CN113832455B - Environment-friendly silicate passivation solution for zinc coating and preparation method and application thereof - Google Patents
Environment-friendly silicate passivation solution for zinc coating and preparation method and application thereof Download PDFInfo
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- CN113832455B CN113832455B CN202111121513.4A CN202111121513A CN113832455B CN 113832455 B CN113832455 B CN 113832455B CN 202111121513 A CN202111121513 A CN 202111121513A CN 113832455 B CN113832455 B CN 113832455B
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- Prior art keywords
- acid
- environment
- sodium
- solution
- zinc coating
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- 238000002161 passivation Methods 0.000 title claims abstract description 125
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000011701 zinc Substances 0.000 title claims abstract description 90
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 90
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000576 coating method Methods 0.000 title claims abstract description 65
- 239000011248 coating agent Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- 238000003756 stirring Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 15
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 15
- 230000003213 activating effect Effects 0.000 claims abstract description 15
- 239000008397 galvanized steel Substances 0.000 claims abstract description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 15
- 239000006172 buffering agent Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 108
- 239000011259 mixed solution Substances 0.000 claims description 40
- 229910000831 Steel Inorganic materials 0.000 claims description 39
- 239000010959 steel Substances 0.000 claims description 39
- 238000007747 plating Methods 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 5
- 239000001263 FEMA 3042 Substances 0.000 claims description 5
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 235000010338 boric acid Nutrition 0.000 claims description 5
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 239000001433 sodium tartrate Substances 0.000 claims description 5
- 229960002167 sodium tartrate Drugs 0.000 claims description 5
- 235000011004 sodium tartrates Nutrition 0.000 claims description 5
- 235000015523 tannic acid Nutrition 0.000 claims description 5
- 229940033123 tannic acid Drugs 0.000 claims description 5
- 229920002258 tannic acid Polymers 0.000 claims description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- 235000019263 trisodium citrate Nutrition 0.000 claims description 5
- 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 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- 229940120146 EDTMP Drugs 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 229910000166 zirconium phosphate Inorganic materials 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 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229940010048 aluminum sulfate Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960002645 boric acid Drugs 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 229960003390 magnesium sulfate Drugs 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229960003975 potassium Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical compound NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 claims 1
- 229960004838 phosphoric acid Drugs 0.000 claims 1
- 238000005260 corrosion Methods 0.000 description 47
- 230000007797 corrosion Effects 0.000 description 39
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 30
- 239000010410 layer Substances 0.000 description 19
- 239000011780 sodium chloride Substances 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 238000004448 titration Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 230000010287 polarization Effects 0.000 description 8
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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- 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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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Abstract
The invention provides an environment-friendly silicate passivation solution for a zinc coating, which comprises the following components in parts by weight: 10-35 g/L of sodium silicate, 2-10 g/L of inorganic auxiliary film forming agent, 3-15 ml/L of organic auxiliary film forming agent, 5-10 g/L of composite oxidant, 5-15 ml/L of activating agent, 2-10 g/L of buffering agent and water. The pH value of the environment-friendly silicate passivation solution of the zinc coating is 1.5-3.5. The invention also provides a preparation method of the environment-friendly silicate passivation solution for the zinc coating, which comprises the step of mixing and stirring sodium silicate, an inorganic auxiliary film forming agent, an organic auxiliary film forming agent, a composite oxidant, an activating agent, a buffering agent and water in a series to obtain the environment-friendly silicate passivation solution for the zinc coating. The invention also provides application of the environment-friendly silicate passivation solution for the zinc coating, and the galvanized steel part or the hot dip galvanized steel part is immersed into the environment-friendly silicate passivation solution for the zinc coating provided by the invention, so that passivation treatment of the zinc coating is realized.
Description
Technical Field
The invention relates to the field of metal material surface treatment, in particular to an environment-friendly silicate passivation solution for a zinc coating and a preparation method and application thereof.
Background
Zinc is widely used as a protective coating for sacrificial anodes on steel products because it is easily passivated in atmospheric conditions and has a potential that is less than that of iron. The zinc coating plays a good role in protecting the iron and steel products in the atmospheric environment, but the corrosion resistance of the zinc coating in the humid atmospheric environment or the marine atmospheric environment containing chloride ions is not ideal, and the corrosion is easy to occur, so that the practical application of the zinc coating and the iron and steel products related to the zinc coating is limited. In order to improve the protection capability of the zinc coating on steel, the zinc coating needs to be passivated after being coated with zinc in engineering, so that a compact conversion film layer is formed on the surface of the zinc coating to improve the corrosion resistance of the zinc coating.
Conventionally, passivation of zinc coatings has been performed using chromates containing hexavalent chromium to form a dense chromium-based oxide protective layer on the surface of the zinc coating. Although the chromate passivation treatment can obviously improve the corrosion resistance of the zinc plating, the chromate passivation solution is easy to cause cancer and causes great pollution to the environment because of containing hexavalent chromium metal ions. Therefore, searching for an environment-friendly passivation solution capable of replacing chromate passivation is an urgent need for industry development.
Recently, commercially applied alternative hexavalent chromium passivation solutions are mainly trivalent chromium passivation solutions. Although the passivation solution can replace hexavalent chromium passivation solution, trivalent chromium is relatively active and can be converted into hexavalent chromium in the actual treatment process, and the environment is polluted. Therefore, the development of truly chromium-free environment-friendly passivation solution is imperative.
Recently, silicate passivation technology has become a hotspot in industry research due to low cost, good stability, no toxicity, no pollution and environmental friendliness of silicate. The silicate passivation solution reported at present consists of sodium silicate as a main film forming agent, hydrogen peroxide as an oxidant, a small amount of additives and the like. However, in practical use, the single silicate passivation cannot provide effective protection, and meanwhile, hydrogen peroxide is used as an oxidant, so that the hydrogen peroxide volatilizes quickly and is unstable, the passivation quality of a product can be influenced, and meanwhile, the production, the transportation, the storage and the use of passivation solution are greatly influenced.
Disclosure of Invention
The invention aims to solve the problems, and aims to provide an environment-friendly silicate passivation solution for zinc plating, and a preparation method and application thereof.
The invention provides an environment-friendly silicate passivation solution for a zinc coating, which has the following characteristics:
the components and the contents of the environment-friendly silicate passivation solution of the zinc coating are respectively as follows: 10-35 g/L of sodium silicate, 2-10 g/L of inorganic auxiliary film forming agent, 3-15 ml/L of organic auxiliary film forming agent, 5-10 g/L of composite oxidant, 5-15 ml/L of activating agent, 2-10 g/L of buffering agent and water. The pH value of the environment-friendly silicate passivation solution of the zinc coating is 1.5-3.5.
The environment-friendly silicate passivation solution for the zinc coating provided by the invention can also have the following characteristics: wherein the inorganic auxiliary film forming agent is any one or more of sodium tungstate, sodium molybdate, sodium vanadate, sodium fluosilicate, sodium fluozirconate, sodium fluoride, sodium bromide, potassium fluozirconate, zinc acetate, nickel acetate, cobalt acetate, magnesium sulfate, aluminum sulfate, cobalt sulfate and nickel sulfate.
The environment-friendly silicate passivation solution for the zinc coating provided by the invention can also have the following characteristics: wherein the organic auxiliary film forming agent is any one or more of oxalic acid, tannic acid, malic acid, benzoic acid, polyphosphoric acid, sodium polyphosphate, phosphoramidate, salicylic acid, ascorbic acid, thiourea, ethylene thiourea, aminotrimethylene phosphonic acid, diethylenetriamine penta-methylene phosphonic acid and ethylenediamine tetra-methylene phosphonic acid.
The environment-friendly silicate passivation solution for the zinc coating provided by the invention can also have the following characteristics: wherein the compound oxidant is any two or more of hypochlorous acid, sodium hypochlorite, perchloric acid, potassium nitrate, sodium nitrate, potassium permanganate, cerium nitrate, aluminum nitrate, zinc nitrate and lanthanum nitrate.
The environment-friendly silicate passivation solution for the zinc coating provided by the invention can also have the following characteristics: wherein the activating agent is any one or more of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, sulfamic acid, nitric acid, citric acid and tartaric acid.
The environment-friendly silicate passivation solution for the zinc coating provided by the invention can also have the following characteristics: wherein the buffer is any one or more of sodium acetate, ammonium bifluoride, trisodium citrate, sodium tartrate, boric acid and potassium citrate.
The invention also provides a preparation method of the environment-friendly silicate passivation solution for zinc plating, which has the characteristics that the preparation method comprises the following steps:
and step 1, mixing an inorganic auxiliary film forming agent, an activating agent, a buffering agent and deionized water, and continuously stirring for 2-5 minutes at the rotating speed of 400-600 rpm to obtain a mixed solution A.
And 2, dissolving the composite oxidant in deionized water to obtain a mixed solution B, dropwise adding the mixed solution B into the mixed solution A under the stirring condition, and continuously stirring for 2-5 minutes at the rotating speed of 400-600 rpm to obtain a mixed solution C.
And step 3, dropwise adding sodium silicate into the mixed solution C under the stirring condition, and continuously stirring for 2-5 minutes at the rotating speed of 800-1200 rpm to obtain the mixed solution D.
And step 4, dropwise adding the organic auxiliary film forming agent into the mixed solution D under the stirring condition, adding deionized water to a constant volume, and continuously stirring for 2-5 minutes at the rotating speed of 800-1200 rpm to obtain the environment-friendly silicate passivation solution of the zinc coating.
The invention also provides an application of the environment-friendly silicate passivation solution for the zinc coating, which has the following characteristics: immersing the electrogalvanized steel piece or the hot-dip galvanized steel piece into the environment-friendly silicate passivation solution of the zinc coating to realize passivation treatment of the zinc coating, wherein the environment-friendly silicate passivation solution of the zinc coating is the environment-friendly silicate passivation solution of the zinc coating.
Effects and effects of the invention
According to the environment-friendly silicate passivation solution for the zinc coating and the preparation method and the application thereof, the components and the contents of the environment-friendly silicate passivation solution for the zinc coating are respectively as follows: 10-35 g/L of sodium silicate, 2-10 g/L of inorganic auxiliary film forming agent, 3-15 ml/L of organic auxiliary film forming agent, 5-10 g/L of composite oxidant, 5-15 ml/L of activating agent, 2-10 g/L of buffering agent, and the pH value of the environment-friendly silicate passivation solution of water and zinc coating is 1.5-3.5. The environment-friendly silicate passivation solution for zinc plating can be used for the post-treatment process of hot galvanizing and electrogalvanizing of steel parts, and the galvanized layer passivation film treated by the passivation solution has bright and transparent film layer, uniform film formation, good corrosion resistance, good film adhesion and simple passivation treatment process.
The environment-friendly silicate passivation solution for the zinc plating layer has the advantages of simple component system, no trivalent chromium, hexavalent chromium and other harmful substances, environment friendliness and no pollution, and can realize clean production of galvanized products.
The zinc plating silicate passivating solution adopts a stable composite oxidant to replace the traditional hydrogen peroxide oxidant which is easy to decompose, has good plating solution stability, greatly prolongs the service life of the plating solution, and simultaneously is convenient for storage and transportation of the passivating solution.
The zinc plating silicate passivation solution fully utilizes the synergistic effect of organic and inorganic film forming to construct the composite passivation film. The organic film and the inorganic film are coordinated with each other, so that the self-repairing function of the passivation film can be effectively improved, the film forming quality is improved, the porosity is reduced, the binding force between the plating layer and the substrate is improved, and the corrosion resistance of the silicate passivation film is greatly improved.
Drawings
FIG. 1 is a graph showing the electrokinetic polarization curves of the test group electrogalvanized steel parts treated with the passivation solution obtained in examples 1 to 3 of the present invention, compared with those of the control group electrogalvanized steel parts untreated with the passivation solution in a 3.5% sodium chloride solution;
FIG. 2 is a graph showing the comparison of the AC impedances of the test galvanized steel parts treated with the passivation solution and the control galvanized steel parts untreated with the passivation solution obtained in examples 1 to 3 of the present invention in a 3.5% sodium chloride solution.
Detailed Description
In order to make the technical means, creation characteristics, achievement purposes and effects of the zinc plating layer easy to understand, the following embodiment is used for describing the environment-friendly silicate passivation solution for the zinc plating layer, the preparation method and the application thereof in detail by combining the accompanying drawings.
Example 1 ]
In the embodiment, an environment-friendly silicate passivation solution for zinc plating and a preparation method and application thereof are provided.
The components and contents of the environment-friendly silicate passivation solution of the zinc coating in the embodiment are as follows: 20g/L of sodium silicate, 5g/L of inorganic auxiliary film forming agent, 5ml/L of organic auxiliary film forming agent, 6g/L of composite oxidant, 5ml/L of activating agent, 3g/L of buffering agent and the balance of water.
The pH value of the environment-friendly silicate passivation solution of the zinc coating in the embodiment is 2.7.
Wherein, the inorganic auxiliary film forming agent is 0.5g/L sodium tungstate, 2g/L sodium molybdate, 0.5g/L sodium fluozirconate, 0.5g/L sodium fluoride and 1.5g/L nickel acetate.
The organic auxiliary film forming agent is oxalic acid 0.5ml/L, tannic acid 0.5ml/L, benzoic acid 0.8ml/L, sodium polyphosphate 0.6ml/L, ethylene thiourea 1ml/L, diethylene triamine penta-methylene phosphonic acid 1.6 ml/L.
The composite oxidant is sodium hypochlorite 0.5g/L, potassium nitrate 2g/L, cerium nitrate 1g/L, aluminum nitrate 1.5g/L and zinc nitrate 1 g/L.
The activator is 3ml/L sulfuric acid, 1ml/L phosphoric acid, 2ml/L nitric acid.
The buffer is 0.5g/L sodium acetate, 0.5g/L trisodium citrate, 1.5g/L sodium tartrate, 0.5g/L boric acid.
The embodiment also provides a preparation method of the environment-friendly silicate passivation solution for the zinc coating, and the specific implementation mode is as follows:
and step 1, mixing an inorganic auxiliary film forming agent, an activating agent, a buffering agent and deionized water, and continuously stirring for 2 minutes at a rotating speed of 500 revolutions per minute to obtain a mixed solution A.
And 2, dissolving the composite oxidant in deionized water to obtain a mixed solution B, dropwise adding the mixed solution B into the mixed solution A under the stirring condition, and continuously stirring for 2 minutes at the rotating speed of 500 revolutions per minute to obtain a mixed solution C.
And 3, dropwise adding sodium silicate into the mixed solution C under the stirring condition, and continuously stirring at the rotating speed of 800 revolutions per minute for 2 minutes to obtain a mixed solution D.
And step 4, dropwise adding the organic auxiliary film forming agent into the mixed solution D under the stirring condition, adding deionized water to a constant volume, and continuously stirring for 2 minutes at the rotating speed of 800 revolutions per minute to obtain the environment-friendly silicate passivation solution of the zinc coating.
The embodiment also provides an application of the environment-friendly silicate passivation solution for the zinc coating, which comprises the following specific application modes:
and (3) washing the galvanized steel part with deionized water, soaking in 3% nitric acid aqueous solution for 5 seconds, taking out, washing with deionized water, immediately soaking in the environment-friendly silicate passivation solution for 3 minutes, taking out, washing with deionized water, and naturally airing to obtain the galvanized steel part experimental group after the passivation solution treatment.
The passivation film of the galvanized steel sheet treated by the passivation solution prepared by the embodiment is colorless and transparent, and the plating layer is uniform and compact and has good adhesive force.
Electrokinetic polarization tests were performed on the electrogalvanized steel pieces of the experimental and control groups obtained in this example in a 3.5% sodium chloride solution. The potentiodynamic polarization curve obtained is shown in figure 1. As can be seen from fig. 1, the experimental group exhibited a more positive corrosion potential and lower corrosion current density in the 3.5% sodium chloride solution than the control group.
Table 1 shows the comparison of the self-corrosion potential, the self-corrosion current density, the corrosion current density of the passivation zone and the passivation zone width of the test group electrogalvanized steel pieces treated with the passivation solution obtained in examples 1 to 3 of the present invention and the control group electrogalvanized steel pieces not passivated under the potentiodynamic polarization test in 3.5% sodium chloride solution.
As is clear from Table 1, the corrosion current density of the experimental group was 7.858X 10 -6 A·dm 2 . This compares with the corrosion current density of the control group (2.153×10 -4 A·dm 2 ) An order of magnitude lower. The self-corrosion potential of the experimental group was-1.20V, which was shifted approximately 80mV forward compared to the self-corrosion potential of the control group. And the experimental group has a larger passivation area, and the passivation area corrosion current density is reduced by nearly an order of magnitude compared with the passivation area corrosion current density of the control group. This demonstrates that the experimental group has good corrosion resistance and self-healing ability.
The electrogalvanized steel parts of the experimental group and the control group obtained in this example were subjected to electrochemical impedance spectroscopy in a 3.5% sodium chloride solution. The obtained electrochemical impedance spectrum is shown in fig. 2. As can be seen from fig. 2, the experimental group had a larger resistance radius in 3.5% sodium chloride solution than the control group steel, which demonstrates that the experimental group had a greater protection against penetration of the corrosive medium than the control group steel.
The electrogalvanized steel parts of the experimental group and the control group obtained in this example were subjected to titration test using 5% copper sulfate aqueous solution. The surface of the zinc coating became black immediately after titration of the steel in the control group, and serious black corrosions formed on the whole surface over time, whereas the test group began to become light black in the local area of the zinc plating layer after titration for more than 90 seconds.
Neutral salt spray test was performed on the electrogalvanized steel pieces of the experimental group and the control group obtained in this example. The control steel began to show white corrosion products after about less than 1 hour in the salt spray box, whereas the experimental group showed white rust for 126 hours. This demonstrates that the experimental group has greater corrosion resistance than the control group steel.
Example 2 ]
In the embodiment, an environment-friendly silicate passivation solution for zinc plating and a preparation method and application thereof are provided.
The components and contents of the environment-friendly silicate passivation solution of the zinc coating in the embodiment are as follows: 25g/L of sodium silicate, 7g/L of inorganic auxiliary film forming agent, 6ml/L of organic auxiliary film forming agent, 6g/L of composite oxidant, 6ml/L of activating agent, 3g/L of buffering agent and the balance of water.
The pH value of the environment-friendly silicate passivation solution of the zinc coating in the embodiment is 2.5.
Wherein, the inorganic auxiliary film forming agent is 0.5g/L sodium tungstate, 2g/L sodium molybdate, 0.5g/L sodium fluozirconate, 1.5g/L sodium fluoride, 1.5g/L cobalt acetate and 2g/L zinc acetate.
The organic auxiliary film forming agent is oxalic acid 0.5ml/L, malic acid 1ml/L, tannic acid 0.5ml/L, benzoic acid 0.5ml/L, polyphosphoric acid 1ml/L, thiourea 1ml/L and aminotrimethylene phosphonic acid 1.5 ml/L.
The composite oxidant is 0.5g/L hypochlorous acid, 0.5g/L perchloric acid, 1g/L potassium nitrate, 1g/L sodium nitrate, 0.5g/L aluminum nitrate, 2g/L zinc nitrate and 0.5g/L lanthanum nitrate.
The activator is 2ml/L sulfuric acid, 1ml/L hydrochloric acid, 1ml/L phosphoric acid, 2ml/L nitric acid.
The buffer is 0.5g/L ammonia acetate, 1g/L trisodium citrate, 1g/L sodium tartrate, 0.5g/L boric acid.
The embodiment also provides a preparation method of the environment-friendly silicate passivation solution for the zinc coating, and the specific implementation mode is as follows:
and step 1, mixing an inorganic auxiliary film forming agent, an activating agent, a buffering agent and deionized water, and continuously stirring for 2 minutes at a rotating speed of 500 revolutions per minute to obtain a mixed solution A.
And 2, dissolving the composite oxidant in deionized water to obtain a mixed solution B, dropwise adding the mixed solution B into the mixed solution A under the stirring condition, and continuously stirring for 2 minutes at the rotating speed of 500 revolutions per minute to obtain a mixed solution C.
And 3, dropwise adding sodium silicate into the mixed solution C under the stirring condition, and continuously stirring at the rotating speed of 800 revolutions per minute for 2 minutes to obtain a mixed solution D.
And step 4, dropwise adding the organic auxiliary film forming agent into the mixed solution D under the stirring condition, adding deionized water to a constant volume, and continuously stirring for 2 minutes at the rotating speed of 800 revolutions per minute to obtain the environment-friendly silicate passivation solution of the zinc coating.
The embodiment also provides an application of the environment-friendly silicate passivation solution for the zinc coating, which comprises the following specific application modes:
and (3) washing the galvanized steel part with deionized water, soaking in 3% nitric acid aqueous solution for 7 seconds, taking out, washing with deionized water, immediately soaking in the environment-friendly silicate passivation solution of the zinc coating prepared in the embodiment for 4 minutes, taking out, washing with deionized water, and naturally airing to obtain the galvanized steel part experimental group after the passivation solution treatment.
The passivation film of the galvanized steel sheet treated by the passivation solution prepared by the embodiment is colorless and transparent, and the plating layer is uniform and compact and has good adhesive force.
Electrokinetic polarization tests were performed on the electrogalvanized steel pieces of the experimental and control groups obtained in this example in a 3.5% sodium chloride solution. The potentiodynamic polarization curve obtained is shown in figure 1. As can be seen from fig. 1, the experimental group exhibited a more positive corrosion potential and lower corrosion current density in the 3.5% sodium chloride solution than the control group.
As is clear from Table 1, the corrosion current density of the experimental group was 1.846X10 -5 A·dm 2 . This compares with the corrosion current density of the control group (2.153×10 -4 A·dm 2 ) An order of magnitude lower. The self-corrosion potential of the experimental group was-1.23V, which was shifted approximately 50mV forward compared to the self-corrosion potential of the control group. And the experimental group has a larger passivation area, and the passivation area corrosion current density is reduced by nearly an order of magnitude compared with the passivation area corrosion current density of the control group. This demonstrates that the experimental group has good corrosion resistance and self-healing ability.
The electrogalvanized steel parts of the experimental group and the control group obtained in this example were subjected to electrochemical impedance spectroscopy in a 3.5% sodium chloride solution. The obtained electrochemical impedance spectrum is shown in fig. 2. As can be seen from fig. 2, the experimental group had a larger impedance radius in 3.5% sodium chloride solution than the control group steel. This demonstrates that the experimental group has greater protection against penetration of corrosive media than the control group steel.
The electrogalvanized steel parts of the experimental group and the control group obtained in this example were subjected to titration test using 5% copper sulfate aqueous solution. The surface of the zinc coating became black immediately after titration of the control steel, and serious black corrosions formed over the whole surface over time, whereas the experimental group began to become light black after titration only in a localized area of the electrogalvanized layer after 85 seconds.
Neutral salt spray test was performed on the electrogalvanized steel pieces of the experimental group and the control group obtained in this example. The control steel starts to show white corrosion products after being placed in the salt spray box for less than about 1 hour, and the experimental group shows white rust for 120 hours. This demonstrates that the experimental group has greater corrosion resistance than the control group steel.
Example 3 ]
In the embodiment, an environment-friendly silicate passivation solution for zinc plating and a preparation method and application thereof are provided.
The components and contents of the environment-friendly silicate passivation solution of the zinc coating in the embodiment are as follows: 30g/L of sodium silicate, 6g/L of inorganic auxiliary film forming agent, 5ml/L of organic auxiliary film forming agent, 7g/L of composite oxidant, 6ml/L of activating agent, 3g/L of buffering agent and the balance of water.
The pH value of the environment-friendly silicate passivation solution of the zinc coating in the embodiment is 2.5.
Wherein, the inorganic auxiliary film forming agent is 0.5g/L sodium vanadate, 2.5g/L sodium molybdate, 0.5g/L sodium fluorozirconate, 2g/L sodium fluoride, 1.5g/L cobalt sulfate and 1g/L aluminum sulfate.
The organic auxiliary film forming agent is oxalic acid 0.5ml/L, salicylic acid 1ml/L, tannic acid 0.5ml/L, malic acid 0.5ml/L, polyphosphoric acid 1ml/L, ethylene thiourea 0.5ml/L and ethylene diamine tetramethylene phosphonic acid 1 ml/L.
The composite oxidant is 0.5g/L hypochlorous acid, 1g/L potassium permanganate, 0.5g/L perchloric acid, 1g/L potassium nitrate, 1g/L sodium nitrate, 0.5g/L cerium nitrate, 2g/L zinc nitrate and 0.5g/L lanthanum nitrate.
The activator is 1ml/L sulfuric acid, 0.5ml/L hydrochloric acid, 2ml/L phosphoric acid, 2ml/L nitric acid, 0.5ml/L sulfamic acid.
The buffer is 1g/L of ammonium bifluoride, 1g/L of trisodium citrate, 0.5g/L of sodium tartrate and 0.5g/L of boric acid.
The embodiment also provides a preparation method of the environment-friendly silicate passivation solution for the zinc coating, and the specific implementation mode is as follows:
and step 1, mixing an inorganic auxiliary film forming agent, an activating agent, a buffering agent and deionized water, and continuously stirring for 2 minutes at a rotating speed of 500 revolutions per minute to obtain a mixed solution A.
And 2, dissolving the composite oxidant in deionized water to obtain a mixed solution B, dropwise adding the mixed solution B into the mixed solution A under the stirring condition, and continuously stirring for 2 minutes at the rotating speed of 500 revolutions per minute to obtain a mixed solution C.
And 3, dropwise adding sodium silicate into the mixed solution C under the stirring condition, and continuously stirring at the rotating speed of 800 revolutions per minute for 2 minutes to obtain a mixed solution D.
And step 4, dropwise adding the organic auxiliary film forming agent into the mixed solution D under the stirring condition, adding deionized water to a constant volume, and continuously stirring for 2 minutes at the rotating speed of 800 revolutions per minute to obtain the environment-friendly silicate passivation solution of the zinc coating.
The embodiment also provides an application of the environment-friendly silicate passivation solution for the zinc coating, which comprises the following specific application modes:
and (3) washing the galvanized steel part with deionized water, soaking in 3% nitric acid aqueous solution for 7 seconds, taking out, washing with deionized water, immediately soaking in the environment-friendly silicate passivation solution of the zinc coating prepared in the embodiment for 5 minutes, taking out, washing with deionized water, and naturally airing to obtain the galvanized steel part experimental group treated by the passivation solution.
The passivation film of the galvanized steel sheet treated by the passivation solution prepared by the embodiment is colorless and transparent, and the plating layer is uniform and compact and has good adhesive force.
Electrokinetic polarization tests were performed on the electrogalvanized steel pieces of the experimental and control groups obtained in this example in a 3.5% sodium chloride solution. The potentiodynamic polarization curve obtained is shown in figure 1. As can be seen from fig. 1, the experimental group exhibited a more positive corrosion potential and lower corrosion current density in the 3.5% sodium chloride solution than the control group.
As is clear from Table 1, the corrosion current density of the experimental group was 1.474×10 -5 A·dm 2 . This compares with the corrosion current density of the control group (2.153×10 -4 A·dm 2 ) An order of magnitude lower. The self-corrosion potential of the experimental group was-1.203V, which was shifted approximately 80mV forward compared to the self-corrosion potential of the control group. And the experimental group has a larger passivation area, and the passivation area corrosion current density is reduced by nearly an order of magnitude compared with the passivation area corrosion current density of the control group. This demonstrates that the experimental group has good corrosion resistance and self-healing ability.
The electrogalvanized steel parts of the experimental group and the control group obtained in this example were subjected to electrochemical impedance spectroscopy in a 3.5% sodium chloride solution. The obtained electrochemical impedance spectrum is shown in fig. 2. As can be seen from fig. 2, the experimental group had a larger impedance radius in 3.5% sodium chloride solution than the control group steel. This demonstrates that the experimental group has greater protection against penetration of corrosive media than the control group steel.
The electrogalvanized steel parts of the experimental group and the control group obtained in this example were subjected to titration test using 5% copper sulfate aqueous solution. The surface of the zinc coating became black immediately after titration of the control steel, and serious black corrosions formed over the whole surface over time, whereas the experimental group began to become light black after 92 seconds after titration in the local area of the electrogalvanized layer.
Neutral salt spray test was performed on the electrogalvanized steel pieces of the experimental group and the control group obtained in this example. The control steel began to show white corrosion products after about less than 1 hour in the salt spray box, while the experimental group showed white rust for 123 hours. This demonstrates that the experimental group has greater corrosion resistance than the control group steel.
TABLE 1
Effects and effects of the examples
According to the environment-friendly silicate passivation solution for zinc plating layers and the preparation method and the application thereof, the components and the contents of the environment-friendly silicate passivation solution for zinc plating layers are as follows: 10-35 g/L of sodium silicate, 2-10 g/L of inorganic auxiliary film forming agent, 3-15 ml/L of organic auxiliary film forming agent, 5-10 g/L of composite oxidant, 5-15 ml/L of activating agent, 2-10 g/L of buffering agent, and the pH value of the environment-friendly silicate passivation solution of water and zinc coating is 1.5-3.5. The environment-friendly silicate passivation solution for zinc plating can be used for the post-treatment process of hot galvanizing and electrogalvanizing of steel parts, and the galvanized layer passivation film treated by the passivation solution has bright and transparent film layer, uniform film formation, good corrosion resistance, good film adhesion and simple passivation treatment process.
The environment-friendly silicate passivation solution for the zinc plating layers in the embodiments 1-3 has simple component system, does not contain trivalent chromium, hexavalent chromium and other harmful substances, is environment-friendly and pollution-free, and can realize clean production of galvanized products.
The zinc plating silicate passivating solutions of embodiments 1-3 adopt a stable composite oxidant to replace the traditional hydrogen peroxide oxidant which is easy to decompose, the stability of the plating solution is good, the service life of the plating solution is greatly prolonged, and meanwhile, the storage and the transportation of the passivating solution are convenient.
The zinc plating silicate passivation solutions of examples 1 to 3 make full use of the synergistic effect of organic and inorganic film formation to construct a composite passivation film. The organic film and the inorganic film are coordinated with each other, so that the self-repairing function of the passivation film can be effectively improved, the film forming quality is improved, the porosity is reduced, the binding force between the plating layer and the substrate is improved, and the corrosion resistance of the silicate passivation film is greatly improved.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (5)
1. An environment-friendly silicate passivation solution for zinc plating is characterized in that:
the components and the contents of the environment-friendly silicate passivation solution of the zinc coating are respectively as follows: 10-35 g/L of sodium silicate, 2-10 g/L of inorganic auxiliary film forming agent, 3-15 ml/L of organic auxiliary film forming agent, 5-10 g/L of composite oxidant, 5-15 ml/L of activator, 2-10 g/L of buffer and water,
the pH value of the environment-friendly silicate passivation solution of the zinc coating is 1.5-3.5,
wherein the inorganic auxiliary film forming agent is any one or more of sodium tungstate, sodium molybdate, sodium vanadate, sodium fluosilicate, sodium fluozirconate, sodium fluoride, sodium bromide, potassium fluozirconate, zinc acetate, nickel acetate, cobalt acetate, magnesium sulfate, aluminum sulfate, cobalt sulfate and nickel sulfate,
the organic auxiliary film forming agent is any one or more of oxalic acid, tannic acid, malic acid, benzoic acid, polyphosphoric acid, sodium polyphosphate, amino phosphoric acid, salicylic acid, ascorbic acid, thiourea, ethylene thiourea, aminotrimethylene phosphonic acid, diethylenetriamine penta-methylene phosphonic acid and ethylenediamine tetra-methylene phosphonic acid,
the composite oxidant is any two or more of hypochlorous acid, sodium hypochlorite, perchloric acid, potassium nitrate, sodium nitrate, potassium permanganate, cerium nitrate, aluminum nitrate, zinc nitrate and lanthanum nitrate.
2. The environment-friendly silicate passivation solution for zinc plating according to claim 1, wherein the passivation solution is characterized in that:
wherein the activating agent is any one or more of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, sulfamic acid, nitric acid, citric acid and tartaric acid.
3. The environment-friendly silicate passivation solution for zinc plating according to claim 1, wherein the passivation solution is characterized in that:
wherein the buffer is any one or more of sodium acetate, ammonium bifluoride, trisodium citrate, sodium tartrate, boric acid and potassium citrate.
4. A method for preparing the environment-friendly silicate passivation solution for zinc plating according to any one of claims 1 to 3, comprising the following steps:
step 1, mixing an inorganic auxiliary film forming agent, an activating agent, a buffering agent and deionized water, and continuously stirring for 2-5 minutes at a rotating speed of 400-600 rpm to obtain a mixed solution A;
step 2, dissolving a composite oxidant in deionized water to obtain a mixed solution B, dropwise adding the mixed solution B into the mixed solution A under the stirring condition, and continuously stirring for 2-5 minutes at the rotating speed of 400-600 rpm to obtain a mixed solution C;
step 3, dropwise adding sodium silicate into the mixed solution C under the stirring condition, and continuously stirring for 2-5 minutes at the rotating speed of 800-1200 rpm to obtain a mixed solution D;
and step 4, dropwise adding the organic auxiliary film forming agent into the mixed solution D under the stirring condition, adding deionized water to a constant volume, and continuously stirring for 2-5 minutes at the rotating speed of 800-1200 rpm to obtain the environment-friendly silicate passivation solution of the zinc coating.
5. An application of an environment-friendly silicate passivation solution for a zinc coating is characterized in that:
immersing the electrogalvanized steel piece or the hot dip galvanized steel piece into the environment-friendly silicate passivation solution of the zinc coating to realize passivation treatment of the zinc coating,
the environment-friendly silicate passivation solution for the zinc coating is any one of claims 1-3.
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