い、同表に示す条件で電解めっきを行った。陽極としては高密度黒鉛板を用いた。陰極としてはS45Cみがき鋼板を用いた。
以下の表1に示す成分を水に添加して、同表に示す組成を有する六価のクロムのめっき液を調製した。得られためっき液を用い、同表に示す条件で電解めっきを行った。陰極は実施例1と同様のものを用いた。陽極としては鉛錫板を用いた。
めっき皮膜の皮膜断面を、レーザー顕微鏡(OLYMPUS社製 LEXTO OLS1100)を用いて400倍の倍率で測定した。
めっき皮膜の皮膜断面を、微小硬さ試験機(ミツトヨ製 HM−103)を用いて、荷重200gf×15secで測定した。
科研式腐食摩耗試験機を用いてめっき皮膜の耐摩耗性を評価した。摩擦の相手となるライナー材として鋳鉄(JIS G 5501−1995に準拠したFC250)を用いた。摩擦試験器における接触荷重は39Nとした。摩擦速度は0.25m/sec、摩擦距離は5400m(=6時間)とした。腐食液として硫酸水溶液(pH=2.0)を用い、1.5ml/minで滴下した。腐食液温度は常温とした。めっき皮膜の摩耗量を測定し、その値を耐摩耗性の指標とした。
めっき物におけるめっき皮膜の面積が1cm2となるようにし、該めっき物を所定のpHに調整された硫酸及び塩酸水溶液(容積1リットル)中に、ビニール製の釣糸で吊り下げた。水溶液の温度を70℃に保ち、水溶液を1時間にわたって攪拌した。その後、水溶液中に溶解したクロムの量をICP発光分析装置(島津製作所社製 ICPS−7510)によって測定し、耐食性の尺度とした。
ここでいう分散度とは、めっき皮膜の断面を観察したときに、単位面積あたりの観察視野に占めるセラミック粒子の面積率のことである。この面積率は次の方法で測定される。すなわち、めっき皮膜の縦断面を、レーザー顕微鏡(OLYMPUS社製 LEXTO OLS1100)を用いて、1000倍の倍率で観察する。そして、30μm四方の枠内に存在するセラミック粒子が占有する面積の比率を、同レーザー顕微鏡を用いて処理計測する。
実施例3で得られためっき物を大気下に400℃で1時間加熱処理を行った。実施例1〜3と同様にしてビッカース硬度を測定したところ1550であり、加熱処理前に比べて高い硬度のめっき皮膜が形成されていることを確認した。
Claims (14)
- 三価クロム化合物、pH緩衝剤(但し、塩化アルミニウムは除く)、アミノカルボン酸化合物、スルファミン酸塩化合物及びアミノカルボニル化合物を含有する水溶液からなり、アミノカルボニル化合物に対するスルファミン酸塩の配合量がモル比で0.4〜1.5である三価クロムめっき液。
- セラミック粒子を更に含有する請求項1に記載の三価クロムめっき液。
- セラミック粒子の凝集防止剤を更に含有する請求項2に記載の三価クロムめっき液。
- 前記三価クロム化合物が、塩化クロム、硝酸クロム、硫酸クロム及びリン酸クロムのうちの少なくとも一種である請求項1ないし3のいずれか一項に記載の三価クロムめっき液。
- 前記pH緩衝剤が、ホウ酸、ホウ酸ナトリウム又はホウ酸カリウムである請求項1ないし4のいずれか一項に記載の三価クロムめっき液。
- 前記アミノカルボン酸化合物が、グリシン又はアラニンである請求項1ないし5のいずれか一項に記載の三価クロムめっき液。
- 前記スルファミン酸塩化合物が、スルファミン酸アンモニウム、スルファミン酸ナトリウム又はスルファミン酸カリウムである請求項1ないし6のいずれか一項に記載の三価クロムめっき液。
- 前記アミノカルボニル化合物が、尿素及びカルバミン酸のうちの少なくとも一種である請求項1ないし7のいずれか一項に記載の三価クロムめっき液。
- 前記セラミック粒子が、20〜100mVのゼータ電位を有するものである請求項2に記載の三価クロムめっき液。
- 前記凝集防止剤が、塩化アルミニウムである請求項3に記載の三価クロムめっき液。
- 摺動部材のめっき液として用いられる請求項1ないし10のいずれか一項に記載の三価クロムめっき液。
- 摺動部材がピストンリング、ロール及びショックアブソーバから選ばれる請求項11に記載の三価クロムめっき液。
- 請求項1ないし12のいずれか一項に記載の三価クロムめっき液を用いるクロムめっき方法。
- 請求項1ないし12のいずれか一項に記載の三価クロムめっき液を用いて形成された皮膜を加熱処理するクロムめっき方法。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4083268A1 (en) | 2021-04-30 | 2022-11-02 | Atotech Deutschland GmbH & Co. KG | Electroplating composition for depositing a chromium or chromium alloy layer on a substrate |
EP4101947A1 (en) | 2021-06-10 | 2022-12-14 | Atotech Deutschland GmbH & Co. KG | Method for electrodepositing a dark chromium layer, substrate comprising same, and electroplating bath thereof |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2014126067A1 (ja) * | 2013-02-13 | 2014-08-21 | 日本化学工業株式会社 | 三価クロムめっき液 |
JP5721766B2 (ja) | 2013-03-29 | 2015-05-20 | 株式会社リケン | 複合硬質クロムめっき皮膜、及びかかる皮膜を被覆した摺動部材 |
CN105506713B (zh) * | 2014-09-25 | 2018-05-08 | 通用电气公司 | 通过电镀形成铬基涂层的方法、所用电解液以及所形成的涂层 |
JP7409998B2 (ja) | 2020-08-27 | 2024-01-09 | 日立Astemo株式会社 | 緩衝器および緩衝器の製造方法 |
WO2024053640A1 (ja) * | 2022-09-07 | 2024-03-14 | 日立Astemo株式会社 | めっき部材およびその製造方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5531122A (en) * | 1978-08-25 | 1980-03-05 | Toyo Soda Mfg Co Ltd | Chrome plating bath |
JPS5531119A (en) * | 1978-08-25 | 1980-03-05 | Toyo Soda Mfg Co Ltd | Chrome plating bath |
JPS62120498A (ja) * | 1985-11-19 | 1987-06-01 | Matsufumi Takatani | 複合クロムめつきおよびめつき方法 |
JPH0995793A (ja) * | 1995-09-29 | 1997-04-08 | Shigeo Hoshino | 熱硬化性を有するクロムめっきを析出する3価クロムめっき浴 |
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2012
- 2012-03-29 WO PCT/JP2012/058300 patent/WO2012133613A1/ja active Application Filing
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5531122A (en) * | 1978-08-25 | 1980-03-05 | Toyo Soda Mfg Co Ltd | Chrome plating bath |
JPS5531119A (en) * | 1978-08-25 | 1980-03-05 | Toyo Soda Mfg Co Ltd | Chrome plating bath |
JPS62120498A (ja) * | 1985-11-19 | 1987-06-01 | Matsufumi Takatani | 複合クロムめつきおよびめつき方法 |
JPH0995793A (ja) * | 1995-09-29 | 1997-04-08 | Shigeo Hoshino | 熱硬化性を有するクロムめっきを析出する3価クロムめっき浴 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4083268A1 (en) | 2021-04-30 | 2022-11-02 | Atotech Deutschland GmbH & Co. KG | Electroplating composition for depositing a chromium or chromium alloy layer on a substrate |
WO2022229373A1 (en) | 2021-04-30 | 2022-11-03 | Atotech Deutschland GmbH & Co. KG | Electroplating composition for depositing a chromium or chromium alloy layer on a substrate |
EP4101947A1 (en) | 2021-06-10 | 2022-12-14 | Atotech Deutschland GmbH & Co. KG | Method for electrodepositing a dark chromium layer, substrate comprising same, and electroplating bath thereof |
WO2022258680A1 (en) | 2021-06-10 | 2022-12-15 | Atotech Deutschland GmbH & Co. KG | Method for electrodepositing a dark chromium layer, substrate comprising same, and electroplating bath thereof |
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JPWO2012133613A1 (ja) | 2014-07-28 |
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