JP7656958B2 - Metal plate having layered double hydroxide on its surface and method for producing same - Google Patents
Metal plate having layered double hydroxide on its surface and method for producing same Download PDFInfo
- Publication number
- JP7656958B2 JP7656958B2 JP2023505484A JP2023505484A JP7656958B2 JP 7656958 B2 JP7656958 B2 JP 7656958B2 JP 2023505484 A JP2023505484 A JP 2023505484A JP 2023505484 A JP2023505484 A JP 2023505484A JP 7656958 B2 JP7656958 B2 JP 7656958B2
- Authority
- JP
- Japan
- Prior art keywords
- layered double
- double hydroxide
- metal
- alloy
- powder
- 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.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 96
- 229910052751 metal Inorganic materials 0.000 title claims description 55
- 239000002184 metal Substances 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000843 powder Substances 0.000 claims description 143
- 239000000758 substrate Substances 0.000 claims description 73
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- 238000000576 coating method Methods 0.000 claims description 47
- 238000000151 deposition Methods 0.000 claims description 44
- 229910021645 metal ion Inorganic materials 0.000 claims description 44
- 230000008021 deposition Effects 0.000 claims description 42
- 239000011777 magnesium Substances 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 37
- 239000000956 alloy Substances 0.000 claims description 35
- 150000004692 metal hydroxides Chemical class 0.000 claims description 35
- 229910045601 alloy Inorganic materials 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000008151 electrolyte solution Substances 0.000 claims description 19
- 229910000838 Al alloy Inorganic materials 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 150000001450 anions Chemical class 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 17
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- -1 permanganate Chemical compound 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 230000005684 electric field Effects 0.000 claims description 12
- 150000004679 hydroxides Chemical class 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 229910018134 Al-Mg Inorganic materials 0.000 claims description 4
- 229910018467 Al—Mg Inorganic materials 0.000 claims description 4
- 229910018571 Al—Zn—Mg Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 239000010962 carbon steel Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229940071182 stannate Drugs 0.000 claims description 3
- 125000005402 stannate group Chemical group 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002659 electrodeposit Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- 238000004070 electrodeposition Methods 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 71
- 229960001545 hydrotalcite Drugs 0.000 description 71
- 229910001701 hydrotalcite Inorganic materials 0.000 description 71
- 238000001652 electrophoretic deposition Methods 0.000 description 66
- 239000010410 layer Substances 0.000 description 60
- 239000003792 electrolyte Substances 0.000 description 48
- 238000005260 corrosion Methods 0.000 description 38
- 230000007797 corrosion Effects 0.000 description 38
- 238000012360 testing method Methods 0.000 description 27
- 150000002500 ions Chemical class 0.000 description 25
- 239000000243 solution Substances 0.000 description 20
- 229910001425 magnesium ion Inorganic materials 0.000 description 19
- 229910000861 Mg alloy Inorganic materials 0.000 description 18
- 239000000203 mixture Substances 0.000 description 13
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910001960 metal nitrate Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical compound O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910009378 Zn Ca Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001234 light alloy Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/10—Electrophoretic coating characterised by the process characterised by the additives used
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/18—Electrophoretic coating characterised by the process using modulated, pulsed, or reversing current
-
- 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
-
- 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
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Description
本発明は、層状複水酸化物を表面に有する金属板及びその製造方法に関する。The present invention relates to a metal plate having a layered double hydroxide on its surface and a method for producing the same.
マグネシウム合金およびアルミニウム合金は輸送機器（自動車、電車など）や家電製品、携帯電子機器、福祉材料（車椅子、杖など）などの軽量化部材として期待されているが、特に塩化物イオンを含む環境での耐食性が低いという課題がある。輸送機器や家電製品は、塩化物イオンを含む雨や海水の飛沫や人の汗に曝される。このため、高耐食性被膜の形成と、部材によっては高耐食性被膜に加えて塗装が必要とされている。
従来のマグネシウム材の耐食性被膜は、クロム、マンガンやフッ素などの環境負荷が高い元素を含むものが主流であったが、ＲｏＨＳやＲＥＡＣＨなどの環境規制が強化されクロメート処理は使用禁止や排除になっている。このため、製造工程での環境負荷が小さく、使用中の環境への安全性も高い元素で構成されている耐食性被膜が求められている。
Magnesium alloys and aluminum alloys are expected to be used as lightweight components for transportation equipment (automobiles, trains, etc.), home appliances, portable electronic devices, and welfare materials (wheelchairs, canes, etc.), but they have a problem of low corrosion resistance, especially in environments containing chloride ions. Transportation equipment and home appliances are exposed to rain, seawater splashes, and human sweat that contain chloride ions. For this reason, the formation of a highly corrosion-resistant coating and, depending on the component, painting in addition to the highly corrosion-resistant coating are required.
Conventional corrosion-resistant coatings for magnesium materials mainly contain elements that have a high environmental impact, such as chromium, manganese, and fluorine, but as environmental regulations such as RoHS and REACH have been strengthened, the use of chromate treatment has been prohibited or eliminated. For this reason, there is a demand for corrosion-resistant coatings that are composed of elements that have a small environmental impact during the manufacturing process and are highly safe for the environment during use.
リン酸を主成分とする環境負荷の低い元素で構成されている溶液中での陽極酸化により形成した高耐食性皮膜（特許文献１）の報告もあるが、陽極酸化は消費電力量が大きいという欠点がある。
また、リン酸、マンガン酸および酸化カルシウムを含む化成処理溶液および陽極酸化用電解液が開発されており（非特許文献１～４）、製造された皮膜は高い耐食性および塗料との密着性を示している。しかし、マンガン酸は廃液処理が必要な物質であることから、さらに環境負荷の低い耐食性皮膜およびその製造方法が望まれている。
There has been a report of a highly corrosion-resistant coating formed by anodizing in a solution composed of environmentally friendly elements, mainly phosphoric acid (Patent Document 1). However, anodizing has the disadvantage of consuming a large amount of power.
In addition, chemical conversion solutions and anodizing electrolytes containing phosphoric acid, manganic acid, and calcium oxide have been developed (Non-Patent Documents 1 to 4), and the films produced therefrom exhibit high corrosion resistance and adhesion to paint. However, since manganic acid is a substance that requires wastewater treatment, there is a need for a corrosion-resistant film with even lower environmental impact and a method for producing the same.
近年、層状複水酸化物（ＬＤＨ：一般式［Ｍ２＋
１－ｘＭ３＋
ｘ（ＯＨ）２］［Ａｎ－
ｘ／ｎ・ｍＨ２Ｏ］）被膜がマグネシウム合金やアルミニウム合金の耐食性被膜として注目されている（特許文献２、３、４参照）。
ＬＤＨはホスト層のＭｇやＡｌなどの金属水酸化物層と陰イオンと水分子で構成されるゲスト層が交互に積層した化合物で、層間には陰イオンだけでなく有機分子を取り込むこともできる。このため、マグネシウム合金やアルミニウム合金の腐食インヒビターを層間に挿入したＬＤＨで被膜を形成すると、被膜のキズの自己修復が促進されることが期待されている。これまでに、オートクレーブ（高温／高圧蒸気）処理によるＡＺ３１合金やＭｇ－Ａｌ－Ｚｎ－Ｃａ合金表面での被膜形成、Ｚｎ（ＮＯ３）２－Ａｌ（ＮＯ３）３などの金属硝酸塩溶液中でのＡＺ９１表面への電解析出による被膜形成や、ＬＤＨスラリー埋没加熱処理による被膜形成、Ａｌ（ＮＯ３）３溶液中での化成処理によるＬＤＨ被膜形成が行われた。
In recent years, layered double hydroxide (LDH: general formula [M 2+ 1-x M 3+ x (OH) 2 ][A n- x/n ·mH 2 O]) coatings have attracted attention as corrosion-resistant coatings for magnesium alloys and aluminum alloys (see Patent Documents 2, 3 and 4).
LDH is a compound in which a host layer of metal hydroxide layers such as Mg or Al and a guest layer consisting of anions and water molecules are alternately laminated, and it can incorporate not only anions but also organic molecules between the layers. For this reason, it is expected that forming a coating with LDH with a corrosion inhibitor for magnesium alloys or aluminum alloys inserted between the layers will promote self-repair of scratches in the coating. To date, coatings have been formed on the surfaces of AZ31 alloys and Mg-Al-Zn-Ca alloys by autoclave (high temperature/high pressure steam) treatment, coatings by electrolytic deposition on the surfaces of AZ91 in metal nitrate solutions such as Zn(NO 3 ) 2 -Al(NO 3 ) 3 , coatings by immersion in LDH slurry and heat treatment, and LDH coatings by chemical conversion treatment in an Al(NO 3 ) 3 solution.
オートクレーブ処理は、基材マグネシウム合金表面からＬＤＨを成長させる手法のため密着性が高いという利点がある一方、処理に時間がかかり、また大型の部材のために大型高圧蒸気窯を設置するなどコストがかかるという欠点がある。スラリー埋没法も、処理時間が長いという欠点がある。電解析出は短時間で被膜形成できるが、金属硝酸塩水溶液のｐＨは低く処理中の基材の腐食が懸念されるため、比較的耐食性が低いＭｇ合金や純Ｍｇへの応用に課題がある。化成処理では比較的短時間に処理できる処理法が開発されているが、基材から溶出するＭｇイオンがＬＤＨ層の主成分になるためＬＤＨ層の組成や形態が基材Ｍｇ合金に大きく依存する。また、電解析出でも化成処理でも、被膜形成後にＬＤＨの層間に任意の陰イオンや有機分子を挿入するのは困難である。これは、ＬＤＨ層間のイオン交換反応は水溶液中で行われるため、イオン交換処理中に基材マグネシウム合金が腐食される可能性が高いためである。 The autoclave treatment has the advantage of high adhesion because it is a method of growing LDH from the surface of the substrate magnesium alloy, but it takes a long time to process and is costly because a large high-pressure steam furnace must be installed for large components. The slurry immersion method also has the disadvantage of a long processing time. Electrolytic deposition can form a film in a short time, but the pH of the metal nitrate solution is low, so there is a concern that the substrate may corrode during processing, and there are problems with application to Mg alloys and pure Mg, which have relatively low corrosion resistance. In chemical conversion treatment, a treatment method that can be performed in a relatively short time has been developed, but the composition and form of the LDH layer are highly dependent on the substrate Mg alloy because Mg ions eluted from the substrate become the main component of the LDH layer. In addition, in both electrolytic deposition and chemical conversion treatment, it is difficult to insert any anion or organic molecule between the LDH layers after the coating is formed. This is because the ion exchange reaction between the LDH layers takes place in an aqueous solution, so there is a high possibility that the substrate magnesium alloy will be corroded during the ion exchange treatment.
マグネシウム合金やアルミニウム合金表面に層状複水酸化物（ＬＤＨ）を被覆する従来の方法には、処理時間が数時間から数日と長い、処理溶液の腐食性が高く処理できる合金組成に制限がある、コストが高いという課題と、ＬＤＨ組成や層間に挿入できるイオンに制限があるという課題がある。Conventional methods for coating the surfaces of magnesium alloys or aluminum alloys with layered double hydroxides (LDHs) have issues such as long treatment times of several hours to several days, highly corrosive treatment solutions that limit the alloy compositions that can be treated, high costs, and limitations on the LDH composition and the ions that can be inserted between the layers.
本発明者は、鋭意研究の結果、電気泳動堆積法を用いることで、処理時間が短縮できると共にＬＤＨ組成や層間に挿入できるイオンが自由に選択できるのではないかと考え、本願発明を想到するに至った。電気泳動堆積法は、電解液中にセラミックス粒子を帯電・分散させ、その懸濁液に電極基板を浸漬し、対極との間に電場を印加することにより、セラミックス粒子を電極基板上に直接堆積させる方法である。電気泳動堆積法の利点として、様々な組成のＬＤＨ粉末を堆積できること、および層間に任意の陰イオンや有機分子を挿入したＬＤＨ粉末を堆積できる点に着目した。
一方、電気泳動堆積法は一般的に、セラミックス粒子堆積層と電極基板の密着性に課題があることが知られている。本発明者は、電解液に金属イオンを添加し、ＬＤＨ粉末と共に水酸化物として電析させることで、堆積層の密着性を向上させることができることを発見し、本発明を完成するに至った。
As a result of intensive research, the inventors of the present invention came up with the idea that the use of electrophoretic deposition may enable the processing time to be shortened and the LDH composition and ions to be inserted between layers to be freely selected. The electrophoretic deposition method is a method in which ceramic particles are charged and dispersed in an electrolyte, an electrode substrate is immersed in the suspension, and an electric field is applied between the counter electrode to directly deposit the ceramic particles on the electrode substrate. The inventors focused on the advantages of the electrophoretic deposition method, such as the ability to deposit LDH powders of various compositions and the ability to deposit LDH powders with any anion or organic molecule inserted between layers.
On the other hand, it is known that the electrophoretic deposition method generally has a problem in adhesion between the ceramic particle deposition layer and the electrode substrate. The present inventor discovered that the adhesion of the deposition layer can be improved by adding metal ions to the electrolyte and electrolytically depositing them as hydroxides together with the LDH powder, and thus completed the present invention.
即ち、本発明は、上述した課題を解決したもので、１分～数十分程度の短時間処理で、様々な組成のＬＤＨ粉末および金属水酸化物を製膜する方法および層間に任意の陰イオンや有機分子（インヒビター）を挿入したＬＤＨ粉末を含む被膜を製膜する方法及び層状複水酸化物を表面に有する金属板を提供するものである。In other words, the present invention solves the above-mentioned problems and provides a method for forming films of LDH powders and metal hydroxides of various compositions in a short treatment time of about one minute to several tens of minutes, a method for forming a coating containing LDH powder with any anion or organic molecule (inhibitor) inserted between the layers, and a metal plate having a layered double hydroxide on the surface.
［１］本発明の層状複水酸化物を表面に有する金属板の製造方法は、例えば図１、図２に示すように、水を含有する電解液１６に金属イオンを添加すると共に、電解液１６中に層状複水酸化物粉末を分散させる工程（Ｓ１００、Ｓ１０２）、又は水を含有する電解液１６に層状複水酸化物粉末を分散させると共に、電解液１６中に金属イオンを添加する工程（Ｓ１０２、Ｓ１００）と、添加した金属イオンを含む電解液１６と層状複水酸化物粉末４０からなる懸濁液に電極基板１２と対極板１４を浸漬する工程（Ｓ１０４）と、電極基板１２と対極板１４との間に電場を印加することにより、電極基板１２上に層状複水酸化物粉末４０と共に前記金属イオンの水酸化物として電析させる工程（Ｓ１０６、Ｓ１０８）を有するものである。ここで、電極基板１２は被覆処理される金属板である。
好ましくは、電極基板１２上の層状複水和物の膜厚が、所定値になるまで、電気泳動堆積を継続する工程（Ｓ１１０）を有するとよい。
[1] The method for producing a metal plate having a layered double hydroxide on its surface according to the present invention comprises the steps of adding metal ions to a water-containing electrolytic solution 16 and dispersing a layered double hydroxide powder in the electrolytic solution 16 (S100, S102), or dispersing a layered double hydroxide powder in a water-containing electrolytic solution 16 and adding metal ions to the electrolytic solution 16 (S102, S100), immersing an electrode substrate 12 and a counter electrode plate 14 in a suspension consisting of electrolytic solution 16 containing the added metal ions and layered double hydroxide powder 40 (S104), and applying an electric field between the electrode substrate 12 and the counter electrode plate 14 to electrodeposit the layered double hydroxide powder 40 and the metal ions as hydroxides on the electrode substrate 12 (S106, S108). Here, the electrode substrate 12 is a metal plate to be coated.
Preferably, the method includes a step (S110) of continuing electrophoretic deposition until the film thickness of the layered double hydrate on the electrode substrate 12 reaches a predetermined value.
［２］本発明の層状複水酸化物を表面に有する金属板の製造方法［１］において、好ましくは、電解液１６は有機溶媒と水の混合溶媒であるとよい。
［３］本発明の層状複水酸化物を表面に有する金属板の製造方法［２］において、好ましくは、有機溶媒と水の体積の割合は、有機溶媒：水＝９９：１～７０：３０であるとよい。
水の体積割合が３０％を超えると、被覆処理溶液中での基材マグネシウム合金やアルミニウム合金の腐食が増大すると共に、水の還元反応で発生する水素ガスが増大して、被膜の欠陥が増える。水の体積割合が１％未満であれば、有機溶媒の濃度が高すぎて、電気泳動堆積に必要な電気伝導度が得られない。水の体積割合が１％以上３０％以下であり、残部を有機溶媒とすれば、緻密な層状複水酸化物層を作製できる。
［４］本発明の層状複水酸化物を表面に有する金属板の製造方法［２］又は［３］において、好ましくは、前記有機溶媒は、エタノール、メタノール、ブタノールエタノール、プロパノール、イソプロパノール、グリセリン、エチレングリコール、アセトン、ジメチルケトン、メチルエチルケトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、ジエチルエーテル、ジメチルスルホキシド、ジメチルフォルムアミド、クロロホルムの何れか１種類を含むとよい。
［５］本発明の層状複水酸化物を表面に有する金属板の製造方法［１］～［４］において、好ましくは、前記金属イオンは、Ｍｇ，Ａｌ，Ｚｎ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｃａ、Ｃｒ、Ｉｎの何れか１種類を含む金属イオンであり、前記金属イオンを生成する金属塩は、硝酸塩、硫酸塩、炭酸塩、カルボン酸塩、リン酸塩、又は塩化物であるとよい。
[2] In the method [1] for producing a metal plate having a layered double hydroxide on its surface according to the present invention, the electrolytic solution 16 is preferably a mixed solvent of an organic solvent and water.
[3] In the method [2] for producing a metal plate having a layered double hydroxide on its surface according to the present invention, the volume ratio of the organic solvent to the water is preferably from 99:1 to 70:30 (organic solvent:water).
If the volumetric percentage of water exceeds 30%, corrosion of the substrate magnesium alloy or aluminum alloy in the coating treatment solution increases, and hydrogen gas generated by the reduction reaction of water increases, resulting in more defects in the coating. If the volumetric percentage of water is less than 1%, the concentration of the organic solvent is too high to obtain the electrical conductivity required for electrophoretic deposition. If the volumetric percentage of water is 1% or more and 30% or less, with the remainder being an organic solvent, a dense layered double hydroxide layer can be produced.
[4] In the method [2] or [3] for producing a metal plate having a layered double hydroxide on its surface according to the present invention, the organic solvent preferably includes any one of ethanol, methanol, butanol, ethanol, propanol, isopropanol, glycerin, ethylene glycol, acetone, dimethyl ketone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ether, dimethyl sulfoxide, dimethylformamide, and chloroform.
[5] In the method [1] to [4] for producing a metal plate having a layered double hydroxide on a surface thereof according to the present invention, preferably, the metal ion is a metal ion containing any one of Mg, Al, Zn, Mn, Fe, Co, Ni, Cu, Ca, Cr, and In, and the metal salt generating the metal ion is preferably a nitrate, sulfate, carbonate, carboxylate, phosphate, or chloride.
［６］本発明の層状複水酸化物を表面に有する金属板の製造方法［１］～［５］において、好ましくは、層状複水酸化物粉末４０は、一般式：［Ｍ２＋
（１－ｘ）Ｍ３＋
ｘ（ＯＨ）２］［Ａｎ－
ｘ／ｎ・ｙＨ２Ｏ］で表されると共に、
Ｍ２＋は、Ｍｇ（マグネシウム），Ｚｎ（亜鉛），Ｃａ（カルシウム），Ｍｎ（マンガン），Ｐｄ（パラジウム），Ｓｒ（ストロンチウム），Ｆｅ（鉄），Ｃｏ（コバルト），Ｎｉ（ニッケル），Ｃｕ（銅）の何れか１種類から選択される二価金属イオンであり、
Ｍ３＋は、Ａｌ（アルミニウム），Ｂｉ（ビスマス），Ｇａ（ガリウム），Ｎｉ，Ｍｎ，Ｖ（バナジウム），Ｃｅ（セリウム），Ｌａ（ランタン），Ｃｒ（クロム），Ｆｅ（鉄），Ｃｏ（コバルト），Ｉｎ（インジウム）の何れか１種類から選択される三価金属イオンであり、
Ａは、ＮＯ３
－，ＣＯ３
２－，ＯＨ－，Ｃｌ－，ＳＯ４
２－，ＳｉＯ４
４－の何れか１種類から選択される陰イオン、又は、リン酸、クロム酸、過マンガン酸、バナジン酸、セレン酸、ホウ酸、フッ化物、カルボン酸、すず酸、アルミン酸、及びモリブデン酸の何れか１種類から選択されるｎ価（ｎ＝１、２、３、又は４）の陰イオンであるとよい。
［７］本発明の層状複水酸化物を表面に有する金属板の製造方法［６］において、好ましくは、層状複水酸化物粉末４０の三価金属イオンは、二価金属イオンを最大モル比Ｍ２＋：Ｍ３＋＝２：１まで置換しているとよい。なお、Ｍ３＋の割合がゼロの場合は、Ｍｇ（ＯＨ）２（ブルーサイト）と呼ばれる。全く置換されていない状態を下限値としておくが、好ましくは二価と三価の金属イオンのモル比は、４：１～２：１の範囲であるとよい。
[6] In the method [1] to [5] for producing a metal plate having a layered double hydroxide on the surface thereof according to the present invention, the layered double hydroxide powder 40 is preferably represented by the general formula: [M 2+ (1-x) M 3+ x (OH) 2 ][A n- x/ n.yH 2 O],
M2 + is a divalent metal ion selected from any one of Mg (magnesium), Zn (zinc), Ca (calcium), Mn (manganese), Pd (palladium), Sr (strontium), Fe (iron), Co (cobalt), Ni (nickel), and Cu (copper);
M3 + is a trivalent metal ion selected from any one of Al (aluminum), Bi (bismuth), Ga (gallium), Ni, Mn, V (vanadium), Ce (cerium), La (lanthanum), Cr (chromium), Fe (iron), Co (cobalt), and In (indium);
A may be an anion selected from any one of NO 3 − , CO 3 2− , OH − , Cl − , SO 4 2− , and SiO 4 4− , or an n-valent (n=1, 2, 3, or 4) anion selected from any one of phosphate, chromate, permanganate, vanadate, selenate, borate, fluoride, carboxylate, stannate, aluminate, and molybdate.
[7] In the method [6] for producing a metal plate having a layered double hydroxide on its surface according to the present invention, the trivalent metal ions in the layered double hydroxide powder 40 are preferably substituted with divalent metal ions up to a maximum molar ratio of M 2+ :M 3+ =2:1. When the proportion of M 3+ is zero, it is called Mg(OH) 2 (brucite). The lower limit is a state where no substitution is present, but the molar ratio of divalent to trivalent metal ions is preferably in the range of 4:1 to 2:1.
［８］本発明の層状複水酸化物を表面に有する金属板の製造方法［６］～［７］において、好ましくは、電極基板１２上に電析された堆積層における層状複水酸化物粉末４０と金属水酸化物の体積の割合は、層状複水酸化物粉末：金属水酸化物＝９０：１０～１０：９０であるよい。
堆積層における層状複水酸化物粉末と金属水酸化物の体積の割合について説明する。粉末の割合の上限は、層状複水酸化物粉末：金属水酸化物＝９０：１０（体積比）である。２種類のサイズのレンズ形粒子をランダムに混ぜた場合のシミュレーションで、最大の充填率が約９０％になるからである。最も広い範囲の下限は、層状複水酸化物粉末：金属水酸化物＝１０：９０(体積比)である。これは、低い電圧や低い金属イオン濃度の電解液中でＥＰＤして作製した堆積層における割合である。好ましい範囲の下限は、層状複水酸化物粉末：金属水酸化物＝５５：４５（体積比）である。均一なサイズの球形粒子をランダムに充填した場合のシミュレーションで最も低い充填率が約５５％になるからである。さらに好ましい範囲の下限は、層状複水酸化物粉末：金属水酸化物＝６８：３２（体積比）である。層状複水酸化物粉末が均一なサイズの球形で体心立方で充填されている場合である。最適範囲の下限は、層状複水酸化物粉末：金属水酸化物＝７４：２６（体積比）である。層状複水酸化物粉末が均一なサイズの球形で最密充填されており、隙間に金属水酸化物が充填されている場合である。
最も広い範囲：層状複水酸化物粉末：金属水酸化物＝９０：１０～１０：９０
好ましい範囲：層状複水酸化物粉末：金属水酸化物＝９０：１０～５５：４５
さらに好ましい範囲：９０：１０～６８：３２
最適範囲：層状複水酸化物粉末：金属水酸化物＝９０：１０～７４：２６
［９］本発明の層状複水酸化物を表面に有する金属板の製造方法［１］～［８］において、好ましくは、電極基板１２は、純Ｍｇ材、純Ａｌ材、純Ｆｅ材、ＡＺ３１（Ｍｇ－３Ａｌ－１Ｚｎ）合金、ＡＺ９１（Ｍｇ－９Ａｌ－１Ｚｎ）合金、ＡＭ６０（Ｍｇ－６Ａｌ－０．４Ｍｎ）合金、ＡＸＭ（Ｍｇ－Ａｌ－（Ｚｎ）－Ｃａ）合金、ＷＥ４３（Ｍｇ－４Ｙ－３ＲＥ）合金、ＺＫ６０（Ｍｇ－６Ｚｎ－０．５Ｚｒ）合金、５０００系Ａｌ合金（Ａｌ－Ｍｇ）、６０００系Ａｌ合金（Ａｌ－Ｍｇ－Ｓｉ）、７０００系Ａｌ合金（Ａｌ－Ｚｎ－Ｍｇ）合金、又は炭素鋼の何れかであるとよい。
［１０］本発明の層状複水酸化物を表面に有する金属板の製造方法［１］～［９］において、好ましくは、電極基板１２に印加される電場は、パルス電圧又は定電圧を用いるとよい。
[8] In the methods [6] to [7] for producing a metal plate having a layered double hydroxide on its surface according to the present invention, the volume ratio of layered double hydroxide powder 40 to metal hydroxide in the deposited layer electrodeposited on the electrode substrate 12 is preferably layered double hydroxide powder:metal hydroxide=90:10 to 10:90.
The volume ratio of the layered double hydroxide powder and the metal hydroxide in the sediment layer will be described. The upper limit of the powder ratio is layered double hydroxide powder:metal hydroxide=90:10 (volume ratio). This is because the maximum packing ratio is about 90% in a simulation in which two types of lenticular particles of different sizes are mixed randomly. The lower limit of the widest range is layered double hydroxide powder:metal hydroxide=10:90 (volume ratio). This is the ratio in a sediment layer produced by EPD in an electrolyte with a low voltage or low metal ion concentration. The lower limit of the preferred range is layered double hydroxide powder:metal hydroxide=55:45 (volume ratio). This is because the lowest packing ratio is about 55% in a simulation in which spherical particles of uniform size are randomly packed. The lower limit of the more preferred range is layered double hydroxide powder:metal hydroxide=68:32 (volume ratio). This is the case in which the layered double hydroxide powder is spherical and packed in a body-centered cubic shape with uniform size. The lower limit of the optimum range is layered double hydroxide powder:metal hydroxide=74:26 (volume ratio), in which the layered double hydroxide powder is packed closely in the form of uniformly sized spheres, with the metal hydroxide filling the gaps.
Widest range: Layered double hydroxide powder: Metal hydroxide = 90:10 to 10:90
Preferred range: layered double hydroxide powder: metal hydroxide=90:10 to 55:45
More preferred range: 90:10 to 68:32
Optimum range: layered double hydroxide powder: metal hydroxide = 90:10 to 74:26
[9] In the methods [1] to [8] for producing a metal plate having a layered double hydroxide on its surface according to the present invention, the electrode substrate 12 is preferably any one of a pure Mg material, a pure Al material, a pure Fe material, an AZ31 (Mg-3Al-1Zn) alloy, an AZ91 (Mg-9Al-1Zn) alloy, an AM60 (Mg-6Al-0.4Mn) alloy, an AXM (Mg-Al-(Zn)-Ca) alloy, a WE43 (Mg-4Y-3RE) alloy, a ZK60 (Mg-6Zn-0.5Zr) alloy, a 5000 series Al alloy (Al-Mg), a 6000 series Al alloy (Al-Mg-Si), a 7000 series Al alloy (Al-Zn-Mg) alloy, or carbon steel.
[10] In the method [1] to [9] for producing a metal plate having a layered double hydroxide on its surface according to the present invention, it is preferable that the electric field applied to the electrode substrate 12 is a pulse voltage or a constant voltage.
［１１］本発明の層状複水酸化物を表面に有する金属板は、層状複水酸化物を表面に有する金属板であって、前記層状複水酸化物は層状複水酸化物粉末－金属水酸化物の混合堆積被膜であり、前記混合堆積被膜の厚さは、０．５μｍ以上１３０μｍ以下である。
［１２］本発明の層状複水酸化物を表面に有する金属板［１１］において、好ましくは、前記金属板は、純Ｍｇ材、純Ａｌ材、純Ｆｅ材、ＡＺ３１（Ｍｇ－３Ａｌ－１Ｚｎ）合金、ＡＺ９１（Ｍｇ－９Ａｌ－１Ｚｎ）合金、ＡＭ６０（Ｍｇ－６Ａｌ－０．４Ｍｎ）合金、ＡＸＭ（Ｍｇ－Ａｌ－（Ｚｎ）－Ｃａ）合金、ＷＥ４３（Ｍｇ－４Ｙ－３ＲＥ）合金、ＺＫ６０（Ｍｇ－６Ｚｎ－０．５Ｚｒ）合金、５０００系Ａｌ合金（Ａｌ－Ｍｇ）、６０００系Ａｌ合金（Ａｌ－Ｍｇ－Ｓｉ）、７０００系Ａｌ合金（Ａｌ－Ｚｎ－Ｍｇ）合金、又は炭素鋼であるとよい。
［１３］本発明の層状複水酸化物を表面に有する金属板［１１］又は［１２］において、好ましくは、前記層状複水酸化物粉末－金属水酸化物の混合堆積被膜における層状複水酸化物粉末と金属水酸化物の体積の割合は、層状複水酸化物粉末：金属水酸化物＝９０：１０～１０：９０であるとよい。
[11] The metal plate having a layered double hydroxide on its surface according to the present invention is a metal plate having a layered double hydroxide on its surface, the layered double hydroxide being a mixed deposited coating of layered double hydroxide powder and metal hydroxide, and the thickness of the mixed deposited coating is 0.5 μm or more and 130 μm or less.
[12] In the metal plate [11] having a layered double hydroxide on a surface thereof according to the present invention, the metal plate is preferably made of a pure Mg material, a pure Al material, a pure Fe material, an AZ31 (Mg-3Al-1Zn) alloy, an AZ91 (Mg-9Al-1Zn) alloy, an AM60 (Mg-6Al-0.4Mn) alloy, an AXM (Mg-Al-(Zn)-Ca) alloy, a WE43 (Mg-4Y-3RE) alloy, a ZK60 (Mg-6Zn-0.5Zr) alloy, a 5000 series Al alloy (Al-Mg), a 6000 series Al alloy (Al-Mg-Si), a 7000 series Al alloy (Al-Zn-Mg) alloy, or a carbon steel.
[13] In the metal plate [11] or [12] having a layered double hydroxide on its surface according to the present invention, the volume ratio of the layered double hydroxide powder to the metal hydroxide in the mixed deposited coating of the layered double hydroxide powder and the metal hydroxide is preferably layered double hydroxide powder:metal hydroxide=90:10 to 10:90.
本発明の層状複水酸化物を表面に有する金属板の製造方法において、電解液に添加する金属イオンとして、金属硝酸塩を添加した電解液中での層状複水酸化物粉末の電気泳動堆積の効果を、従来技術と対比して説明する。
１） 層状複水酸化物粉末を主原料としている。このため、層状複水酸化物粉末の組成や層間の陰イオンや有機分子の自由度が高い。
２） 電気泳動堆積法は比較的短時間で数マイクロメートル以上の厚い被膜を形成できる手法のため、被覆時間を短くできる。
３） 電気泳動堆積では、合金組成によらず層状複水酸化物被膜を形成できる。これに対して、化成処理やオートクレーブ処理では、基材マグネシウム合金中のＭｇやＡｌが被膜に取り込まれて層状複水酸化物を形成しているため、被膜組成が基材合金の組成に依存する。
４） 実施例のように、電解液に添加する金属イオンとして、金属硝酸塩を添加する場合、電解析出法と電気泳動堆積法を組み合わせた手法になっている。金属水酸化物と層状複水酸化物粉末の同時析出・堆積により、粉末の密着性を向上できる。
In the method of manufacturing a metal plate having a layered double hydroxide on its surface according to the present invention, the effect of electrophoretic deposition of layered double hydroxide powder in an electrolyte solution containing a metal nitrate as the metal ion added thereto will be explained in comparison with the prior art.
1) Layered double hydroxide powder is used as the main raw material. This allows for a high degree of freedom in the composition of the layered double hydroxide powder and the anions and organic molecules between the layers.
2) Electrophoretic deposition is a technique that can form a thick coating of several micrometers or more in a relatively short time, so the coating time can be shortened.
3) Electrophoretic deposition can form layered double hydroxide coatings regardless of the alloy composition, whereas chemical conversion coating and autoclave treatment incorporate Mg and Al from the magnesium alloy substrate into the coating to form layered double hydroxide, so the coating composition depends on the composition of the substrate alloy.
4) When metal nitrates are added to the electrolyte as metal ions as in the examples, the electrolytic deposition method and the electrophoretic deposition method are combined. The simultaneous deposition and deposition of metal hydroxide and layered double hydroxide powders can improve the adhesion of the powders.
本発明の層状複水酸化物を表面に有する金属板によれば、被膜が耐食性を発揮して金属板の腐食を抑制するという効果がある。A metal plate having the layered double hydroxide of the present invention on its surface has the effect of suppressing corrosion of the metal plate by providing a coating with corrosion resistance.
以下、図面を用いて本発明を説明する。
図１は、本発明の層状複水酸化物を表面に有する金属板を製造するために用いる電気泳動堆積装置の概要図である。図１において、電気泳動堆積装置は、電解槽１０、スターラー２０、直流電源３０、関数発生器３６を備えている。電解槽１０は、表面処理溶液１６を収容していると共に、表面処理溶液１６に被処理金属基板としての基材１２、対極板１４が浸されており、攪拌子２２が表面処理溶液１６の下部に位置している。基材１２には、電気泳動堆積法による処理の進行に従って、その表面に堆積した金属水酸化物１８が存在する。
The present invention will now be described with reference to the drawings.
Fig. 1 is a schematic diagram of an electrophoretic deposition apparatus used to produce a metal plate having the layered double hydroxide of the present invention on its surface. In Fig. 1, the electrophoretic deposition apparatus comprises an electrolytic cell 10, a stirrer 20, a DC power supply 30, and a function generator 36. The electrolytic cell 10 contains a surface treatment solution 16 in which a substrate 12 as a metal substrate to be treated and a counter electrode plate 14 are immersed, and a stirrer 22 is positioned below the surface treatment solution 16. As treatment by electrophoretic deposition progresses, metal hydroxide 18 is present on the surface of the substrate 12.
直流電源３０の一方の極と基材１２との間は、電線３２で結線されている。直流電源３０の他方の極と対極板１４との間は、電線３４で結線されている。基材１２と対極板１４との間で生ずる電位差によって、表面処理溶液１６の内部でＬＤＨ粉末４０と添加金属イオン４２が対極板１４から基材１２に移動して、堆積したＬＤＨ粉末４０と金属水酸化物１８の層が形成される。直流電源３０の電圧は、電気泳動堆積に必要な電圧としている。電気泳動堆積では、帯電した粉末が電場の力（Ｆ＝ｑＥ．Ｆ：力、ｑ：クーロン力、Ｅ：電圧）で電極基板上に押し付けられている。One pole of the DC power supply 30 is connected to the substrate 12 by an electric wire 32. The other pole of the DC power supply 30 is connected to the counter electrode plate 14 by an electric wire 34. Due to the potential difference between the substrate 12 and the counter electrode plate 14, the LDH powder 40 and the added metal ions 42 move from the counter electrode plate 14 to the substrate 12 inside the surface treatment solution 16, forming a layer of the deposited LDH powder 40 and metal hydroxide 18. The voltage of the DC power supply 30 is set to the voltage required for electrophoretic deposition. In electrophoretic deposition, the charged powder is pressed onto the electrode substrate by the force of an electric field (F = qE.F: force, q: Coulomb force, E: voltage).
このように構成された電気泳動堆積装置の動作を説明する。
電気泳動堆積装置では、粉末を堆積させる基板である基材１２を陰極、ステンレス板等の対極板１４を陽極にして電場を印加する。このため、電解液中でプラスに帯電している粉末および陽イオン（カチオン）が陰極に引き付けられ、陰イオン（アニオン）が陽極側に引き付けられる。陰極に引き付けられた粉末は電場により押し付けられた状態となっている。同時に陰極表面では水の電気分解が起こり、水素発生とｐＨ上昇が起こる。このため、陰極に引き付けられた陽イオン（カチオン）は高ｐＨ環境で水酸化物として陰極表面に析出する。
本発明の層状複水酸化物を表面に有する金属板を製造するために用いる電気泳動堆積装置では、陰極Ｍｇ合金表面で、電場によるＬＤＨ粉末の押しつけと同時に、Ｍｇイオンおよび／もしくはＡｌイオンのｐＨ上昇による水酸化物としての析出や、ＬＤＨ粉末に吸着した状態での析出、または有機溶媒との化合物である有機金属化合物としての析出が同時に起こっている。ＬＤＨ粉末に吸着した金属イオンは大気中の水と反応して水酸化物や酸化物になり、有機金属化合物は加水分解されると水酸化物や酸化物になる。このため、金属水酸化物をバインダー（糊）としてＬＤＨ粉末がＭｇ合金表面に固着することができる。
本発明では、金属イオンの水酸化物としての析出を並行して起こすことを狙っているが、金属イオンの析出反応の詳細はわかっていない。本発明で析出した金属水酸化物がどの反応で水酸化物になったかは現時点では不明である。一番考えやすいのが水から生成した水酸化物イオンと金属イオンの反応であるが、証明されたわけではない。
The operation of the electrophoretic deposition apparatus thus configured will now be described.
In the electrophoretic deposition apparatus, an electric field is applied between the substrate 12, which is the substrate on which the powder is deposited, as the cathode and the counter electrode plate 14, such as a stainless steel plate, as the anode. As a result, the powder and positively charged ions (cations) in the electrolyte are attracted to the cathode, and the negative ions (anions) are attracted to the anode. The powder attracted to the cathode is pressed against it by the electric field. At the same time, water is electrolyzed on the surface of the cathode, generating hydrogen and increasing the pH. As a result, the positive ions (cations) attracted to the cathode are precipitated on the surface of the cathode as hydroxides in a high pH environment.
In the electrophoretic deposition apparatus used to manufacture a metal plate having a layered double hydroxide on its surface according to the present invention, the LDH powder is pressed against the cathode Mg alloy surface by an electric field, and simultaneously, Mg ions and/or Al ions are precipitated as hydroxides due to an increase in pH, precipitated in a state adsorbed to the LDH powder, or precipitated as organometallic compounds that are compounds with an organic solvent. The metal ions adsorbed to the LDH powder react with water in the air to become hydroxides or oxides, and the organometallic compounds are hydrolyzed to become hydroxides or oxides. Therefore, the LDH powder can be fixed to the Mg alloy surface using the metal hydroxide as a binder (glue).
In the present invention, we aim to cause the precipitation of metal ions as hydroxides in parallel, but the details of the precipitation reaction of metal ions are not known. It is currently unknown which reaction caused the metal hydroxide precipitated in the present invention to become hydroxide. The most likely scenario is a reaction between hydroxide ions generated from water and metal ions, but this has not been proven.
層状複水酸化物は、一般式：［Ｍ２＋
（１－ｘ）Ｍ３＋
ｘ（ＯＨ）２］［Ａｎ－
ｘ／ｎ・ｙＨ２Ｏ］で表される（成田榮一、粘土科学，４６（４），２０７－２１８（２００７）参照）。
ここで、基本層のＭ２＋は、Ｍｇ（マグネシウム），Ｚｎ（亜鉛），Ｃａ（カルシウム），Ｍｎ（マンガン），Ｐｄ（パラジウム），Ｓｒ（ストロンチウム），Ｆｅ（鉄），Ｃｏ（コバルト），Ｎｉ（ニッケル），Ｃｕ（銅），などの二価金属イオンである。
基本層のＭ３＋は、Ａｌ（アルミニウム），Ｂｉ（ビスマス），Ｇａ（ガリウム），Ｎｉ，Ｍｎ，Ｖ（バナジウム），Ｃｅ（セリウム），Ｌａ（ランタン），Ｃｒ（クロム），Ｆｅ（鉄），Ｃｏ（コバルト），Ｉｎ（インジウム）などの三価金属イオンである。
水酸化物基本層中の三価金属イオンは、二価金属イオンを最大モル比Ｍ２＋：Ｍ３＋＝２：１まで置換することができる。
中間層の陰イオンＡは、ＮＯ３
－，ＣＯ３
２－，ＯＨ－，Ｃｌ－，ＳＯ４
２－，ＳｉＯ４
４－などの陰イオン、又は、リン酸、クロム酸、過マンガン酸、バナジン酸、セレン酸、ホウ酸、フッ化物、カルボン酸、モリブデン酸、すず酸、アルミン酸、クロム酸などのｎ価の陰イオンである。特に、中間層の陰イオンＡとしては、腐食インヒビターとして機能することから、上記ｎ価の陰イオンのうち、バナジン酸イオン（ＶＯ４
３－、［ＶＯ３］ｎ
ｎ－等）、モリブデン酸イオン（ＭｏＯ４
２－等）、すず酸イオン（ＳｎＯ３
２－）、アルミン酸イオン（Ａｌ（ＯＨ）４
―）、クロム酸イオン（ＣｒＯ４
２－）等が含まれることが好ましい。
Layered double hydroxides are represented by the general formula: [M 2+ (1-x) M 3+ x (OH) 2 ][A n- x/n ·yH 2 O] (see Eiichi Narita, Clay Science, 46(4), 207-218 (2007)).
Here, M2 + in the basic layer is a divalent metal ion such as Mg (magnesium), Zn (zinc), Ca (calcium), Mn (manganese), Pd (palladium), Sr (strontium), Fe (iron), Co (cobalt), Ni (nickel), or Cu (copper).
The M3 + in the basic layer is a trivalent metal ion such as Al (aluminum), Bi (bismuth), Ga (gallium), Ni, Mn, V (vanadium), Ce (cerium), La (lanthanum), Cr (chromium), Fe (iron), Co (cobalt), or In (indium).
Trivalent metal ions in the hydroxide based layer can replace divalent metal ions up to a maximum molar ratio M 2+ :M 3+ =2:1.
The anion A of the intermediate layer is an anion such as NO 3 - , CO 3 2- , OH - , Cl - , SO 4 2- , SiO 4 4- or an n-valent anion such as phosphoric acid, chromic acid, permanganic acid, vanadic acid, selenic acid, boric acid, fluoride, carboxylic acid, molybdic acid, stannic acid, aluminic acid, chromic acid, etc. In particular, the anion A of the intermediate layer preferably includes vanadate ions (VO 4 3- , [VO 3 ] n n-, etc.), molybdic acid ions (MoO 4 2-, etc.), stannic acid ions (SnO 3 2- ), aluminic acid ions (Al(OH) 4 - ), chromate ions (CrO 4 2- ), etc., among the above n-valent anions, because they function as corrosion inhibitors.
表面処理溶液１６は、表面処理用の電解液であって、その組成は電気泳動の溶液として次の様になっている。
有機溶媒―水混合溶媒：有機溶媒は、アルコール系として、エタノール、メタノール、ブタノールエタノール、プロパノール、イソプロパノール、グリセリン、エチレングリコールなどがある。ケトン系として、アセトン、ジメチルケトン、メチルエチルケトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどがある。エーテル系として、ジエチルエーテルなどがある。その他として、ジメチルスルホキシド、ジメチルフォルムアミド、クロロホルムなどがある。
The surface treatment solution 16 is an electrolyte for surface treatment, and has the following composition as an electrophoretic solution:
Organic solvent-water mixed solvent: Organic solvents include alcohols such as ethanol, methanol, butanol, propanol, isopropanol, glycerin, and ethylene glycol. Ketones include acetone, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ethers include diethyl ether. Others include dimethyl sulfoxide, dimethylformamide, and chloroform.
電解液に分散させるＬＤＨ粉末の濃度は、電解液に対する体積比率として、０％以上１０％以下であるとよい。ＬＤＨ粉末の濃度が１０％を超えると、懸濁液中での粒子間距離が近くなって凝集し、沈降しやすくなるという技術的課題が生じる。
電解液に添加する金属イオンとして、金属硝酸塩を添加する場合、Ｍｇ（ＮＯ３）２およびＡｌ（ＮＯ３）３濃度範囲は、例えば次の比率とするとよい。
Ｍｇ（ＮＯ３）２：Ａｌ（ＮＯ３）３＝１：０～０：１
マグネシウムイオンは、ＬＤＨ粉末表面に吸着してＬＤＨ粉末と共に負極側に泳動し、負極表面でゲル状水酸化マグネシウムとして析出するため、水酸化マグネシウムがＬＤＨ粉末を負極表面や粉末同士に接着させる糊としての働くという技術的効果がある。アルミニウムイオンも、マグネシウムイオンと同様にＬＤＨ粉末表面に吸着して泳動し、ＬＤＨ粉末を負極表面や粉末同士に接着させる糊としての働くという技術的効果がある。マグネシウムイオンとアルミニウムイオンを同時に添加すると、負極表面でマグネシウムとアルミニウムの複水酸化物として析出し、ＬＤＨ粉末を負極表面や粉末同士に接着させる糊として働く。
The concentration of the LDH powder dispersed in the electrolyte is preferably 0% or more and 10% or less in volume ratio to the electrolyte. If the concentration of the LDH powder exceeds 10%, the distance between particles in the suspension becomes short, causing aggregation and making the particles more likely to settle, which is a technical problem.
When metal nitrates are added as metal ions to the electrolyte, the concentration ranges of Mg(NO 3 ) 2 and Al(NO 3 ) 3 may be, for example, in the following ratio.
Mg(NO 3 ) 2 :Al(NO 3 ) 3 =1:0 to 0:1
Magnesium ions are adsorbed to the surface of the LDH powder and migrate to the negative electrode side together with the LDH powder, and precipitate as gel-like magnesium hydroxide on the surface of the negative electrode, which has the technical effect of acting as a glue to bond the LDH powder to the negative electrode surface and to other powders. Aluminum ions, like magnesium ions, are adsorbed to the surface of the LDH powder and migrate to the negative electrode surface, which has the technical effect of acting as a glue to bond the LDH powder to the negative electrode surface and to other powders. When magnesium ions and aluminum ions are added simultaneously, they precipitate as double hydroxides of magnesium and aluminum on the surface of the negative electrode, and act as a glue to bond the LDH powder to the negative electrode surface and to other powders.
図２は、本発明の層状複水酸化物を表面に有する金属板を製造する工程を説明する流れ図である。
まず、電解液１６に金属イオンを添加する（Ｓ１００）。次に、電解液１６中にＬＤＨ粉末を分散させる（Ｓ１０２）。この場合には、例えばスターラーを用いて攪拌する。なお、先に電解液１６中にＬＤＨ粉末を分散させ（Ｓ１０２）、次にこの電解液１６に金属イオンを添加してもよい（Ｓ１００）。ＬＤＨ粉末は電解液１６中で自発的に帯電する。
次に、添加した金属イオンを含む電解液１６とＬＤＨ粉末４０からなる懸濁液に電極基板１２及び対極板１４を浸漬する（Ｓ１０４）。電極基板１２と対極板１４との間に電場を印加する（Ｓ１０６）。電場の印加は、例えば直流電源３０の一方の極と基材１２との間を電線３２で結線し、直流電源３０の他方の極と対極板１４との間を電線３４で結線し、直流電源３０から所定電位の定電圧やパルス電圧により電場を印加する。すると、電極基板１２上にＬＤＨ粉末４０と共に前記金属イオンの水酸化物として電析する（Ｓ１０８）。
電極基板１２上の層状複水酸化物の膜厚が、所定値になるまで、電気泳動堆積を継続する（Ｓ１１０）。電気泳動堆積を継続させる時間は、直接電極基板１２上の層状複水酸化物の膜厚を測定してもよく、また直流電源３０から供給した電荷の総量や電気泳動堆積前後の基材の重量変化から定めてもよい。
FIG. 2 is a flow chart illustrating the process for producing a metal plate having the layered double hydroxide on its surface according to the present invention.
First, metal ions are added to the electrolytic solution 16 (S100). Next, LDH powder is dispersed in the electrolytic solution 16 (S102). In this case, stirring is performed using a stirrer, for example. Alternatively, the LDH powder may be dispersed in the electrolytic solution 16 first (S102), and then the metal ions may be added to the electrolytic solution 16 (S100). The LDH powder spontaneously becomes charged in the electrolytic solution 16.
Next, the electrode substrate 12 and the counter electrode plate 14 are immersed in a suspension consisting of the electrolyte 16 containing the added metal ions and the LDH powder 40 (S104). An electric field is applied between the electrode substrate 12 and the counter electrode plate 14 (S106). For example, the electric field is applied by connecting one pole of a DC power source 30 to the substrate 12 with an electric wire 32, connecting the other pole of the DC power source 30 to the counter electrode plate 14 with an electric wire 34, and applying an electric field by a constant voltage or pulse voltage of a predetermined potential from the DC power source 30. Then, the metal ions are electrodeposited as hydroxides on the electrode substrate 12 together with the LDH powder 40 (S108).
Electrophoretic deposition is continued until the thickness of the layered double hydroxide on the electrode substrate 12 reaches a predetermined value (S110). The time for which electrophoretic deposition is continued may be determined by directly measuring the thickness of the layered double hydroxide on the electrode substrate 12, or may be determined from the total amount of charge supplied from the DC power source 30 or the change in weight of the substrate before and after electrophoretic deposition.
実施例では、ＬＤＨ粉末として市販のハイドロタルサイト（ＨＴ）粉末等を用いた。ＨＴは層間にＣＯ３
２－イオンが挿入されたＭｇ－Ａｌ系ＬＤＨである。基材には、Ｍｇ－３ｍａｓｓ％ Ａｌ－１ｍａｓｓ％ Ｚｎ（ＡＺ３１）合金および純Ｍｇ板等を用いた。ＡＺ３１合金は、現在、自動車やカメラ、パソコン、携帯電話等の部材に使用されている汎用マグネシウム合金である。
以下の実施例では、基材の種類、ＬＤＨの種類及び濃度、溶媒の組成及び組成比、印加する電圧等を変えて層状複水酸化物層を作製した。
In the examples, commercially available hydrotalcite (HT) powder or the like was used as the LDH powder. HT is an Mg-Al-based LDH with CO 3 2- ions inserted between layers. As the substrate, an Mg-3 mass% Al-1 mass% Zn (AZ31) alloy and a pure Mg plate or the like were used. The AZ31 alloy is a general-purpose magnesium alloy currently used in components for automobiles, cameras, personal computers, mobile phones, etc.
In the following examples, layered double hydroxide layers were produced by changing the type of substrate, the type and concentration of LDH, the composition and composition ratio of the solvent, the applied voltage, and the like.
＜参考例１＞ＨＴ粉末のみの電気泳動堆積
Ｍｇ－３ｍａｓｓ％ Ａｌ－１ｍａｓｓ％ Ｚｎ（ＡＺ３１）板表面を＃１２００の耐水研磨紙で仕上げ、基材とした。電解液には、エタノール：水＝４：１（体積比）の溶媒に粒径約１μｍの市販のハイドロタルサイト（ＨＴ）粉末を１～５ｗ／ｖ％（ｗｅｉｇｈｔ／ｖｏｌｕｍｅ％）で懸濁した溶液を用いた。同懸濁液を撹拌しながら、作用極として基材ＡＺ３１板および対極としてステンレス鋼メッシュ板を挿入した。ＡＺ３１板を陰極として対極との間にピーク―ピーク（ｐ－ｐ）電圧１０Ｖ、周波数０．１Ｈｚ、デューティー比９８％のパルス電圧を１０分間印加し、電気泳動堆積（ＥＰＤ）を行った。ＥＰＤ後のＡＺ３１板を１００℃で１時間乾燥した後、イソプロパノール溶液で超音波洗浄し、ＬＤＨ堆積表面を得た。なお、超音波洗浄前の表面は目視ではＨＴ粉末で均一に覆われていたが、超音波洗浄によりＨＴ粉末の多くが基材表面から脱落した。
Reference Example 1: Electrophoretic deposition of HT powder only The surface of an Mg-3 mass% Al-1 mass% Zn (AZ31) plate was finished with #1200 waterproof abrasive paper to form a substrate. For the electrolyte, a solution was used in which commercially available hydrotalcite (HT) powder with a particle size of about 1 μm was suspended at 1 to 5 w/v% (weight/volume%) in a solvent of ethanol:water = 4:1 (volume ratio). While stirring the suspension, the substrate AZ31 plate was inserted as the working electrode and a stainless steel mesh plate as the counter electrode. A pulse voltage of peak-peak (pp) voltage 10V, frequency 0.1 Hz, and duty ratio 98% was applied between the AZ31 plate as the cathode and the counter electrode for 10 minutes to perform electrophoretic deposition (EPD). The AZ31 plate after EPD was dried at 100°C for 1 hour, and then ultrasonically cleaned with an isopropanol solution to obtain an LDH-deposited surface. Incidentally, the surface before the ultrasonic cleaning was visually observed to be uniformly covered with HT powder, but most of the HT powder fell off from the substrate surface after the ultrasonic cleaning.
ＥＰＤにおいて、ＨＴ濃度を１ｗ／ｖ％、２ｗ／ｖ％、３ｗ／ｖ％、５ｗ／ｖ％としたときのＨＴ堆積表面の電子顕微鏡写真を図３に示す。表面にＨＴ粉末の凝集体が付着していた。電解液中のＨＴ粉末濃度の増加に伴い、ＨＴ粉末の付着量は増加したが、超音波洗浄によるＨＴ粉末の脱落により基材表面が露出し、充分な量のＨＴ粉末を付着させることができなかった。Figure 3 shows electron microscope photographs of the HT deposition surface when the HT concentration in EPD was 1 w/v%, 2 w/v%, 3 w/v%, and 5 w/v%. Agglomerates of HT powder were found attached to the surface. As the HT powder concentration in the electrolyte increased, the amount of HT powder attached increased, but the HT powder fell off during ultrasonic cleaning, exposing the substrate surface, and it was not possible to attach a sufficient amount of HT powder.
＜実施例２＞電解液にＭｇイオンおよび／またはＡｌイオンを添加した場合のＨＴ粉末の電気泳動堆積
基材には、表面を＃１２００の耐水研磨紙で仕上げたＡＺ３１板を用いた。電解液には、エタノール：水＝４：１（体積比）の溶媒に、硝酸マグネシウムおよび硝酸アルミニウムを表１の濃度で溶解し、ＬＤＨとして粒径約１μｍの市販のＨＴ粉末を３ｗ／ｖ％で懸濁した溶液を用いた。表１は、ハイドロタルサイト（ＨＴ）粉末を含むエタノール－水電解液に添加したＭｇイオンおよびＡｌイオン濃度及びＭｇ：Ａｌ濃度比とサンプル名を示している。
次に、同懸濁液を撹拌しながら、作用極として基材ＡＺ３１板および対極としてステンレス鋼メッシュ板を挿入した。ＡＺ３１板を陰極として対極との間にピーク―ピーク（ｐ－ｐ）電圧１０Ｖ、周波数０．１Ｈｚ、デューティー比９８％のパルス電圧を１０分間印加し、ＥＰＤを行った。ＥＰＤ後のＡＺ３１板を１００℃で１時間乾燥した後、イソプロパノール溶液で超音波洗浄し、ＬＤＨ－金属水酸化物の混合堆積層を得た。
Example 2: Electrophoretic deposition of HT powder when Mg ions and/or Al ions are added to the electrolyte An AZ31 plate with the surface finished with #1200 waterproof abrasive paper was used as the substrate. For the electrolyte, magnesium nitrate and aluminum nitrate were dissolved in a solvent of ethanol:water = 4:1 (volume ratio) at the concentrations shown in Table 1, and a solution of commercially available HT powder with a particle size of about 1 μm was suspended as LDH at 3 w/v% was used. Table 1 shows the Mg ion and Al ion concentrations and Mg:Al concentration ratios added to an ethanol-water electrolyte containing hydrotalcite (HT) powder, as well as the sample names.
Next, while stirring the suspension, the substrate AZ31 plate was inserted as the working electrode and a stainless steel mesh plate as the counter electrode. A pulse voltage with a peak-to-peak (pp) voltage of 10 V, a frequency of 0.1 Hz, and a duty ratio of 98% was applied between the AZ31 plate and the counter electrode as the cathode for 10 minutes to perform EPD. The AZ31 plate after EPD was dried at 100°C for 1 hour and then ultrasonically cleaned with an isopropanol solution to obtain a mixed deposition layer of LDH-metal hydroxide.
表１の電解液中に３ｗ／ｖ％のＨＴ粉末を添加してＥＰＤした混合堆積層の電子顕微鏡写真を図４に示す。図４では、参考例１（図１の「３％ＨＴ」）と比較すると、電解液へのＭｇイオンおよび／またはＡｌイオンの添加でＨＴ粉末の付着量が増加し、超音波洗浄後でも基材表面がＨＴ粉末で充分に覆おわれたことが示されている。
図５に表１の電解液中に３ｗ／ｖ％のＨＴ粉末を添加してＥＰＤした混合堆積層のＸ線回折パターンを示しており、（Ａ）はＡｌイオンまたはＭｇイオンのみを添加した場合、（Ｂ）はＭｇイオンおよびＡｌイオンの両方を添加した場合を示している。いずれの電解液中でもＨＴ粉末に由来するＸＲＤピークが得られた。ＭｇイオンおよびＡｌイオンの両方を添加した電解液中で形成した混合堆積層のＨＴ粉末ピークの方が、ＭｇイオンもしくはＡｌイオンのどちらか一方を添加した電解液中で形成した混合堆積層のＨＴ粉末ピークよりもピーク強度が高かった。また、低い濃度のＭｇイオンおよびＡｌイオンを添加した電解液中で形成した混合堆積層も明瞭なＨＴ粉末ピークを示した。
Fig. 4 shows an electron microscope photograph of a mixed deposit layer subjected to EPD with 3 w/v % HT powder added to the electrolyte in Table 1. In Fig. 4, in comparison with Reference Example 1 ("3% HT" in Fig. 1), the amount of HT powder attached was increased by adding Mg ions and/or Al ions to the electrolyte, and the substrate surface was sufficiently covered with HT powder even after ultrasonic cleaning.
FIG. 5 shows the X-ray diffraction patterns of the mixed deposition layer subjected to EPD by adding 3 w/v% HT powder to the electrolyte of Table 1, where (A) shows the case where only Al ions or Mg ions were added, and (B) shows the case where both Mg ions and Al ions were added. In both electrolytes, XRD peaks derived from HT powder were obtained. The HT powder peak of the mixed deposition layer formed in the electrolyte to which both Mg ions and Al ions were added had a higher peak intensity than the HT powder peak of the mixed deposition layer formed in the electrolyte to which either Mg ions or Al ions were added. In addition, the mixed deposition layer formed in the electrolyte to which low concentrations of Mg ions and Al ions were added also showed a clear HT powder peak.
ワンショット３Ｄ形状測定機（キーエンス製、検出感度：１μｍ以上）で計測した混合堆積層厚さと電解液のＭｇイオンとＡｌイオンの合計濃度との関係を図６に示す。混合堆積層は１μｍから１３０μｍの厚さを示し、電解液のＭｇおよびＡｌイオン濃度の増加に伴い厚くなる傾向を示した。The relationship between the thickness of the mixed deposition layer measured with a one-shot 3D shape measuring instrument (Keyence, detection sensitivity: 1 μm or more) and the total concentration of Mg ions and Al ions in the electrolyte is shown in Figure 6. The mixed deposition layer showed thicknesses from 1 μm to 130 μm, and showed a tendency to become thicker as the Mg and Al ion concentrations in the electrolyte increased.
＜実施例３＞実施例２で作製したサンプルの乾湿繰り返し試験
基材にＡＺ３１を用いて作製した表２に示すサンプルの乾湿繰り返し試験を行った。表２は、乾湿繰り返し試験に用いたＬＤＨ－金属水酸化物混合堆積サンプルを示している。
サンプル表面に１ｇ／ｍ２のＮａＣｌを付着させた後、相対湿度ＲＨ３０％に８時間、ＲＨ９５％に８時間、ＲＨ３０％に８時間を１サイクルとしてサンプル周囲の相対湿度を変化させる乾湿繰り返し試験を、合計４サイクル行った。図７にＬＤＨ－金属水酸化物混合堆積表面の乾湿繰り返し試験後の外観写真を示す。比較のために、同様の乾湿繰り返し試験を行った研磨ままＡＺ３１の外観写真を示す。研磨ままＡＺ３１では、全面で腐食が発生し、深い腐食孔が局所的にみられた。これに対し、ＬＤＨの一種であるＨＴ粉末と金属水酸化物の混合堆積層を被覆すると、目視でわかる深い腐食孔の発生頻度が大幅に減少した。ＬＤＨ－金属水酸化物混合堆積層は耐食被膜として働くことが示された。
A wet-dry cycle test was carried out on the samples shown in Table 2, which were prepared using AZ31 as the substrate. Table 2 shows the LDH-metal hydroxide mixed deposition samples used in the wet-dry cycle test.
After 1 g/ m2 of NaCl was applied to the sample surface, a wet-dry cycle test was performed in which the relative humidity around the sample was changed to 30% RH for 8 hours, 95% RH for 8 hours, and 30% RH for 8 hours, for a total of 4 cycles. Figure 7 shows an appearance photograph of the LDH-metal hydroxide mixed deposition surface after the wet-dry cycle test. For comparison, an appearance photograph of as-polished AZ31, which was subjected to a similar wet-dry cycle test, is shown. In the as-polished AZ31, corrosion occurred over the entire surface, and deep corrosion pits were observed locally. In contrast, when the mixed deposition layer of HT powder, a type of LDH, and metal hydroxide was coated, the frequency of occurrence of deep corrosion pits visible to the naked eye was significantly reduced. It was shown that the LDH-metal hydroxide mixed deposition layer acts as a corrosion-resistant coating.
＜実施例４＞基材純Ｍｇまたは基材ＡＺ３１上へのＬＤＨ－金属水酸化物の混合堆積層の作製及び腐食試験
基材には、表面を＃１２００の耐水研磨紙で仕上げた純ＭｇおよびＡＺ３１を用いた。電解液には、エタノール：水＝４：１（体積比）の溶媒に、硝酸マグネシウムおよび硝酸アルミニウムを表３の濃度で溶解し、ＬＤＨとして粒径約１μｍの市販のＨＴ粉末を５ｗ／ｖ％で懸濁した溶液を用いた。表３は、乾湿繰り返し試験用に作製したハイドロタルサイト（ＨＴ）粉末濃度５％の場合のＬＤＨ－金属水酸化物混合堆積サンプルを示している。
同懸濁液を撹拌しながら、作用極として基材ＡＺ３１板又は純Ｍｇ板および対極としてステンレス鋼メッシュ板を挿入した。ＡＺ３１板又は純Ｍｇを陰極として対極との間にピーク―ピーク（ｐ－ｐ）電圧１０Ｖ、周波数０．１Ｈｚのパルス電圧をデューティー比９８％で１０分間、もしくはデューティー比５０％で２０分間印加し、ＥＰＤを行った。ＥＰＤ後の純Ｍｇ板およびＡＺ３１板を１００℃で１時間乾燥した後、アセトン中で超音波洗浄し、ＬＤＨ－金属水酸化物の混合堆積層を得た。
The substrates used were pure Mg and AZ31, the surfaces of which had been finished with #1200 waterproof abrasive paper. The electrolyte used was a solution in which magnesium nitrate and aluminum nitrate were dissolved in a solvent of ethanol:water = 4:1 (volume ratio) at the concentrations shown in Table 3, and a commercially available HT powder with a particle size of about 1 μm was suspended as the LDH at 5 w/v%. Table 3 shows LDH-metal hydroxide mixed deposition samples with a hydrotalcite (HT) powder concentration of 5% prepared for wet-dry cycle testing.
While stirring the suspension, a substrate AZ31 plate or pure Mg plate was inserted as a working electrode and a stainless steel mesh plate as a counter electrode. A pulse voltage with a peak-to-peak (pp) voltage of 10 V and a frequency of 0.1 Hz was applied between the AZ31 plate or pure Mg as a cathode and the counter electrode at a duty ratio of 98% for 10 minutes or a duty ratio of 50% for 20 minutes to perform EPD. The pure Mg plate and the AZ31 plate after EPD were dried at 100°C for 1 hour and then ultrasonically cleaned in acetone to obtain a mixed deposition layer of LDH-metal hydroxide.
表３に示すサンプルの乾湿繰り返し試験を行った。サンプル表面に１ｇ／ｍ２のＮａＣｌを付着させた後、相対湿度ＲＨ３０％に８時間、ＲＨ９５％に８時間、ＲＨ２０％に８時間を１サイクルとしてサンプル周囲の相対湿度を変化させる乾湿繰り返し試験を、合計４サイクル行った。
図８に乾湿繰り返し試験前後のサンプル外観写真を示しており、（Ａ）は純Ｍｇ板、（Ｂ）はＡＺ３１板を示している。ＬＤＨの一種であるＨＴと金属水酸化物の混合堆積層を被覆すると、純Ｍｇでも腐食面積が５０％程度に大幅に減少した。ＡＺ３１では目視でわかる顕著な腐食はみられなかった。作製したＬＤＨ－金属水酸化物混合堆積層は、基材Ｍｇ合金の組成に関わらず耐食被膜として働くことを示した。
A wet-dry cycle test was carried out on the samples shown in Table 3. After 1 g/ m2 of NaCl was attached to the surface of the sample, a wet-dry cycle test was carried out in which the relative humidity around the sample was changed to 30% RH for 8 hours, 95% RH for 8 hours, and 20% RH for 8 hours, for a total of 4 cycles.
Figure 8 shows photos of the appearance of samples before and after the wet-dry cycle test, with (A) showing a pure Mg plate and (B) showing an AZ31 plate. When coated with a mixed deposition layer of HT, a type of LDH, and metal hydroxide, the corroded area was significantly reduced to about 50%, even for pure Mg. No significant corrosion visible to the naked eye was observed for AZ31. This shows that the prepared LDH-metal hydroxide mixed deposition layer functions as a corrosion-resistant coating regardless of the composition of the substrate Mg alloy.
＜実施例５＞定電圧の電気泳動堆積法による基材ＡＺ３１上へのＬＤＨ－金属水酸化物の混合堆積層の作製
基材には、表面を＃１２００の耐水研磨紙で仕上げたＡＺ３１板を用いた。電解液には、イソプロパノール：水＝９８：２もしくは９６：４（体積比）の溶媒に硝酸マグネシウムを表４の濃度で溶解し、ＬＤＨとして粒径約１μｍの市販のＨＴ粉末を４ｗ／ｖ％で懸濁した溶液を用いた。表４は、イソプロパノール－水電解液に添加したＭｇイオン濃度及び印加電圧とサンプル名を示している。
作用極として基材ＡＺ３１板および対極としてステンレス鋼板を挿入した。ＡＺ３１板を陰極として対極との間に定電圧５０～２００Ｖ、を１分間印加し、ＥＰＤを行った。ＥＰＤ後のＡＺ３１板は室温で乾燥した。表面を手袋をした手で軽くこすってもＨＴ粉末の剥落はなかったため、超音波洗浄は行わなかった。実施例１～４よりも高電圧の印加で、ＨＴ粉末の付着性が向上した。
図９に混合堆積層の電子顕微鏡写真を示す。１分間という短時間で緻密なＬＤＨ－金属水酸化物混合堆積層が形成されたことがわかる。実施例２～４よりも溶媒中の水の体積比を小さくすると、定電圧でのＥＰＤで均質なＬＤＨ－金属水酸化物混合堆積層が形成できることが示された。
Example 5: Preparation of a mixed deposition layer of LDH-metal hydroxide on a substrate AZ31 by constant voltage electrophoretic deposition method An AZ31 plate with the surface finished with #1200 waterproof abrasive paper was used as the substrate. For the electrolyte, magnesium nitrate was dissolved in a solvent of isopropanol:water = 98:2 or 96:4 (volume ratio) at the concentrations shown in Table 4, and a solution of commercially available HT powder with a particle size of about 1 μm was suspended as LDH at 4 w/v% was used. Table 4 shows the Mg ion concentration and applied voltage added to the isopropanol-water electrolyte, and the sample name.
An AZ31 substrate plate was inserted as the working electrode and a stainless steel plate as the counter electrode. A constant voltage of 50 to 200 V was applied between the AZ31 plate as the cathode and the counter electrode for 1 minute to perform EPD. The AZ31 plate after EPD was dried at room temperature. Since the HT powder did not peel off even when the surface was lightly rubbed with a gloved hand, ultrasonic cleaning was not performed. The application of a higher voltage than in Examples 1 to 4 improved the adhesion of the HT powder.
An electron microscope photograph of the mixed deposition layer is shown in Figure 9. It can be seen that a dense LDH-metal hydroxide mixed deposition layer was formed in a short time of one minute. It was shown that a homogeneous LDH-metal hydroxide mixed deposition layer can be formed by EPD at a constant voltage when the volume ratio of water in the solvent is made smaller than in Examples 2 to 4.
＜実施例６＞定電圧の電気泳動堆積法による基材純Ａｌまたは純Ｆｅ上へのモリブデン酸イオンを含むＬＤＨ－金属水酸化物の混合堆積層の作製及び腐食試験
基材には、純Ａｌおよび純Ｆｅの２種類を用いた。基材表面に堆積する層状複水酸化物（ＬＤＨ）粉末には、層間にモリブデン酸イオン（ＭｏＯ４
２－）を含むＭｏＬＤＨ粉末もしくは層間に炭酸イオン（ＣＯ３
２－）を含むハイドロタルサイト（ＨＴ）粉末の２種類を用いた。
２種類の板材表面を＃１２００の耐水研磨紙で仕上げ、基板とした。電解液には、イソプロパノール：水＝４０：１（体積比）の溶媒に、０．０４ｍｏｌ／Ｌの硝酸マグネシウムおよび０．０１ｍｏｌ／Ｌの硝酸アルミニウムを溶解し、ＭｏＬＤＨ粉末もしくはＨＴ粉末を２ｗ／ｖ％（ｗｅｉｇｈｔ／ｖｏｌｕｍｅ％）で懸濁した溶液を用いた。電解液に作用極として基板、および対極としてステンレス鋼板又はカーボン板を挿入した。基板を陰極として対極との間に定電圧１００Ｖを１分間印加し、電気泳動堆積（ＥＰＤ）を行った。ＥＰＤ後の基板を１００℃で１時間乾燥し、ＭｏＬＤＨ粉末－金属水酸化物の混合堆積被覆サンプルもしくはＨＴ粉末－金属水酸化物の混合堆積被覆サンプルを得た。作製したサンプルのサンプル名を表５に示す。
Example 6: Preparation of a mixed deposition layer of LDH-metal hydroxide containing molybdate ions on a pure Al or Fe substrate by constant voltage electrophoretic deposition method and corrosion test Two types of substrates were used: pure Al and pure Fe. For the layered double hydroxide (LDH) powder deposited on the substrate surface, two types were used: MoLDH powder containing molybdate ions (MoO 4 2− ) between layers, or hydrotalcite (HT) powder containing carbonate ions (CO 3 2− ) between layers.
The surfaces of the two types of plate materials were finished with #1200 waterproof abrasive paper to prepare the substrate. For the electrolyte, a solution was used in which 0.04 mol/L magnesium nitrate and 0.01 mol/L aluminum nitrate were dissolved in a solvent of isopropanol:water = 40:1 (volume ratio), and MoLDH powder or HT powder was suspended at 2 w/v% (weight/volume%). The substrate was inserted as the working electrode, and a stainless steel plate or a carbon plate as the counter electrode into the electrolyte. A constant voltage of 100V was applied between the substrate as the cathode and the counter electrode for 1 minute to perform electrophoretic deposition (EPD). The substrate after EPD was dried at 100°C for 1 hour to obtain a mixed deposition coating sample of MoLDH powder-metal hydroxide or a mixed deposition coating sample of HT powder-metal hydroxide. The sample names of the prepared samples are shown in Table 5.
純Ａｌと純Ｆｅの、ＭｏＬＤＨ粉末の被覆表面の電子顕微鏡像を図１０に、ＨＴ粉末の被覆表面の電子顕微鏡像を図１１に示す。ＭｏＬＤＨ粉末もしくはＨＴ粉末を含む堆積層が表面に形成したことがわかる。純Ａｌと純Ｆｅの、ＭｏＬＤＨ粉末の被覆表面のＸ線回折パターンを図１２に、ＨＴ粉末の被覆表面のＸ線回折パターンを図１３に示す。ＭｏＬＤＨ粉末被覆表面およびＨＴ粉末被覆表面では、それぞれＭｏＬＤＨ粉末およびＨＴ粉末に由来するＸ線回折ピークに加えて、粉末と共に析出した金属水酸化物およびそれぞれの基材からの回折ピークが得られた。析出した金属水酸化物の回折ピークはＭｏＬＤＨまたはＨＴの回折ピークの低角度側の肩ピークとして現れていることから、ＬＤＨの一種であることが示唆される。図１０～図１３の結果より被覆層は、ＭｏＬＤＨ粉末もしくはＨＴ粉末および電解液から析出したＬＤＨで構成されることが明らかになった。 Electron microscope images of the MoLDH powder coating surface of pure Al and pure Fe are shown in Figure 10, and electron microscope images of the HT powder coating surface are shown in Figure 11. It can be seen that a deposition layer containing MoLDH powder or HT powder was formed on the surface. X-ray diffraction patterns of the MoLDH powder coating surface of pure Al and pure Fe are shown in Figure 12, and X-ray diffraction patterns of the HT powder coating surface are shown in Figure 13. In addition to the X-ray diffraction peaks derived from MoLDH powder and HT powder, the MoLDH powder coating surface and the HT powder coating surface showed diffraction peaks from metal hydroxides precipitated with the powder and from the respective substrates. The diffraction peaks of the precipitated metal hydroxides appear as shoulder peaks on the low-angle side of the diffraction peaks of MoLDH or HT, suggesting that they are a type of LDH. From the results of Figures 10 to 13, it became clear that the coating layer was composed of MoLDH powder or HT powder and LDH precipitated from the electrolyte.
表５に示すＭｏＬＤＨもしくはＨＴ被覆サンプルの乾湿繰り返し試験を行った。サンプル表面に１ｇ／ｍ２のＮａＣｌを付着させた後、相対湿度ＲＨ３０％に８時間、ＲＨ９５％に８時間、ＲＨ３０％に８時間を１サイクルとしてサンプル周囲の相対湿度を変化させる乾湿繰り返し試験を、合計７サイクル行った。 A wet-dry cycle test was carried out on the MoLDH or HT coated samples shown in Table 5. After 1 g/ m2 of NaCl was attached to the sample surface, a wet-dry cycle test was carried out in which the relative humidity around the sample was changed to 30% RH for 8 hours, 95% RH for 8 hours, and 30% RH for 8 hours, for a total of 7 cycles.
図１４にＭｏＬＤＨ粉末被覆表面およびＨＴ粉末被覆表面の乾湿繰り返し試験後の外観写真を示す。比較のために、同様の乾湿繰り返し試験を行った未被覆純Ａｌおよび未被覆純Ｆｅの外観写真を示す。乾湿繰り返し試験後の未被覆Ａｌ表面は変色している領域がみられるのに対し、ＭｏＬＤＨ－Ａｌ表面およびＨＴ－Ａｌ表面では肉眼でわかる変化はみられなかった。未被覆Ｆｅ表面全体には錆が斑点状に形成され、ほぼ全面で腐食が発生したことがわかる。一方、ＭｏＬＤＨ－Ｆｅ表面およびＨＴ－Ｆｅ表面では一部に錆（変色して暗くみえる箇所）がみられるが、腐食箇所の面積は大きく減少し、ＭｏＬＤＨ－Ｆｅ表面の方がＨＴ－Ｆｅ表面よりも腐食面積は小さかった。 Figure 14 shows photographs of the appearance of the MoLDH powder-coated surface and the HT powder-coated surface after a wet-dry cycle test. For comparison, photographs of the appearance of uncoated pure Al and uncoated pure Fe, which were subjected to a similar wet-dry cycle test, are shown. Discolored areas were visible on the uncoated Al surface after the wet-dry cycle test, whereas no changes visible to the naked eye were observed on the MoLDH-Al and HT-Al surfaces. Rust was spotted over the entire uncoated Fe surface, indicating that corrosion had occurred over almost the entire surface. Meanwhile, rust (discolored and dark areas) was visible in some areas on the MoLDH-Fe and HT-Fe surfaces, but the area of corroded areas had significantly decreased, and the corroded area was smaller on the MoLDH-Fe surface than on the HT-Fe surface.
図１５に、乾湿繰り返し試験前後でのサンプルの重量変化を示す。（ａ）では、基材に純Ａｌを用い、（ｂ）では、基材にＦｅを用いた。未被覆Ａｌおよび未被覆Ｆｅは乾湿繰り返し試験後に重量が減少し、試験後の水洗いにより腐食生成物が一部溶解して重量が減少したことがわかった。一方、ＭｏＬＤＨ粉末もしくはＨＴ粉末被覆サンプルでは、乾湿繰り返し試験後に重量が増加し、水洗いで腐食生成物は溶解しないことがわかった。したがって、ＭｏＬＤＨ粉末もしくはＨＴ粉末被覆サンプルでは、重量変化が大きいほど腐食量が大きい。純Ａｌおよび純Ｆｅの両方とも、ＭｏＬＤＨ粉末被覆サンプルの方がＨＴ粉末被覆サンプルよりも重量変化が小さかった。これは、腐食インヒビターを含有したＭｏＬＤＨ粉末被覆表面の方がＨＴ粉末被覆表面よりも耐食性が高いこと示している。 Figure 15 shows the weight change of the samples before and after the wet-dry cycle test. In (a), pure Al was used as the substrate, and in (b), Fe was used as the substrate. The weight of uncoated Al and uncoated Fe decreased after the wet-dry cycle test, and it was found that the corrosion products were partially dissolved by washing with water after the test, resulting in a weight loss. On the other hand, the weight of the MoLDH powder or HT powder-coated samples increased after the wet-dry cycle test, and it was found that the corrosion products were not dissolved by washing with water. Therefore, the greater the weight change in the MoLDH powder or HT powder-coated samples, the greater the amount of corrosion. For both pure Al and pure Fe, the weight change of the MoLDH powder-coated samples was smaller than that of the HT powder-coated samples. This indicates that the MoLDH powder-coated surface containing the corrosion inhibitor is more corrosion-resistant than the HT powder-coated surface.
図１４および図１５の結果は、モリブデン酸イオンのような腐食インヒビターを含むＭｏＬＤＨを被覆すると、乾湿繰り返し試験中にＭｏＬＤＨから放出されたモリブデン酸イオンが、基材純Ａｌや純Ｆｅの腐食発生もしくは腐食進展を抑制したことを示している。したがって、本発明の方法はインヒビターを層間に挿入したＬＤＨの被覆法として有効なこと、および被覆されたインヒビター含有ＬＤＨ被膜は自己修復性発揮に必要な、腐食環境でのインヒビターの放出を起こすことが明らかになった。 The results of Figures 14 and 15 show that when MoLDH containing a corrosion inhibitor such as molybdate ions was coated, the molybdate ions released from MoLDH during the dry-wet cycle test suppressed the onset or progression of corrosion of the substrates pure Al and pure Fe. Therefore, it was clarified that the method of the present invention is effective as a coating method for LDH with an inhibitor inserted between layers, and that the coated inhibitor-containing LDH coating causes the release of inhibitors in a corrosive environment, which is necessary for the self-repairing property to be exhibited.
上記の実施例２～６によれば、次の効果がある。
（１）電解液の溶媒にエタノール－水混合溶媒もしくはイソプロパノール－水混合溶媒を用いることで、マグネシウム合金の腐食原因である水の影響を低減した。マグネシウム合金の腐食反応におけるカソード反応は水の還元反応であることから、水の割合を低下させることで、マグネシウム合金の腐食を抑制できる。また、水の還元反応で発生する水素ガスを減らすことができるため、被膜の欠陥を減らすことができる。なお、エタノールやイソプロパノールに変えてエチレングリコールやグリセリンなどの有機溶媒を用いることもできる。
（２）エタノール－水混合溶媒にＬＤＨ粉末を懸濁させたのみの電解液中で堆積させた参考例１等のＬＤＨ層では、アセトンもしくはイソプロパノール中での超音波洗浄によりほとんどのＬＤＨ粉末が脱落してしまった。
一方、エタノール－水混合溶媒にＭｇ（ＮＯ３）２および／もしくはＡｌ（ＮＯ３）３を添加した電解液中で堆積させたＬＤＨ粉末―金属水酸化物混合堆積層では、アセトンもしくはイソプロパノール中での超音波洗浄後でもほぼ均一な混合堆積層が残っていた。これより、電解液中への金属硝酸塩の添加は、ＬＤＨ粉末の密着性向上に有効であることがわかる。
（３）水の体積比が小さいイソプロパノール－水混合溶媒にＭｇ（ＮＯ３）２を添加した電解液中で、高電圧で堆積させたＬＤＨ粉末―金属水酸化物混合堆積層は、ＥＰＤままの表面を手袋をはめた手で軽くこすっても剥落しなかった。ＬＤＨ粉末―金属水酸化物混合堆積層の付着性の向上には印加電圧の増加が有効であることがわかる。
（４）本願実施形態に係る方法は、腐食インヒビターを層間に含有したＬＤＨ粉末―金属水酸化物混合堆積層の形成に有効であり、本願実施形態に係る方法によれば、耐食性に非常に優れたＬＤＨ被膜が形成されることがわかる。
According to the above embodiments 2 to 6, the following effects are obtained.
(1) By using an ethanol-water mixed solvent or an isopropanol-water mixed solvent as the solvent for the electrolyte, the effect of water, which is the cause of magnesium alloy corrosion, was reduced. Since the cathodic reaction in the corrosion reaction of magnesium alloys is a reduction reaction of water, the corrosion of magnesium alloys can be suppressed by lowering the proportion of water. In addition, the hydrogen gas generated by the reduction reaction of water can be reduced, which reduces defects in the coating. Note that organic solvents such as ethylene glycol and glycerin can also be used instead of ethanol or isopropanol.
(2) In the LDH layer of Reference Example 1 and the like, which was deposited in an electrolyte solution consisting only of LDH powder suspended in an ethanol-water mixed solvent, most of the LDH powder fell off upon ultrasonic cleaning in acetone or isopropanol.
On the other hand, in the case of the LDH powder-metal hydroxide mixed deposition layer deposited in an electrolyte containing Mg(NO 3 ) 2 and/or Al(NO 3 ) 3 added to an ethanol-water mixed solvent, a nearly uniform mixed deposition layer remained even after ultrasonic cleaning in acetone or isopropanol. This shows that the addition of metal nitrates to the electrolyte is effective in improving the adhesion of the LDH powder.
(3) The LDH powder-metal hydroxide mixed deposition layer deposited at high voltage in an electrolyte containing Mg( NO3 ) 2 added to an isopropanol-water mixed solvent with a small volume ratio of water did not peel off even when the EPD surface was lightly rubbed with a gloved hand. This shows that increasing the applied voltage is effective in improving the adhesion of the LDH powder-metal hydroxide mixed deposition layer.
(4) The method according to the present embodiment is effective for forming an LDH powder-metal hydroxide mixed deposition layer containing a corrosion inhibitor between the layers, and it is found that the method according to the present embodiment forms an LDH coating film with extremely excellent corrosion resistance.
以上詳細に説明したように、本発明の層状複水酸化物を表面に有する金属板の製造方法によればマグネシウム合金およびアルミニウム合金において、高耐食性被膜の形成と、用途によっては高耐食性被膜に加えて塗装も容易に行えるので、これら軽合金を輸送機器や家電製品に用いる場合に、塩化物イオンを含む雨や海水の飛沫や人の汗に曝されても耐久性が高まる。As explained in detail above, the manufacturing method of metal plate having the layered double hydroxide of the present invention on the surface thereof makes it possible to easily form a highly corrosion-resistant coating on magnesium alloys and aluminum alloys, and in some applications, painting can also be performed in addition to the highly corrosion-resistant coating. Therefore, when these light alloys are used in transportation equipment or home appliances, their durability is increased even when they are exposed to rain or seawater containing chloride ions or human sweat.
１０：電解槽
１２：基材（被処理金属基板、電極基板）
１４：対極板
１６：表面処理溶液（電解液）
１８：堆積した金属水酸化物
２０：スターラー
２２：攪拌子
３０：直流電源
３６：関数発生器
４０：ＬＤＨ（層状複水酸化物）粉末
４２：添加金属イオン
10: Electrolytic cell 12: Base material (metal substrate to be treated, electrode substrate)
14: Counter electrode plate 16: Surface treatment solution (electrolyte)
18: deposited metal hydroxide 20: stirrer 22: stirring bar 30: DC power supply 36: function generator 40: LDH (layered double hydroxide) powder 42: added metal ions
Claims (14)
添加した前記金属イオンを含む前記電解液と前記層状複水酸化物粉末からなる懸濁液に電極基板と対極板を浸漬する工程であって、前記電極基板は被覆処理される金属板であり、
前記電極基板と前記対極板との間に電場を印加することにより、前記電極基板上に前記層状複水酸化物粉末と共に前記金属イオンの水酸化物として電析させる工程を有すると共に、
前記電析では前記金属イオンからの金属の電析を含まないことを特徴とする、
層状複水酸化物を表面に有する金属板の製造方法。 a step of adding metal ions to an electrolytic solution containing water and dispersing a layered double hydroxide powder in the electrolytic solution, or a step of dispersing a layered double hydroxide powder in the electrolytic solution containing water and adding metal ions to the electrolytic solution;
a step of immersing an electrode substrate and a counter electrode plate in a suspension composed of the electrolytic solution containing the added metal ions and the layered double hydroxide powder, the electrode substrate being a metal plate to be coated;
a step of applying an electric field between the electrode substrate and the counter electrode plate to electrodeposit the metal ions as hydroxides together with the layered double hydroxide powder on the electrode substrate;
The electrodeposition does not include electrodeposition of a metal from the metal ions.
A method for producing a metal plate having a layered double hydroxide on its surface.
前記金属イオンを生成する金属塩は、硝酸塩、硫酸塩、炭酸塩、カルボン酸塩、リン酸塩又は塩化物である、
ことを特徴とする請求項１乃至４の何れか１項に記載の層状複水酸化物を表面に有する金属板の製造方法。 The metal ion is any one of Mg, Al, Zn, Mn, Fe, Co, Ca, Cr, and In,
The metal salt that generates the metal ion is a nitrate, sulfate, carbonate, carboxylate, phosphate or chloride.
A method for producing a metal plate having the layered double hydroxide according to any one of claims 1 to 4 on its surface.
Ｍ２＋は、Ｍｇ（マグネシウム），Ｚｎ（亜鉛），Ｃａ（カルシウム），Ｍｎ（マンガン），Ｐｄ（パラジウム），Ｓｒ（ストロンチウム），Ｆｅ（鉄），Ｃｏ（コバルト），Ｎｉ（ニッケル），Ｃｕ（銅）の何れか１種類から選択される二価金属イオンであり、
Ｍ３＋は、Ａｌ（アルミニウム），Ｂｉ（ビスマス），Ｇａ（ガリウム），Ｎｉ（ニッケル），Ｍｎ，Ｖ（バナジウム），Ｃｅ（セリウム），Ｌａ（ランタン），Ｃｒ（クロム），Ｆｅ（鉄），Ｃｏ（コバルト），Ｉｎ（インジウム）の何れか１種類から選択される三価金属イオンであり、
前記Ａは、ＮＯ３ －，ＣＯ３ ２－，ＯＨ－，Ｃｌ－，ＳＯ４ ２－，ＳｉＯ４ ４－の何れか１種類から選択される陰イオン、又は、リン酸、クロム酸、過マンガン酸、バナジン酸、セレン酸、ホウ酸、フッ化物、カルボン酸、すず酸、アルミン酸、及びモリブデン酸の何れか１種類から選択されるｎ価（ｎ＝１、２、３、又は４）の陰イオンである、
請求項１乃至５の何れか１項に記載の層状複水酸化物を表面に有する金属板の製造方法。 The layered double hydroxide powder is represented by the general formula: [M 2+ (1-x) M 3+ x (OH) 2 ][A n- x/n ·yH 2 O],
M2 + is a divalent metal ion selected from any one of Mg (magnesium), Zn (zinc), Ca (calcium), Mn (manganese), Pd (palladium), Sr (strontium), Fe (iron), Co (cobalt), Ni (nickel), and Cu (copper);
M3 + is a trivalent metal ion selected from any one of Al (aluminum), Bi (bismuth), Ga (gallium), Ni (nickel), Mn, V (vanadium), Ce (cerium), La (lanthanum), Cr (chromium), Fe (iron), Co (cobalt), and In (indium);
A is an anion selected from any one of NO 3 − , CO 3 2− , OH − , Cl − , SO 4 2− , and SiO 4 4− , or an n-valent (n=1, 2, 3, or 4) anion selected from any one of phosphate, chromate, permanganate, vanadate, selenate, borate, fluoride, carboxylate, stannate, aluminate, and molybdate;
A method for producing a metal plate having the layered double hydroxide according to any one of claims 1 to 5 on its surface.
請求項６又は７に記載の層状複水酸化物を表面に有する金属板の製造方法。 the volume ratio of the layered double hydroxide powder to the metal hydroxide in the deposition layer electrodeposited on the electrode substrate is layered double hydroxide powder:metal hydroxide=90:10 to 10:90;
A method for producing a metal plate having the layered double hydroxide according to claim 6 or 7 on its surface.
請求項１乃至８の何れか１項に記載の層状複水酸化物を表面に有する金属板の製造方法。 The electrode substrate is a pure Mg material, a pure Al material, a pure Fe material, an AZ31 (Mg-3Al-1Zn) alloy, an AZ91 (Mg-9Al-1Zn) alloy, an AM60 (Mg-6Al-0.4Mn) alloy, an AXM (Mg-Al-(Zn)-Ca) alloy, a WE43 (Mg-4Y-3RE) alloy, or a ZK60 (Mg-6Zn-0.5Zr) alloy, a 5000 series Al alloy (Al-Mg), a 6000 series Al alloy (Al-Mg-Si), a 7000 series Al alloy (Al-Zn-Mg) alloy, or a carbon steel;
A method for producing a metal plate having the layered double hydroxide according to any one of claims 1 to 8 on its surface.
前記層状複水酸化物は層状複水酸化物粉末－金属水酸化物の混合堆積被膜であり、
前記混合堆積被膜の厚さは、０．５μｍ以上１３０μｍ以下である、
層状複水酸化物を表面に有する金属板であって、
前記混合堆積被膜には前記金属水酸化物の金属が電析していないことを特徴とする、
層状複水酸化物を表面に有する金属板。 A metal plate having a layered double hydroxide on a surface thereof,
The layered double hydroxide is a mixed deposited coating of layered double hydroxide powder and metal hydroxide,
The thickness of the mixed deposition coating is 0.5 μm or more and 130 μm or less.
A metal plate having a layered double hydroxide on a surface thereof,
The mixed deposition coating is characterized in that no metal of the metal hydroxide is electrodeposited on the mixed deposition coating.
A metal plate having a layered double hydroxide on its surface.
Ｍ２＋は、Ｍｇ（マグネシウム），Ｚｎ（亜鉛），Ｃａ（カルシウム），Ｍｎ（マンガン），Ｐｄ（パラジウム），Ｓｒ（ストロンチウム），Ｆｅ（鉄），Ｃｏ（コバルト），Ｎｉ（ニッケル），Ｃｕ（銅）の何れか１種類から選択される二価金属イオンであり、
Ｍ３＋は、Ａｌ（アルミニウム），Ｂｉ（ビスマス），Ｇａ（ガリウム），Ｎｉ（ニッケル），Ｍｎ，Ｖ（バナジウム），Ｃｅ（セリウム），Ｌａ（ランタン），Ｃｒ（クロム），Ｆｅ（鉄），Ｃｏ（コバルト），Ｉｎ（インジウム）の何れか１種類から選択される三価金属イオンであり、
前記Ａは、ＮＯ３ －，ＣＯ３ ２－，ＯＨ－，Ｃｌ－，ＳＯ４ ２－，ＳｉＯ４ ４－の何れか１種類から選択される陰イオン、又は、リン酸、クロム酸、過マンガン酸、バナジン酸、セレン酸、ホウ酸、フッ化物、カルボン酸、すず酸、アルミン酸、及びモリブデン酸の何れか１種類から選択されるｎ価（ｎ＝１、２、３、又は４）の陰イオンである、
請求項１１又は１２に記載の層状複水酸化物を表面に有する金属板。 The layered double hydroxide powder is represented by the general formula: [M 2+ (1-x) M 3+ x (OH) 2 ][A n- x/n ·yH 2 O],
M2 + is a divalent metal ion selected from any one of Mg (magnesium), Zn (zinc), Ca (calcium), Mn (manganese), Pd (palladium), Sr (strontium), Fe (iron), Co (cobalt), Ni (nickel), and Cu (copper);
M3 + is a trivalent metal ion selected from any one of Al (aluminum), Bi (bismuth), Ga (gallium), Ni (nickel), Mn, V (vanadium), Ce (cerium), La (lanthanum), Cr (chromium), Fe (iron), Co (cobalt), and In (indium);
A is an anion selected from any one of NO 3 − , CO 3 2− , OH − , Cl − , SO 4 2− , and SiO 4 4− , or an n-valent (n=1, 2, 3, or 4) anion selected from any one of phosphate, chromate, permanganate, vanadate, selenate, borate, fluoride, carboxylate, stannate, aluminate, and molybdate;
A metal plate having the layered double hydroxide according to claim 11 or 12 on its surface.
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