CN107419310A - A kind of trivalent chrome plating and preparation method thereof - Google Patents
A kind of trivalent chrome plating and preparation method thereof Download PDFInfo
- Publication number
- CN107419310A CN107419310A CN201710899809.6A CN201710899809A CN107419310A CN 107419310 A CN107419310 A CN 107419310A CN 201710899809 A CN201710899809 A CN 201710899809A CN 107419310 A CN107419310 A CN 107419310A
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- China
- Prior art keywords
- acid
- weight
- parts
- trivalent
- base material
- Prior art date
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000007747 plating Methods 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000011651 chromium Substances 0.000 claims abstract description 85
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 80
- 239000000463 material Substances 0.000 claims abstract description 66
- 150000003839 salts Chemical group 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 229910001868 water Inorganic materials 0.000 claims abstract description 35
- 239000000872 buffer Substances 0.000 claims abstract description 25
- 238000009713 electroplating Methods 0.000 claims abstract description 25
- 239000010410 layer Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000011247 coating layer Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 43
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 38
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 34
- VTUAYVWUPOHGAU-UHFFFAOYSA-N 2-amino-1,3-benzothiazole-7-carboxylic acid Chemical compound C1=CC(C(O)=O)=C2SC(N)=NC2=C1 VTUAYVWUPOHGAU-UHFFFAOYSA-N 0.000 claims description 28
- 235000019253 formic acid Nutrition 0.000 claims description 26
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 23
- 235000018417 cysteine Nutrition 0.000 claims description 23
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 22
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 22
- 150000001868 cobalt Chemical class 0.000 claims description 22
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 21
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 19
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 19
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 19
- 235000011152 sodium sulphate Nutrition 0.000 claims description 19
- 239000004327 boric acid Substances 0.000 claims description 18
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 17
- 239000004471 Glycine Substances 0.000 claims description 17
- 239000001630 malic acid Substances 0.000 claims description 17
- 235000011090 malic acid Nutrition 0.000 claims description 17
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 17
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 17
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000012811 non-conductive material Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 7
- 235000009508 confectionery Nutrition 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000004475 Arginine Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 claims description 3
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229960003067 cystine Drugs 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229930182817 methionine Natural products 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- FTCLAXOKVVLHEG-UHFFFAOYSA-N sodium;3-sulfanylpropane-1-sulfonic acid Chemical compound [Na].OS(=O)(=O)CCCS FTCLAXOKVVLHEG-UHFFFAOYSA-N 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 125000000151 cysteine group Chemical group N[C@@H](CS)C(=O)* 0.000 claims description 2
- 241000432824 Asparagus densiflorus Species 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000002460 imidazoles Chemical class 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 44
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- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 22
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
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- 238000010438 heat treatment Methods 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
- 235000011182 sodium carbonates Nutrition 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241001272567 Hominoidea Species 0.000 description 1
- 229910000806 Latten Inorganic materials 0.000 description 1
- 241000218194 Laurales Species 0.000 description 1
- 229920005479 Lucite® Polymers 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- WWLOCCUNZXBJFR-UHFFFAOYSA-N azanium;benzenesulfonate Chemical compound [NH4+].[O-]S(=O)(=O)C1=CC=CC=C1 WWLOCCUNZXBJFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940049706 benzodiazepine Drugs 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 235000012839 cake mixes Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 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
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009736 wetting Methods 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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)
Abstract
The present invention relates to trivalent chromium plating field, and in particular to a kind of trivalent chrome plating and preparation method thereof.A kind of preparation method of trivalent chrome plating, including at least following steps：Base material is immersed in trivalent chromium plating solution, electroplated using described base material as negative electrode, electroplating temperature is 20~45 DEG C, current density 6A/dm2~25A/dm2, electroplating time is 5~30min；Trivalent chromium coating layer is on described base material；Described substrate surface, which comprises at least, a conductive layer；Described trivalent chromium plating solution, including at least following components：Tri-valent water soluble chromic salts：15~20 parts by weight；Cobalt salt：12~16 parts by weight；Conducting salt：20~35 parts by weight；Complexant：4~6 parts by weight；Buffer：7~10 parts by weight；Black agent：0.5~1.6 parts by weight；Brightener：0.01~0.5 parts by weight；Deionized water：100 parts by weight.
Description
Technical field
The present invention relates to trivalent chromium plating field, and in particular to a kind of trivalent chrome plating and preparation method thereof.
Background technology
A kind of special coating that black chromium plating belongs in feature chromium coating, because it has good physics, chemical property,
Serious magnificent outward appearance and good wear-resisting, anti-corrosion, heat resistance, application are quite varied.The main component of black chromium plating is
Crome metal and chromium oxide, chrome oxide particle are dispersed in crome metal medium, due to the band-to-band transition and chrome oxide particle of crome metal
Resonance cause black chromium plating that there is very strong absorption to solar radiation.Camera, optical instrument, military issue weapons and instrument
On the parts such as system, the diffusing reflection of light is prevented frequently with black chromium plating；In order to realize to the more effective utilization of solar energy, people
Also electroplating black chromium processing often is carried out to solar collector surface.
The electroplate liquid using chromic anhydride as main component that traditional electroplating black chromium uses, it has high toxicity and high pollution,
At present by the strict limitation of countries in the world.Research is had important using trivalent chromium system instead of hexavalent chromate systems electroplating black chromium
Meaning.Currently substantial amounts of work has been done in the research both at home and abroad to trivalent chromium plating solution, wherein substituting sexavalence with trivalent chromium plating solution
Chromium plating bath progressively popularization and application in terms of decoration chrome plating, but the research of the black chromium of trivalent chromium plating is less, and substantially all
For chloride system, anti-impurity ability be present, anode has chlorine generation to ask the seriously corroded, plating solution maintenance difficulty etc. of coating bath
Topic, and current black chromium plating also has that surface is dark, and bright property is bad, and the porosity of coating is high, corrosion resistance difference and plating
The problems such as layer and the bad adhesion of base material.
For above-mentioned technical problem, research of the invention is based primarily upon the feature of environmental protection and the more preferable sulfate system of stability,
The invention provides a kind of trivalent chrome plating and preparation method thereof, trivalent chrome plating of the invention is by chromium, cobalt, hydrogen, oxygen, sulphur, phosphorus
Formed Deng element, color and luster is pitch black and color is homogeneous, has good melanism degree, and the adhesion of coating and base material is strong, coating
Densification, porosity is low, has extraordinary corrosion resistance.
The content of the invention
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of preparation side of trivalent chrome plating
Method, including at least following steps：Base material is immersed in trivalent chromium plating solution, electroplated using described base material as negative electrode, is electroplated
Temperature is 20~45 DEG C, current density 6A/dm2~25A/dm2, electroplating time is 5~30min；Trivalent chromium coating layer is in institute
On the base material stated；Described substrate surface comprises at least a conductive layer；
Described trivalent chromium plating solution, including at least following components：Tri-valent water soluble chromic salts：15~20 parts by weight；Cobalt salt：
12~16 parts by weight；Conducting salt：20~35 parts by weight；Complexant：4~6 parts by weight；Buffer：7~10 parts by weight；Black agent：
0.5~1.6 parts by weight；Brightener：0.01~0.5 parts by weight；Deionized water：100 parts by weight.
As a kind of preferable technical scheme of the present invention, described tri-valent water soluble chromic salts is chromium sulfate；Described cobalt salt
One or more in cobaltous sulfate, cobalt nitrate, cobalt acetate；Described conducting salt is the mixture of sodium sulphate and ammonium sulfate,
Described sodium sulphate and the mass ratio of ammonium sulfate are 1：0.3~1.2.
As a kind of preferable technical scheme of the present invention, described complexant is the mixing of formic acid, glycine and malic acid
Thing, the mass ratio of described formic acid, glycine and malic acid is 1：0.5~3：0.2~2.
As a kind of preferable technical scheme of the present invention, described buffer is the mixture of boric acid and sodium dihydrogen phosphate,
Described boric acid and the mass ratio of sodium dihydrogen phosphate are 2~6：1.
As a kind of preferable technical scheme of the present invention, described black agent be selected from aspartic acid, methionine, cystine,
One or more in cysteine, arginine, glycine, 2- aminobenzothiazole -7- formic acid.
As a kind of preferable technical scheme of the present invention, described black agent be cysteine with 2- aminobenzothiazoles-
The mass ratio of the mixture of 7- formic acid, described cysteine and 2- aminobenzothiazole -7- formic acid is 1：0.1~0.5.
As a kind of preferable technical scheme of the present invention, described brightener is selected from 2- amino -3- (3- hydroxyls-thio third
Acyl group)-benzene sulfonic acid, thiocarbamide, 3-sulfydryl-1-propane sulfonic acid sodium, 2-methylimidazole, one kind in 2-mercaptobenzimidazole or more
Kind.
As a kind of preferable technical scheme of the present invention, described brightener is 2- amino -3- (3- hydroxyls-thio propionyl
Base)-benzene sulfonic acid.
As a kind of preferable technical scheme of the present invention, described trivalent chromium plating solution also includes auxiliary agent, described auxiliary agent
One or more in stabilizer, dispersant, the agent that walks.
In order to solve the above-mentioned technical problem, the second aspect of the invention provides a kind of trivalent chrome plating, with described
The preparation method of trivalent chrome plating is prepared；Its composition comprises at least：Chromium, cobalt, hydrogen, oxygen, sulphur, P elements；Described base material
Base material or surface for conductive material have the base material of the non-conductive material of a conductive layer；Wherein, the base material of described conductive material
And one kind in iron, stainless steel, copper, nickel, silver, gold, conductivity ceramics of the conductive layer of the substrate surface of non-conductive material or
A variety of alloys；The base material of described non-conductive material be plastics, ceramics, glass it is any.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Beneficial effect：
(1) preparation method of trivalent chrome plating of the invention uses the feature of environmental protection and the more preferable sulfate system of stability,
It is environmentally safe and toxicity is electroplated far below the trivalent chromium of Cr VI, it is the plating side for meeting national clean manufacturing
Method.
(2) trivalent chrome plating of the invention, is made up of, color and luster is pitch black and color is equal chromium, cobalt, hydrogen, oxygen, sulphur and P elements
One, there is good melanism degree, and the adhesion of coating and base material is strong, and plated layer compact, porosity is low, has extraordinary resistance to
Corrosion.
Embodiment
Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When contradiction be present, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as entirety.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item that describes thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to represent that the present invention is not limited to this
Quantity, include the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.It is approximate in some examples
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article " one kind " before key element of the present invention or component and "one" to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of preparation side of trivalent chrome plating
Method, including at least following steps：Base material is immersed in trivalent chromium plating solution, electroplated using described base material as negative electrode, is electroplated
Temperature is 20~45 DEG C, current density 6A/dm2~25A/dm2, electroplating time is 5~30min；Trivalent chromium coating layer is in institute
On the base material stated；Described substrate surface comprises at least a conductive layer；
Described trivalent chromium plating solution, including at least following components：Tri-valent water soluble chromic salts：15~20 parts by weight；Cobalt salt：
12~16 parts by weight；Conducting salt：20~35 parts by weight；Complexant：4~6 parts by weight；Buffer：7~10 parts by weight；Black agent：
0.5~1.6 parts by weight；Brightener：0.01~0.5 parts by weight；Deionized water：100 parts by weight.
As a kind of preferable technical scheme of the present invention, the preparation method of described trivalent chrome plating, including at least following
Step：Base material is immersed in trivalent chromium plating solution, electroplated using described base material as negative electrode, electroplating temperature is 28~36 DEG C,
Current density is 14A/dm2~20A/dm2, electroplating time is 10~20min；Trivalent chromium coating layer is on described base material；Institute
The substrate surface stated, which comprises at least, a conductive layer；
Described trivalent chromium plating solution, including at least following components：Tri-valent water soluble chromic salts：18 parts by weight；Cobalt salt：13 weights
Measure part；Conducting salt：27 parts by weight；Complexant：4.8 parts by weight；Buffer：8 parts by weight；Black agent：1.2 parts by weight；Brightener：
0.3 parts by weight；Deionized water：100 parts by weight.
As a kind of preferable technical scheme of the present invention, described tri-valent water soluble chromic salts is chromium sulfate；Described cobalt salt
One or more in cobaltous sulfate, cobalt nitrate, cobalt acetate.
As a kind of preferable technical scheme of the present invention, described cobalt salt is cobalt acetate.
As a kind of preferable technical scheme of the present invention, the mass ratio of described tri-valent water soluble chromic salts and cobalt salt is 1.2
~1.5：1.
Conducting salt
Electrical conductivity is one of important parameter for evaluating electroplate liquid performance.The good conductivity of electroplate liquid, i.e. electrical conductivity are high, not only
The voltage of electroplating bath can be reduced, saves electric energy, and the dispersibility of electroplate liquid can be improved.Chromic salt electroplate liquid is led
Electrical property need to add conducting salt than relatively low.The effect of conducting salt is to improve the electric conductivity of plating solution, reduces tank voltage, improves plating
The dispersibility of liquid.Conducting salt is mostly the chloride or sulfate of potassium, sodium, ammonium.
As a kind of preferable technical scheme of the present invention, described conducting salt is in potassium sulfate, sodium sulphate, ammonium sulfate
It is one or more.
As a kind of preferable technical scheme of the present invention, described conducting salt is the mixture of sodium sulphate and ammonium sulfate, institute
The sodium sulphate and the mass ratio of ammonium sulfate stated are 1：0.3~1.2.
As a kind of preferable technical scheme of the present invention, described conducting salt is the mixture of sodium sulphate and ammonium sulfate, institute
The sodium sulphate and the mass ratio of ammonium sulfate stated are 1：0.8.
Cr3+Ability with greatly generation complex, in the simple aqueous solution without other complexing agents,
Cr3+Typically with stable d2sp3The form of type complex ion is present, wherein [Cr (H2O)6]3+For octahedral structure, belong to interior rail
Type complex compound, there is larger kinetic inertness, electronics is hardly resulted on negative electrode and obtains qualified chrome plating, therefore electrodeposited chromium
Negative electrode can separate out hydrogen in large quantities, cause the pH value near cathode surface to rise.Work as pH>When 4, [Cr (H2O)6]3+It can occur
The list of ol bridgeization reaction generation ol bridge formula gathers or poly-compounds, and these polymer complexes are very stable, chromium is difficult to from polymerization shape
Abjection and in cathodic reduction in formula, causes electrodeposited chromium to be difficult to continue；They are mixed in coating simultaneously, also cause coating
Crystallize loose, or even come off and can not thicken.Therefore, the electro-deposition of trivalent chromium is realized, it is necessary to add complexant and moisture
Son exchanges, and makes [Cr (H2O)6]3+Change into the electro-deposition that the trivalent chromium complex with electro-chemical activity causes trivalent chromium
It is easy to carry out.
Complexant
In trivalent chromium plating solution, complexant and chromium ion are coordinated to form more stable coordination ion, make trivalent chromium from
Son is more easy to discharge, and promotes the deposition of crome metal.It is complexant that organic acid is selected in trivalent chromium plating, they and Cr3+Coordination ratio
It is relatively stable, and it is easy to decomplexing and wastewater treatment, and to improve plating effect, generally use double base or polynary complexing agent.
As a kind of preferable technical scheme of the present invention, described complexant is organic acid.
As a kind of preferable technical scheme of the present invention, described complexant is selected from monocarboxylic acid, dicarboxylic acids, hydroxyl carboxylic
One or more in acid, amino carboxylic acid.
It is specifiable to have formic acid, acetic acid, propionic acid, butyric acid etc. for monocarboxylic acid.
It is specifiable to have ethanedioic acid, malonic acid, succinic acid, glutaric acid etc. for dicarboxylic acids.
It is specifiable to have hydroxyacetic acid, lactic acid, hydroxysuccinic acid, tartaric acid, citric acid, glucose for hydroxycarboxylic acid
Acid etc..
It is specifiable to have glycine, alanine, aspartic acid, iminodiacetic acid, glutamic acid, ammonia for amino carboxylic acid
Triacetic acid, ethylenediamine tetra-acetic acid etc..
As a kind of preferable technical scheme of the present invention, described complexant is selected from formic acid, acetic acid, propionic acid, butyric acid, second two
Acid, malonic acid, succinic acid, glutaric acid, hydroxyacetic acid, lactic acid, hydroxysuccinic acid, tartaric acid, citric acid, gluconic acid, sweet ammonia
One or more in acid, alanine, aspartic acid, iminodiacetic acid, glutamic acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid.
As a kind of preferable technical scheme of the present invention, described complexant is the mixing of formic acid, glycine and malic acid
Thing, the mass ratio of described formic acid, glycine and malic acid is 1：0.5~3：0.2~2.
As a kind of preferable technical scheme of the present invention, described complexant is the mixing of formic acid, glycine and malic acid
Thing, the mass ratio of described formic acid, glycine and malic acid is 1：1.2：0.7.
Buffer
The main function for adding buffer is the pH value for adjusting electroplate liquid, solution ph stabilization in electroplating process is existed
Certain scope, be advantageous to the formation of chrome plating.
As a kind of preferable technical scheme of the present invention, described buffer is selected from boric acid, acetate, citrate, phosphorus
One or more in hydrochlorate, ammonium salt, carbonate.
As a kind of preferable technical scheme of the present invention, described buffer is the mixture of boric acid and sodium dihydrogen phosphate,
Described boric acid and the mass ratio of sodium dihydrogen phosphate are 2~6：1.
As a kind of preferable technical scheme of the present invention, described buffer is the mixture of boric acid and sodium dihydrogen phosphate,
Described boric acid and the mass ratio of sodium dihydrogen phosphate are 4.5：1.
Black agent
Black agent is mainly nitrogenous, the organic or inorganic compound of sulfur-bearing, and one kind is the compound of sulfur-bearing, including thio ammonia
Base urea, thiocarbamide, thioacetic acid, rhodanide etc., such compound cathode adsorptivity is stronger, can suppress metal ion in negative electrode
Reduction；Especially low current density area, the region liberation of hydrogen can be caused substantially to increase, caused hydrogen penetrates into coating, easily causes coating
Phenomena such as bubbling, be numb, adhesion is bad with other materials, it is necessary to be balanced, but its stability is preferable, gained tint one
As it is partially yellow black；Another kind of material is amino acids, such as aspartic acid, cysteine, arginine, glycine, such
Compound effect is preferable, the typically inclined blue-black of gained tint and without preceding class compound the defects of, but with it is very multi-component simultaneous
Capacitive is poor and is oxidized easily decomposition.
As a kind of preferable technical scheme of the present invention, described black agent is amino acids.
As a kind of preferable technical scheme of the present invention, described black agent be selected from aspartic acid, methionine, cystine,
One or more in cysteine, arginine, glycine, 2- aminobenzothiazole -7- formic acid.
As a kind of preferable technical scheme of the present invention, described black agent be cysteine and 2- aminobenzothiazoles-
The mass ratio of the mixture of 7- formic acid, the cysteine and 2- aminobenzothiazole -7- formic acid is 1：0.1~0.5.
As a kind of preferable technical scheme of the present invention, described black agent be cysteine with 2- aminobenzothiazoles-
The mass ratio of the mixture of 7- formic acid, described cysteine and 2- aminobenzothiazole -7- formic acid is 1：0.2.
The CAS of described 2- aminobenzothiazole -7- formic acid：71224-95-8, its preparation method, including at least following step
Suddenly：
A. 11.3g 3- aminobenzoic acids and 75mL chlorobenzenes are added in 250mL there-necked flasks, stirring, is dripped at -5~0 DEG C
Add the 2.1mL 98wt% concentrated sulfuric acid, drip and finish in 30min, continue to react 25min.Add 6.8g sodium sulfocyanates, stirring reaction
0.22g benzyltriethylammoinium chlorides, 100 DEG C of isothermal reaction 10h are added after 5min.Filter, wash, dry, obtain N- (3- carboxyl benzene
Base) thiocarbamide.
B. 8.4g N- (3- carboxyl phenyls) thiocarbamide is added in 250mL there-necked flasks, 2.2mL Br is added dropwise2With 30mL chlorine
The mixture of benzene, finish in being dripped in 1h, react 4h at 70 DEG C of constant temperature.Cooling, 25mL ether is added, filter, be dried to obtain solids
Matter.Described solid matter is added in 70mL ethyl acetate and is heated to reflux 3h, is cooled down, is filtered, is dried, is obtained described
2- aminobenzothiazole -7- formic acid.
Brightener
Brightener is added in electroplate liquid can improve the brightness of coating.The brightness effect of brightener is one and integrated
Journey, rather than a kind of exercising result of brightener.At lower voltages, brightener can significantly increase cathodic polarization.It is bright
The addition of agent, plating solution is set to obtain the coating of light in suitable current density range, and will not after brightener addition
Change the electro-deposition behavior of trivalent chromium chrome plating.
As a kind of preferable technical scheme of the present invention, described brightener is selected from 2- amino -3- (3- hydroxyls-thio third
Acyl group)-benzene sulfonic acid, thiocarbamide, 3-sulfydryl-1-propane sulfonic acid sodium, 2-methylimidazole, one kind in 2-mercaptobenzimidazole or more
Kind.
As a kind of preferable technical scheme of the present invention, described brightener is 2- amino -3- (3- hydroxyls-thio propionyl
Base)-benzene sulfonic acid.
The preparation method of described 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid, including at least following steps：
A. by 50ml solvents and 0.1mol aniline, four mouthfuls equipped with agitator, dropping funel, condenser and thermometer are added
In bottle, 98wt% concentrated sulfuric acid 6mL is slowly added dropwise at 50 DEG C in stirring, controlling reaction temperature；Drop finishes, and is kept at 50 DEG C
30min, 168~172 DEG C are then to slowly warm up to, keeps 7h at this temperature；During reaction, solvent is constantly instilled, simultaneously
Solvent is constantly distilled out of again, keeps total solvent amount in reactor to be basically unchanged；Reaction cools after terminating, with 20wt% sodium carbonates
The pH of solution in bottle is adjusted to 8~9 by solution, filtering, discards filter residue, with 20wt% dilute sulfuric acid acidified filtrate to pH=2；Through
Filtering, washing, drying obtain 2- amino-benzene sulfonic acid；Described solvent is the mixture of No. 180 solvent naphthas and petroleum ether, No. 180
The volume ratio of solvent naphtha and petroleum ether is 4：1；No. 180 described solvent naphthas are purchased from Suzhou Angel promise Electron Material Co., Ltd；
B. 0.2mol 2- ammonia is added equipped with the 500mL there-necked flasks of mechanical agitator and constant pressure funnel at one
Base-benzene sulfonic acid, 0.8mol sodium sulfocyanates and 260mL formic acid, stirring, are cooled down with frozen water, are slowly added dropwise at 0~5 DEG C
0.4mol bromines, continue 2~3h of stirring, reactant mixture is poured into 500mL frozen water, filtered after stirring 5min, filter cake and 200mL
Water mixes, wherein remaining acid is neutralized with saturated sodium bicarbonate solution, filters, and neutrality is washed with water in filter cake, is dried in vacuo, obtains
Crude product, crude product obtain 2- amino -3- sulfo groups-phenyl isothiocyanate after re-crystallizing in ethyl acetate；
C., 0.25mol amion acetic acids and 0.2mol 2- amino -3- sulfo groups-phenyl isothiocyanate are added to 125mL second
In alcohol, 2.5h is stirred at room temperature, and solution is gradually become cloudy, and has solid precipitation, is evaporated under reduced pressure and removes solvent, and gained solid is used
15wt% watery hydrochloric acid and water washing three times, dry crude product.Recrystallize, dry in petroleum ether and chloroform, obtain described 2-
Amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid.
As a kind of preferable technical scheme of the present invention, described trivalent chromium plating solution also includes auxiliary agent, described auxiliary agent
One or more in stabilizer, dispersant and the agent that walks.
Stabilizer
Stabilizer belongs to compound reducing agent, can eliminate oxidant present in plating solution, can suppress trivalent chromium plating
Middle Cr6+Generation, makes bath stability.
As a kind of preferable technical scheme of the present invention, described stabilizer is selected from ascorbic acid, bromide, formaldehyde, sulphur
One or more in sour ferrous iron.
Dispersant
Dispersant can significantly improve the dispersibility and covering power of plating solution, and strong guarantor is provided to obtain uniform coating
Card, can use nitrogenous class aromatic organic compounds, such as benzene sulfonic acid amine.The surface-active with peptizaiton can also be used
Agent, but these are required for being used cooperatively with suitable additive.
Walk agent
The agent that walks is remarkably improved the mixed solution of the covering power of solution, usually organic matter and inorganic matter, some productions
Product use the compound of a certain amount of iron family element；Some then uses surfactant, such as polyethylene glycol, polyoxyethylene laural
Ether, APES, polysorbate etc..
The preparation method of described trivalent chromium plating solution, including at least following steps：
According to parts by weight, ionized water is removed, is heated to 55 DEG C, adds trivalent solubility chromic salts and cobalt salt, stirring and dissolving；So
After sequentially add conducting salt, complexant, buffer, black agent and brightener, after stirring and dissolving, by obtained solution at room temperature
12h is aged, the pH that solution is then adjusted with 20wt% dilute sulfuric acids and 15wt% ammoniacal liquor obtains described trivalent for 2.6~3.8
Chromium plating bath.
As a kind of preferable technical scheme of the present invention, the preparation method of described trivalent chrome plating includes heat treatment and walked
Suddenly, the described base material for being coated with trivalent chrome plating is is put into vacuum drying chamber by described heat treatment step, 220~280
3~5h is handled at DEG C.
In order to solve the above-mentioned technical problem, the second aspect of the invention provides a kind of trivalent chrome plating, with described
The preparation method of trivalent chrome plating is prepared；Its composition comprises at least：Chromium, cobalt, hydrogen, oxygen, sulphur, P elements；Described base material
Base material or surface for conductive material have the base material of the non-conductive material of a conductive layer；Wherein, the base material of conductive material and not
The conductive layer of the substrate surface of conductive material is one or more in iron, stainless steel, copper, nickel, silver, gold, conductivity ceramics
Alloy；The base material of non-conductive material be plastics, ceramics, glass it is any.
The inventors discovered that the present invention, which is prepared in trivalent chrome plating, has used cobalt salt and chromic salts, pass through conducting salt, coordination
Uniform black is presented in the trivalent chromium coating surface that agent, buffer, the compounding of black agent and brightener obtain, and brightness is good, instead
It is low to penetrate rate, and coating has extraordinary adhesion with base material, and the coating even compact of acquisition, porosity is low, and corrosion resistance is good.This
Inventor guesses that the reason for possible is present invention uses the system that cobalt and chromium are co-deposited, and passes through complexant, black agent
Regulate and control the sedimentation rate of cobalt and chromium with the coordination of brightener, so that coating has good performance.The present invention uses
Black agent and brightener compatibility it is good, and there is reproducibility, it is suppressed that the generation of Cr VI, strengthen the stability of electroplate liquid.
Carboxyl and sulfo group are acid strong in 2- aminobenzothiazole -7- formic acid and 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid,
Strengthen the electrical conductivity and dispersiveness of solution, and the electron-withdrawing of them makes other groups on phenyl ring have with metal ion
Good is coordinating, makes plated layer compact bright, and they are also possible to form intramolecular hydrogen bond in addition, helps to destroy in electricity for a long time
The ol bridge of trivalent chromic ion and hydroxide ion acts on during plating, further enhancing the stability of system.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available.
Embodiment 1：
Embodiment 1 provides a kind of preparation method of trivalent chrome plating, including at least following steps：Base material is immersed into trivalent
In chromium plating bath, electroplated using described base material as negative electrode, electroplating temperature is 20 DEG C, current density 6A/dm2, during plating
Between be 5min；Trivalent chromium coating layer is on described base material；Described substrate surface, which comprises at least, a conductive layer；
Described trivalent chromium plating solution, including at least following components：Tri-valent water soluble chromic salts：15 parts by weight；Cobalt salt：12 weights
Measure part；Conducting salt：20 parts by weight；Complexant：4 parts by weight；Buffer：7 parts by weight；Black agent：0.5 parts by weight；Brightener：
0.01 parts by weight；Deionized water：100 parts by weight.
Described tri-valent water soluble chromic salts is chromium sulfate；Described cobalt salt is cobaltous sulfate；Described conducting salt is sodium sulphate
With the mixture of ammonium sulfate, the mass ratio of described sodium sulphate and ammonium sulfate is 1：0.3；Described complexant is formic acid, sweet ammonia
The mixture of acid and malic acid, the mass ratio of described formic acid, glycine and malic acid is 1：0.5：0.2；Described buffer
For boric acid and the mixture of sodium dihydrogen phosphate, the mass ratio of described boric acid and sodium dihydrogen phosphate is 2：1；Described black agent is
The mixture of cysteine and 2- aminobenzothiazole -7- formic acid, described cysteine and 2- aminobenzothiazole -7- formic acid
Mass ratio be 1：0.1；Described brightener is 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid.
The preparation method of described 2- aminobenzothiazole -7- formic acid, including at least following steps：
A. 11.3g 3- aminobenzoic acids and 75mL chlorobenzenes are added in 250mL there-necked flasks, stirring, is added dropwise at -2 DEG C
The 2.1mL 98wt% concentrated sulfuric acid, the interior drops of 30min finish, continue to react 25min.Add 6.8g sodium sulfocyanates, stirring reaction 5min
0.22g benzyltriethylammoinium chlorides, 100 DEG C of isothermal reaction 10h are added afterwards.Filter, wash, dry, obtain N- (3- carboxyl benzene
Base) thiocarbamide.
B. 8.4g N- (3- carboxyl phenyls) thiocarbamide is added in 250mL there-necked flasks, 2.2mL Br is added dropwise2With 30mL chlorine
The mixture of benzene, finish in being dripped in 1h, react 4h at 70 DEG C of constant temperature.Cooling, 25mL ether is added, filter, be dried to obtain solids
Matter.Described solid matter is added in 70mL ethyl acetate and is heated to reflux 3h, is cooled down, is filtered, is dried, is obtained described
2- aminobenzothiazole -7- formic acid.
The preparation method of described 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid, including at least following steps：
A. by 50ml solvents and 0.1mol aniline, four mouthfuls equipped with agitator, dropping funel, condenser and thermometer are added
In bottle, 98wt% concentrated sulfuric acid 6mL is slowly added dropwise at 50 DEG C in stirring, controlling reaction temperature；Drop finishes, and is kept at 50 DEG C
30min, 170 DEG C are then to slowly warm up to, keeps 7h at this temperature；During reaction, solvent is constantly instilled, while solvent is again
Constantly it is distilled out of, keeps total solvent amount in reactor to be basically unchanged；Reaction cools after terminating, will with 20wt% aqueous sodium carbonates
The pH of solution in bottle is adjusted to 8, filtering, discards filter residue, with 20wt% dilute sulfuric acid acidified filtrate to pH=2；It is filtered, wash
Wash, dry and obtain 2- amino-benzene sulfonic acid；Described solvent is the mixture of No. 180 solvent naphthas and petroleum ether, No. 180 solvent naphthas
Volume ratio with petroleum ether is 4：1；No. 180 described solvent naphthas are purchased from Suzhou Angel promise Electron Material Co., Ltd；
B. 0.2mol 2- ammonia is added equipped with the 500mL there-necked flasks of mechanical agitator and constant pressure funnel at one
Base-benzene sulfonic acid, 0.8mol sodium sulfocyanates and 260mL formic acid, stirring, are cooled down with frozen water, 0.4mol are slowly added dropwise at 0 DEG C
Bromine, continuing to stir 2.5h, reactant mixture is poured into 500mL frozen water, filtered after stirring 5min, filter cake mixes with 200mL water,
Wherein remaining acid is neutralized with saturated sodium bicarbonate solution, is filtered, and neutrality is washed with water in filter cake, is dried in vacuo, is obtained crude product,
Crude product obtains 2- amino -3- sulfo groups-phenyl isothiocyanate after re-crystallizing in ethyl acetate；
C., 0.25mol amion acetic acids and 0.2mol 2- amino -3- sulfo groups-phenyl isothiocyanate are added to 125mL second
In alcohol, 2.5h is stirred at room temperature, and solution is gradually become cloudy, and has solid precipitation, is evaporated under reduced pressure and removes solvent, and gained solid is used
15wt% watery hydrochloric acid and water washing three times, dry crude product.Recrystallize, dry in petroleum ether and chloroform, obtain described 2-
Amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid.
Embodiment 2：
Embodiment 2 provides a kind of preparation method of trivalent chrome plating, including at least following steps：Base material is immersed into trivalent
In chromium plating bath, electroplated using described base material as negative electrode, electroplating temperature is 20 DEG C, current density 6A/dm2, during plating
Between be 5min；Trivalent chromium coating layer is on described base material；Described substrate surface, which comprises at least, a conductive layer；
Described trivalent chromium plating solution, including at least following components：Tri-valent water soluble chromic salts：20 parts by weight；Cobalt salt：16 weights
Measure part；Conducting salt：35 parts by weight；Complexant：6 parts by weight；Buffer：10 parts by weight；Black agent：1.6 parts by weight；Brightener：
0.5 parts by weight；Deionized water：100 parts by weight.
Described tri-valent water soluble chromic salts is chromium sulfate；Described cobalt salt is cobaltous sulfate；Described conducting salt is sodium sulphate
With the mixture of ammonium sulfate, the mass ratio of described sodium sulphate and ammonium sulfate is 1：0.3；Described complexant is formic acid, sweet ammonia
The mixture of acid and malic acid, the mass ratio of described formic acid, glycine and malic acid is 1：0.5：0.2；Described buffer
For boric acid and the mixture of sodium dihydrogen phosphate, the mass ratio of described boric acid and sodium dihydrogen phosphate is 2：1；Described black agent is
The mixture of cysteine and 2- aminobenzothiazole -7- formic acid, described cysteine and 2- aminobenzothiazole -7- formic acid
Mass ratio be 1：0.1；Described brightener is 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid.
The preparation method of described 2- aminobenzothiazole -7- formic acid is the same as embodiment 1.
The preparation method of described 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid is the same as embodiment 1.
Embodiment 3：
Embodiment 3 provides a kind of preparation method of trivalent chrome plating, including at least following steps：Base material is immersed into trivalent
In chromium plating bath, electroplated using described base material as negative electrode, electroplating temperature is 20 DEG C, current density 6A/dm2, during plating
Between be 5min；Trivalent chromium coating layer is on described base material；Described substrate surface, which comprises at least, a conductive layer；
Described trivalent chromium plating solution, including at least following components：Tri-valent water soluble chromic salts：18 parts by weight；Cobalt salt：13 weights
Measure part；Conducting salt：27 parts by weight；Complexant：4.8 parts by weight；Buffer：8 parts by weight；Black agent：1.2 parts by weight；Brightener：
0.3 parts by weight；Deionized water：100 parts by weight.
Described tri-valent water soluble chromic salts is chromium sulfate；Described cobalt salt is cobaltous sulfate；Described conducting salt is sodium sulphate
With the mixture of ammonium sulfate, the mass ratio of described sodium sulphate and ammonium sulfate is 1：0.3；Described complexant is formic acid, sweet ammonia
The mixture of acid and malic acid, the mass ratio of described formic acid, glycine and malic acid is 1：0.5：0.2；Described buffer
For boric acid and the mixture of sodium dihydrogen phosphate, the mass ratio of described boric acid and sodium dihydrogen phosphate is 2：1；Described black agent is
The mixture of cysteine and 2- aminobenzothiazole -7- formic acid, described cysteine and 2- aminobenzothiazole -7- formic acid
Mass ratio be 1：0.1；Described brightener is 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid.
The preparation method of described 2- aminobenzothiazole -7- formic acid is the same as embodiment 1.
The preparation method of described 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid is the same as embodiment 1.
Embodiment 4：
Embodiment 4 provides a kind of preparation method of trivalent chrome plating, including at least following steps：Base material is immersed into trivalent
In chromium plating bath, electroplated using described base material as negative electrode, electroplating temperature is 20 DEG C, current density 6A/dm2, during plating
Between be 5min；Trivalent chromium coating layer is on described base material；Described substrate surface, which comprises at least, a conductive layer；
Described trivalent chromium plating solution, including at least following components：Tri-valent water soluble chromic salts：18 parts by weight；Cobalt salt：13 weights
Measure part；Conducting salt：27 parts by weight；Complexant：4.8 parts by weight；Buffer：8 parts by weight；Black agent：1.2 parts by weight；Brightener：
0.3 parts by weight；Deionized water：100 parts by weight.
Described tri-valent water soluble chromic salts is chromium sulfate；Described cobalt salt is cobalt nitrate；Described conducting salt is sodium sulphate
With the mixture of ammonium sulfate, the mass ratio of described sodium sulphate and ammonium sulfate is 1：1.2；Described complexant is formic acid, sweet ammonia
The mixture of acid and malic acid, the mass ratio of described formic acid, glycine and malic acid is 1：3：2；Described buffer is boron
The mass ratio of the mixture of acid and sodium dihydrogen phosphate, described boric acid and sodium dihydrogen phosphate is 6：1；Described black agent is half Guang
The mixture of propylhomoserin and 2- aminobenzothiazole -7- formic acid, the matter of described cysteine and 2- aminobenzothiazole -7- formic acid
Amount is than being 1：0.5；Described brightener is 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid.
The preparation method of described 2- aminobenzothiazole -7- formic acid is the same as embodiment 1.
The preparation method of described 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid is the same as embodiment 1.
Embodiment 5：
Embodiment 5 provides a kind of preparation method of trivalent chrome plating, including at least following steps：Base material is immersed into trivalent
In chromium plating bath, electroplated using described base material as negative electrode, electroplating temperature is 20 DEG C, current density 6A/dm2, during plating
Between be 5min；Trivalent chromium coating layer is on described base material；Described substrate surface, which comprises at least, a conductive layer；
Described trivalent chromium plating solution, including at least following components：Tri-valent water soluble chromic salts：18 parts by weight；Cobalt salt：13 weights
Measure part；Conducting salt：27 parts by weight；Complexant：4.8 parts by weight；Buffer：8 parts by weight；Black agent：1.2 parts by weight；Brightener：
0.3 parts by weight；Deionized water：100 parts by weight.
Described tri-valent water soluble chromic salts is chromium sulfate；Described cobalt salt is cobalt acetate；Described conducting salt is sodium sulphate
With the mixture of ammonium sulfate, the mass ratio of described sodium sulphate and ammonium sulfate is 1：0.8；Described complexant is formic acid, sweet ammonia
The mixture of acid and malic acid, the mass ratio of described formic acid, glycine and malic acid is 1：1.2：0.7；Described buffer
For boric acid and the mixture of sodium dihydrogen phosphate, the mass ratio of described boric acid and sodium dihydrogen phosphate is 4.5：1；Described black agent
For cysteine and the mixture of 2- aminobenzothiazole -7- formic acid, described cysteine and 2- aminobenzothiazole -7- first
The mass ratio of acid is 1：0.2；Described brightener is 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid.
The preparation method of described 2- aminobenzothiazole -7- formic acid is the same as embodiment 1.
The preparation method of described 2- amino -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid is the same as embodiment 1.
Embodiment 6：
The embodiment of embodiment 6 is with embodiment 5, and difference is, electroplating temperature is 45 DEG C, and current density is
25A/dm2, electroplating time 30min.
Embodiment 7：
The embodiment of embodiment 7 is with embodiment 5, and difference is, electroplating temperature is 28 DEG C, and current density is
14A/dm2, electroplating time 10min.
Embodiment 8：
The embodiment of embodiment 8 is with embodiment 5, and difference is, electroplating temperature is 36 DEG C, and current density is
20A/dm2, electroplating time 20min.
Embodiment 9：
The embodiment of embodiment 9 is with embodiment 8, and difference is, described trivalent chromium plating solution also includes
Dispersant PEG400.
Comparative example 1：
The embodiment of comparative example 1 is with embodiment 9, and difference is, described trivalent chromium plating solution does not include
Brightener.
Comparative example 2：
The embodiment of comparative example 2 is with embodiment 9, and difference is, described trivalent chromium plating solution does not include
Black agent.
Comparative example 3：
The embodiment of comparative example 3 is with embodiment 9, and difference is, described black agent is cysteine.
Comparative example 4：
The embodiment of comparative example 4 is with embodiment 9, and difference is, described black agent is 2- amino benzos
Thiazole -7- formic acid.
Comparative example 5：
With embodiment 9, difference is the embodiment of comparative example 5, in described black agent cysteine and
The quality of 2- aminobenzothiazole -7- formic acid is 1：0.6.
Performance evaluation：
In accordance with the following methods, embodiment 1~9 and the trivalent chromium plating solution described in comparative example 1~5 are prepared：
According to parts by weight, ionized water is removed, is heated to 55 DEG C, adds trivalent solubility chromic salts and cobalt salt, stirring and dissolving；So
After sequentially add conducting salt, complexant, buffer, black agent and brightener, after stirring and dissolving, by obtained solution at room temperature
12h is aged, is then 2.8 with 20wt% dilute sulfuric acids and 15wt% ammoniacal liquor adjustment pH, that is, obtains described trivalent chromium plating solution.
Electroplating experiments are carried out using Hull groove, trivalent chromium plating solution volume is 250mL.Negative electrode is described base material, anode
For DSA coated titanium anode plates, size is 50mm × 100mm × 2mm.
For the base material that this experiment uses for commercially available H62 latten(-tin)s, size is 50mm × 100mm × 0.2mm, and described base material exists
Needed before plating respectively with the liquid honing of 200 mesh and 600 mesh to light, then with non-phosphor degreaser oil removing cleaning fluid (Shanghai
Yao Yan Chemical Companies manufacture) remove the grease of substrate surface, finally washing is clean and can be electroplated after drying, electricity
Plating process is stirred using compressed air.
Base material is put into the electroplate liquid described in embodiment 1~9 and comparative example 1~5, electroplated, trivalent chromium coating layer
In described substrate surface, the base material for being plated with trivalent chrome plating is put into vacuum drying chamber and is heat-treated, i.e., at 260 DEG C
Lower processing 3.5h, then test the performance of coating.
Outward appearance
The outward appearance of coating is detected using range estimation brightness experience rating method.Estimate point of brightness experience rating method
Level normative reference is as follows：
A.-level (entire bright) coating surface is bright, can clearly find out face and face；
B. two level (light) coating surface is bright, it is seen that face, face, but picture is apprehensive；
C. three-level (half is bright) coating slightly brightness, face can only find out profile；
D. level Four (no light) coating surface is substantially matt, does not see face contour.
Reflectivity (%) of the coating to light is tested using ultraviolet-uisible spectrophotometer.Solar radiation energy is concentrated mainly on
200~5000nm scopes, wave-length coverage account for more than the 60% of solar radiation gross energy, therefore test waves in 200~900nm light
Long scope elects 200~900nm as.For lighttight material, the transmitance of light can be neglected, the sum of reflectivity and absorptivity
For 1.Caused a variety of colors is their results to the different wave length selective absorbing in the range of visible light wave on object.When
Object absorbs to all visible light wave equivalent, and when absorptivity is up to more than 90%, then object shows as black；When absorptivity reaches
When more than 96%, object is in aterrimus.
Adhesion
Thermal shock test：The base material electroplated is incubated 1h under the conditions of 300 DEG C, after taking-up in frozen water chilling, repeatedly 10
It is secondary to have no that coating peeling comes off to be qualified.
Porosity
Using patch filter paper method measurement porosity, described trivalent chrome plating, matrix is steel, and coating is chromium, so selection
Test solution is the mixed solution of the potassium ferricyanide, ammonium chloride and sodium chloride, and it forms as follows substantially：Potassium ferricyanide K3Fe(CN)6
10g/L, ammonium chloride NH4Cl 30g/L, sodium chloride nacl 60g/L, solvent are deionized water.
Method of testing：The filter paper of detection solution will be impregnated with, be close on the substrate surface electroplated, between filter paper and surface
There should not be bubble, while can constantly add detection solution, filter paper is kept wetting, after waiting filter paper to be labelled to 10min, take off and be printed on
The filter paper of blue spot, with distilled water flushing, then it is placed on cleaning panes, the number in space is calculated after drying.
The computational methods of porosity：To draw has the glass plate of grid (grid area is 1cm2), it is placed on and is printed on hole spot
Filter paper on, count include coloured spot number in every grid respectively, then porosity (the spot of calculating coating to base material
Number/cm2)：Porosity=n/S, n refers to hole spot number in formula；S refers to tested plate areas, cm2；Measure 3 times, takes it
Average value is as measurement result.
When calculating porosity, the direct size of spot is specified below：In below lmm, one is pressed spot diameter
One hole calculates；Spot diameter is pressed 3 holes for one and calculated within 1~3mm；Spot diameter is within 3~5mm, and one
It is individual to press 10 holes calculating.
Corrosion resistance
Acetic acid salt spray test (CASS experiments) is accelerated to investigate corrosion resistance by copper.Testing liquid compound method is：By chlorination
Sodium (NaCl, AR) is dissolved in deionized water, and it is 50 ± 1g/L to make its concentration, then adds dichloride copper (CuCl2, AR), make
Its concentration is 0.26 ± 0.02g/L.The pH value of this solution is adjusted between 3.1~3.3 with glacial acetic acid.
Base material to be measured is placed in salt-mist corrosion tester, makes base material to be measured with vertical line into 30 °, salt fog cabinet is set
Vapo(u)rizing temperature is 50 DEG C, and saturation temperature is 55 DEG C.Continuous spraying 16h.After the completion of take out base material, rinsed with deionized water, then
Dry up respectively.
Corrosion resistance Classified Protection is：
One block of transparent stroke lucite for having grid (5mm × 5mm) is covered in sample coating major surfaces, is divided into
Some grids, calculate grid sum N and contain the grid η of one or more hot spots in these grids：Rate of corrosion γ (%)
=η/N
The rate of corrosion of the every kind of six pieces of tested samples of coating of sequentially determining, averages as the rate of corrosion of this kind of coating.Root
Corrosion resistance rating result is determined according to following table.Described 0~0.5 refers to rate of corrosion between 0% to 0.5%, including 0.5%
But do not include 0%.
| Rate of corrosion γ (%) | 0 | 0~0.25 | 0.25~0.5 | 0.5~1 | 1~2 | 2~4 | 4~8 | 8~16 | 16~32 | 32~64 | >64 |
| Rating | 10 | 9 | 8 | 7 | 6 | 5 | 4 | 3 | 2 | 1 | 0 |
The performance characterization of table 1 is tested
As can be seen from Table 1, the trivalent chrome plating in the present invention is in aterrimus, and bright property is good, reflectivity to sunshine
It is low, absorptivity is high, and the adhesion of coating and base material is good, and plated layer compact, porosity is low, has extraordinary anticorrosion effect
Fruit.
Foregoing example is merely illustrative, for explaining some features of the method for the invention.Appended right will
Ask and be intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible implementation
The explanation of the embodiment of the selection of the combination of example.Therefore, the purpose of applicant is that appended claim is not illustrated this hair
The selectional restriction of the example of bright feature.Some number ranges used also include sub- model within the claims
Enclose, the change in these scopes should be also construed to by appended claim covering in the conceived case.
Claims (10)
1. a kind of preparation method of trivalent chrome plating, it is characterised in that including at least following steps：Base material is immersed into trivalent chromium electricity
In plating solution, electroplated using described base material as negative electrode, electroplating temperature is 20~45 DEG C, current density 6A/dm2~25A/
dm2, electroplating time is 5~30min；Trivalent chromium coating layer is on described base material；Described substrate surface, which comprises at least, to be had
One conductive layer；
Described trivalent chromium plating solution, including at least following components：Tri-valent water soluble chromic salts：15~20 parts by weight；Cobalt salt：12~
16 parts by weight；Conducting salt：20~35 parts by weight；Complexant：4~6 parts by weight；Buffer：7~10 parts by weight；Black agent：0.5
~1.6 parts by weight；Brightener：0.01~0.5 parts by weight；Deionized water：100 parts by weight.
2. the preparation method of trivalent chrome plating as claimed in claim 1, it is characterised in that described tri-valent water soluble chromic salts is
Chromium sulfate；One or more of the described cobalt salt in cobaltous sulfate, cobalt nitrate, cobalt acetate；Described conducting salt is sodium sulphate
With the mixture of ammonium sulfate, the mass ratio of described sodium sulphate and ammonium sulfate is 1：0.3~1.2.
3. the preparation method of trivalent chrome plating as claimed in claim 1, it is characterised in that described complexant is formic acid, sweet
The mixture of propylhomoserin, malic acid, the mass ratio of described formic acid, glycine and tartaric acid is 1：0.5~3：0.2~2.
4. the preparation method of trivalent chrome plating as claimed in claim 1, it is characterised in that described buffer is boric acid and phosphorus
The mass ratio of the mixture of acid dihydride sodium, described boric acid and sodium dihydrogen phosphate is 2~6：1.
5. the preparation method of trivalent chrome plating as claimed in claim 1, it is characterised in that described black agent is selected from asparagus fern ammonia
One or more in acid, methionine, cystine, cysteine, arginine, glycine, 2- aminobenzothiazole -7- formic acid.
6. the preparation method of trivalent chrome plating as claimed in claim 1, it is characterised in that described black agent is cysteine
With the mixture of 2- aminobenzothiazole -7- formic acid, the quality of described cysteine and 2- aminobenzothiazole -7- formic acid is
1：0.1~0.5.
7. the preparation method of trivalent chrome plating as claimed in claim 1, it is characterised in that described brightener is selected from 2- ammonia
Base -3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid, thiocarbamide, 3-sulfydryl-1-propane sulfonic acid sodium, 2-methylimidazole, 2- sulfydryl benzene
And the one or more in imidazoles.
8. the preparation method of trivalent chrome plating as claimed in claim 1, it is characterised in that described brightener be 2- amino-
3- (3- hydroxyls-thiopropionyl)-benzene sulfonic acid.
9. the preparation method of trivalent chrome plating as claimed in claim 1, it is characterised in that described trivalent chromium plating solution also wraps
Include auxiliary agent, one or more of the described auxiliary agent in stabilizer, dispersant, the agent that walks.
10. a kind of trivalent chrome plating, it is characterised in that be prepared with the preparation method described in any one of claim 1~9；
Its composition comprises at least：Chromium, cobalt, hydrogen, oxygen, sulphur, P elements；Described base material has a conduction for the base material of conductive material or surface
The base material of the non-conductive material of layer；Wherein, the conductive layer of the base material of conductive material and the substrate surface of non-conductive material is selected from
One or more alloys in iron, stainless steel, copper, nickel, silver, gold, conductivity ceramics；The base material of non-conductive material is plastics, pottery
Any of porcelain, glass.
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| CN110117782A (en) * | 2019-05-14 | 2019-08-13 | 广州超邦化工有限公司 | A kind of non-cyanide plating cadmium titanium alloy and trivalent chromium passivation coating and preparation method thereof |
| CN111962105A (en) * | 2020-09-11 | 2020-11-20 | 广东涂乐师新材料科技有限公司 | Trivalent black chromium electroplating agent simple to mix and preparation method thereof |
| CN113403650A (en) * | 2021-06-21 | 2021-09-17 | 集美大学 | Method for improving coating uniformity of release agent by using discrete crystal nuclei |
| TWI743671B (en) * | 2018-02-09 | 2021-10-21 | 日商日本製鐵股份有限公司 | Steel plate for container and method for manufacturing steel plate for container |
| CN116024623A (en) * | 2022-12-27 | 2023-04-28 | 南通申海工业科技有限公司 | Tail pipe mist black chromium plating process |
| CN116770375A (en) * | 2023-06-06 | 2023-09-19 | 中山博美新材料科技有限公司 | Plating solution for black chromium plating layer, and preparation method and application thereof |
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| EP4023793A1 (en) * | 2021-01-05 | 2022-07-06 | Coventya SAS | Electroplating bath for depositing chromium or chromium alloy from a trivalent chromium bath and process for depositing chromium or chromium alloy |
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| CN113403650A (en) * | 2021-06-21 | 2021-09-17 | 集美大学 | Method for improving coating uniformity of release agent by using discrete crystal nuclei |
| CN116024623A (en) * | 2022-12-27 | 2023-04-28 | 南通申海工业科技有限公司 | Tail pipe mist black chromium plating process |
| CN116770375A (en) * | 2023-06-06 | 2023-09-19 | 中山博美新材料科技有限公司 | Plating solution for black chromium plating layer, and preparation method and application thereof |
| CN116770375B (en) * | 2023-06-06 | 2024-01-02 | 中山博美新材料科技有限公司 | Plating solution for black chromium plating layer, and preparation method and application thereof |
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