CN114855152A - 一种金属表面环保铁系无磷皮膜处理组合物、处理剂及其制备方法、应用 - Google Patents
一种金属表面环保铁系无磷皮膜处理组合物、处理剂及其制备方法、应用 Download PDFInfo
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- CN114855152A CN114855152A CN202210421046.5A CN202210421046A CN114855152A CN 114855152 A CN114855152 A CN 114855152A CN 202210421046 A CN202210421046 A CN 202210421046A CN 114855152 A CN114855152 A CN 114855152A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 233
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 117
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 110
- 239000002184 metal Substances 0.000 title claims abstract description 110
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 51
- -1 accelerant Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000000872 buffer Substances 0.000 claims abstract description 7
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 7
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 230000000536 complexating effect Effects 0.000 claims description 10
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 9
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 229960002413 ferric citrate Drugs 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000006172 buffering agent Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- XCXKNNGWSDYMMS-UHFFFAOYSA-N 2-methyl-1-nitroguanidine Chemical compound CNC(N)=N[N+]([O-])=O XCXKNNGWSDYMMS-UHFFFAOYSA-N 0.000 claims description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- SFOKDWPZOYRZFF-UHFFFAOYSA-H 2,3-dihydroxybutanedioate;iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O SFOKDWPZOYRZFF-UHFFFAOYSA-H 0.000 claims description 2
- JLLRXSCNTCSLFX-UHFFFAOYSA-H 2-hydroxybutanedioate;iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C(O)CC([O-])=O.[O-]C(=O)C(O)CC([O-])=O.[O-]C(=O)C(O)CC([O-])=O JLLRXSCNTCSLFX-UHFFFAOYSA-H 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- CHYQSXLXQCXPAA-UHFFFAOYSA-H butanedioate;iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)CCC([O-])=O.[O-]C(=O)CCC([O-])=O.[O-]C(=O)CCC([O-])=O CHYQSXLXQCXPAA-UHFFFAOYSA-H 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000007739 conversion coating Methods 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- WHRBSMVATPCWLU-UHFFFAOYSA-K iron(3+);triformate Chemical compound [Fe+3].[O-]C=O.[O-]C=O.[O-]C=O WHRBSMVATPCWLU-UHFFFAOYSA-K 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 21
- 230000007797 corrosion Effects 0.000 abstract description 14
- 238000005260 corrosion Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 7
- 239000007769 metal material Substances 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002161 passivation Methods 0.000 description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 12
- 239000010960 cold rolled steel Substances 0.000 description 12
- 239000004317 sodium nitrate Substances 0.000 description 11
- 235000010344 sodium nitrate Nutrition 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 9
- 239000004246 zinc acetate Substances 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000011640 ferrous citrate Substances 0.000 description 5
- 235000019850 ferrous citrate Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011684 sodium molybdate Substances 0.000 description 5
- 235000015393 sodium molybdate Nutrition 0.000 description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 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 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000002444 silanisation Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 229960004642 ferric ammonium citrate Drugs 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 229920003063 hydroxymethyl cellulose Chemical class 0.000 description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 2
- 239000004313 iron ammonium citrate Substances 0.000 description 2
- 235000000011 iron ammonium citrate Nutrition 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229960000355 copper sulfate Drugs 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical class C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- AXKBOWBNOCUNJL-UHFFFAOYSA-M sodium;2-nitrophenolate Chemical compound [Na+].[O-]C1=CC=CC=C1[N+]([O-])=O AXKBOWBNOCUNJL-UHFFFAOYSA-M 0.000 description 1
- CURNJKLCYZZBNJ-UHFFFAOYSA-M sodium;4-nitrophenolate Chemical compound [Na+].[O-]C1=CC=C([N+]([O-])=O)C=C1 CURNJKLCYZZBNJ-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Images
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- 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
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- 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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- 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
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- 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
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Abstract
本申请涉及金属皮膜剂技术领域，具体公开了一种金属表面环保铁系无磷皮膜处理组合物、处理剂及其制备方法、应用。一种金属表面环保铁系无磷皮膜处理剂，包括溶剂和如下组分：铁源、络合缓冲剂、促进剂、表面活性剂、添加剂；所述铁源为有机酸铁盐、无机酸铁盐、铁氧化物、铁氢氧化物、高分子聚合铁中的一种或多种；所述处理剂体系的pH值范围为0‑6。本申请的金属表面环保铁系无磷皮膜处理剂可用于冷轧铁材、热轧铁材、铸铁件、镀锌件、压铸铝等金属材料工件的表面处理成膜，其具有漆膜结合力高、耐腐蚀性能好的优点。
Description
技术领域
本申请涉及金属皮膜剂技术领域，更具体地说，它涉及一种金属表面环保铁系无磷皮膜处理组合物、处理剂及其制备方法、应用。
背景技术
金属工件如钢铁制品、锌制品、铝制品等在涂装前，需要进行预处理，目前主要的处理工艺是采用磷酸盐皮膜剂在金属工件表面转化处理，使其表面生成一层具有一定粗糙度、多孔性、吸附性的黑色、银灰色或彩色的磷酸盐转化皮膜，如磷酸铁膜，磷酸锌膜等，以增强工件表面的耐腐蚀性，同时也能够提高工件表面与涂层、漆膜等其他有机表面处理层之间的附着力。
磷化盐处理工艺经过100多年的发展，已经非常成熟。钢铁工件表面经过磷化后再进行涂装，具有优异的抗腐蚀性能，能够耐800小时以上中性盐雾。但是，磷化工艺存在着严重的磷污染、亚硝酸盐污染和镍污染，会对生态环境造成巨大危害，并且产生的有害废水的处理难度很大，会浪费大量人力物力，导致生产成本急剧增加。
进入20世纪以后，技术人员开发出钢铁或锌工件表面的无磷皮膜剂：纳米陶化剂和硅烷化皮膜剂，纳米陶化剂首先由德国汉高公司开发，近年来我国一些公司也开发了有自己的陶化剂，如申请公布号为CN103046039A的中国专利申请文件公开了一种一步法无磷皮膜剂。陶化剂是以氟锆酸或氟钛酸为代表，在钢铁表面生产一层锆化膜或钛化膜，该层膜在一定程度上增强了漆膜结合力，工艺环保。但是涂装后与漆膜的结合力还不够优异，能耐250小时的中性盐雾，与磷化膜相比相差很远。
硅烷化皮膜剂最先由美国凯米特公司开发，近年来我国的一些公司也相继开发了自己的硅烷化皮膜剂，如申请公布号为CN112048716A的中国专利申请文件公开了一种浓缩型硅烷皮膜剂及其制备方法。硅烷化皮膜剂的原理是在钢铁表面生成一种硅烷化膜，能够增强漆膜的结合力和耐腐蚀性。同样的，硅烷化膜涂装后，耐腐蚀性差，也仅能够耐250小时左右的中性盐雾，与磷化膜相比相差仍然较远。
针对上述的一些无磷皮膜剂，其性能相较于磷化膜有很大的差距，目前实际上还没有开发出一种能够完全替代磷化盐皮膜剂的无磷皮膜剂，因此亟需找到一种全新的具有优异耐腐蚀性、能够耐较长时间中性盐雾的无磷皮膜剂。
发明内容
为了改善无磷皮膜剂处理金属工件成膜后漆膜结合力差，不能长时间耐中性盐雾的问题，本申请提供一种金属表面环保铁系无磷皮膜处理组合物、处理剂及其制备方法、应用。
第一方面，本申请提供一种金属表面环保铁系无磷皮膜处理组合物，采用如下的技术方案：
一种金属表面环保铁系无磷皮膜处理组合物，包括如下重量份数的原料：
铁源：1-200份；
络合缓冲剂：5-300份；
成膜促进剂：0.1-100份；
表面活性剂：2-150份；
所述铁源为有机酸铁盐、无机酸铁盐、铁氧化物、铁氢氧化物、高分子聚合铁中的一种或多种。
第二方面，本申请提供一种金属表面环保铁系无磷皮膜处理剂，采用如下的技术方案：
一种金属表面环保铁系无磷皮膜处理剂，包括溶剂，每升处理剂中包含有如下重量的组分：
铁源：1g-200g；
络合缓冲剂：5g-300g；
成膜促进剂：0.1g-100g；
表面活性剂：2g-150g；
所述铁源为有机酸铁盐、无机酸铁盐、铁氧化物、铁氢氧化物、高分子聚合铁中的一种或多种；所述处理剂的pH值范围为0-6。
通过采用上述技术方案，金属工件表面在经过成膜处理后，能够在工件表面形成一层致密的钝化膜，对金属工件起到非常好的防护作用。并且，钝化膜中含有铁系复合化合物，能够与漆膜、涂层等有机涂装膜层之间的产生很高的结合力，成膜后漆膜结合力测试(百格测试)可达国家0级标准。另外，金属工件在涂装后具有优异的耐腐蚀性，能够耐800小时以上的中性盐雾测试。同时，由于本申请的金属表面环保铁系无磷皮膜处理剂中不含磷系化合物，经过污水处理后符合RoHS标准，绿色环保，非常适合推广。
可选的，所述有机酸铁盐为柠檬酸铁盐、甲酸铁盐、乙酸铁盐、酒石酸铁盐、苹果酸铁盐、丙二酸铁盐、丁二酸铁盐中的一种或多种。
通过采用上述技术方案，优化和调整有机酸铁盐中阴离子的种类组成，这些有机酸根与铁离子之间产生螯合作用，改善钝化膜的成膜状态，使得钝化膜更加致密均匀。
可选的，所述无机酸铁盐为盐酸铁盐、硫酸铁盐、氨基磺酸铁盐、硝酸铁盐中的一种或多种。
通过采用上述技术方案，试验和优化无机酸铁盐中的阴离子种类组成，这些无机酸根离子能够参与到有机酸根离子的螯合反应，并且具有较合适的离子半径和空间位阻，优化成膜过程，进一步改善钝化膜的微观层结构，提升钝化膜与漆膜的结合力，改善长期耐腐蚀性能。
可选的，所述铁氧化物为氧化铁。
可选的，所述铁氢氧化物为氢氧化铁。
可选的，所述络合缓冲剂为有机酸、有机碱、无机酸、无机碱、有机酸盐、无机酸盐中的一种或多种；所述有机酸为柠檬酸、酒石酸、乙酸、乙二酸、丙二酸、丁二酸、苹果酸、邻苯二甲酸中的一种或多种。
可选的，所述有机碱为乙二胺、乙醇胺、二乙醇胺、三乙醇胺、丁二胺中的一种或多种。
可选的，所述无机酸为硫酸、盐酸、硝酸中的一种或多种。
可选的，所述无机碱为氢氧化钠、氢氧化钾、氨水中的至少一种。
可选的，所述有机碱盐为乙二胺盐、乙醇胺盐、二乙醇胺盐、三乙醇胺盐、丁二胺盐中的一种或多种。
可选的，所述有机酸盐为柠檬酸盐、酒石酸盐、乙二酸盐、丙二酸盐、丁二酸盐、苹果酸盐、邻苯二甲酸盐中的一种或多种。
通过采用上述技术方案，优化和调整络合缓冲剂的种类组成，为钝化膜的成膜提供一个合适的酸碱环境，并且有机酸、有机碱等组分可以与铁源中的有机酸铁盐产生螯合竞争作用，以使得钝化膜的成膜过程更加均匀。
可选的，促进剂为硝酸、亚硝酸、硝酸盐、亚硝酸盐、钼酸盐、胍基化合物、硝基苯磺酸盐、硝基苯酚、硫酸羟胺、盐酸羟胺、氯酸盐、过硫酸盐中的一种或多种。
可选的，所述胍基化合物为硝基胍、1-甲基-3-硝基胍中的至少一种。
进一步可选的，所述促进剂为亚硝酸、亚硝酸钠、硫酸羟胺、盐酸羟胺、对硝基苯酚、邻硝基苯酚、间硝基苯酚、硝酸钠、硝酸钾、硝酸、钼酸钠、钼酸铵、钼酸钾、硝基胍、1-甲基-3-硝基胍、对硝基苯磺酸钠、邻硝基苯磺酸钠、间硝基苯磺酸钠、氯酸钾、过硫酸钾中的一种或多种。
通过采用上述技术方案，优化和调整促进剂的种类组成，使得钝化膜的成膜过程更加平稳高效，成膜后钝化膜的各向同性好，成膜质量更高。
可选的，所述表面活性剂为非离子表面活性剂或阳离子表面活性剂。
可选的，所述非离子表面活性剂为X-100、OP-10、吐温-80、AEO系列中的一种或多种。
可选的，所述阳离子离子表面活性剂为甜菜碱系列、季铵盐系列中的至少一种。
可选的，控制处理剂中表面活性剂的浓度为20g/L-60g/L。
可选的，控制处理剂中表面活性剂的浓度为80g/L-120g/L。
可选的，控制处理剂中表面活性剂的浓度为40g/L-55g/L。
可选的，每升处理剂中还包括有0.1g-100g的添加剂，所述添加剂为金属硝酸盐、金属硫酸盐、乙酸盐、氟锆酸、氨水、铵盐、氟钛酸、金属氟锆酸盐、金属氟钛酸盐、氧化锌、聚乙二醇、聚丙烯酰胺、聚丙烯酸、聚乙烯醇、羟甲基纤维素盐中的一种或多种。
进一步可选的，所述添加剂包括硝酸锌、硫酸锌、氧化锌、乙酸锌、硝酸镍、硫酸镍、乙酸镍、硝酸锰、硫酸锰、乙酸锰、硫酸铜、乙酸铜、氟锆酸、氟锆酸钠、氟锆酸钾、氟钛酸、氟钛酸钾、氨水、氯化铵、硫酸铵、硝酸钴、硫酸钴、聚乙二醇、聚丙烯酰胺、聚丙烯酸、聚乙烯醇、羟甲基纤维素钠中的一种或多种。
进一步可选的，所述金属表面环保铁系无磷皮膜处理剂中还可以加入一些其他类型对成膜影响不大的无机物和有机物，不影响本申请金属表面环保铁系无磷皮膜处理剂的使用。
第三方面，本申请提供一种金属表面环保铁系无磷皮膜处理剂的制备方法，采用如下的技术方案：
一种金属表面环保铁系无磷皮膜处理剂的制备方法，包括如下的步骤：
S1：将配方量的铁源、络合缓冲剂、促进剂、表面活性剂、溶剂混合均匀制得浓缩液；
S2：调节浓缩液的pH值范围为0-6后即得。
可选的，所述步骤S1中还包括加入添加剂的步骤。
通过采用上述技术方案，将上述的配方量的组分混合均匀，然后调节至合适的pH值范围，使得成膜过程更加稳定，成膜质量更好。
第四方面，本申请提供一种金属表面环保铁系无磷皮膜处理剂的应用，采用如下的技术方案：
一种金属表面环保铁系无磷皮膜处理剂的应用，包括如下的步骤：
I、将上述的金属表面环保铁系无磷皮膜处理剂对金属工件表面进行化学转化膜处理；II、成膜后水洗处理即可。
通过采用上述技术方案，可以对包括冷轧铁材、热轧铁材、铸铁件、镀锌件、压铸铝等金属材料制成的工件进行成膜处理，并经过除油、水洗前处理工序，使得钝化膜的成膜质量更好，与漆膜的结合力更高，耐腐蚀性能优异。
可选的，本申请的金属表面环保铁系无磷皮膜处理剂可以处理各种金属材料制成的金属工件。
进一步可选的，金属材料可以是但不仅限于冷轧铁材、热轧铁材、铸铁件、镀锌件、锌合金、铸铝等金属材料，处理后均可成膜。
可选的，所述步骤I中还包括对金属工件进行除油、除氧化层、水洗中一种或多种的工序步骤。
通过采用上述技术方案，去除金属工件表面的油渍、氧化层，然后再进行水洗处理，能够为成膜过程提供一个洁净、稳定的成膜环境，以保证成膜质量。
综上所述，本申请具有以下有益效果：
1、由于本申请采用铁源、缓冲络合体系、促进剂体系、表面活性剂体系及其他添加剂进行复配使用制得金属表面环保铁系无磷皮膜剂，对金属工件表面进行成膜处理后形成一层致密的钝化膜，具有很好的漆膜结合力和优异的耐腐蚀性能，漆膜结合力可达国家0级标准，可耐800h以上的中性盐雾测试。并且本申请形成的钝化膜稳定性和耐腐蚀性与国际著名公司锆化液处理后相比提升巨大，本申请金属工件表面的漆膜能够在3.5％氯化钠盐水中煮沸5小时，折弯，漆膜无任何脱落，而国际著名公司锆化液处理后的金属工件表面的漆膜在在3.5％氯化钠盐水中煮沸15分钟，折弯后就完全脱落。
2、本申请的金属表面环保铁系无磷皮膜剂不含有磷系化合物，金属工件进行成膜处理时不产生含磷废水，污水的处理成本更低，也不对环境产生过多的危害。另外，本申请金属表面环保铁系无磷皮膜剂中的铁源原料价格低廉，远低于锆处理液的原料价格，综合生产成本很低，生产效益更高。
3、本申请的金属表面环保铁系无磷皮膜剂能够对多种金属材料工件如热轧钢、铸铁、镀锌铁板、锌合金、压铸铝等进行成膜处理，应用范围广泛，同时不产生有害污水，符合绿色生产、生态友好的生产理念，适合推广应用。
附图说明
图1为本申请实施例1中的冷轧钢板经金属表面环保铁系无磷皮膜处理剂处理后的成膜情况；其中，冷轧钢板的a部分(上部)为成膜状态，b部分(下部)为未成膜状态。
图2为本申请实施例2中冷轧钢板经环保铁系无磷皮膜处理剂处理后的成膜的电子显微镜成像图。
图3为本申请实施例3中镀锌板经环保铁系无磷皮膜处理剂处理成膜后与对比例1中常规锆化液皮膜剂处理后形成的锆化膜比较图；其中，a为铁系皮膜剂处理后的镀锌板；b为常规锆化液皮膜处理后的镀锌板。
图4为本申请实施例3中镀锌板经环保铁系无磷皮膜处理剂处理成膜后与对比例1中常规锆化液皮膜剂处理后形成的锆化膜的耐腐蚀试验比较图；其中，a为铁系皮膜剂处理后的镀锌板；b为常规锆化液皮膜处理后的镀锌板。
图5为本申请实施例中金属表面环保铁系无磷皮膜处理剂处理冷轧钢板成膜工艺示意图。
图6为本申请实施例中金属表面环保铁系无磷皮膜处理剂处理镀锌件成膜工艺示意图。
图7为本申请实施例中金属表面环保铁系无磷皮膜处理剂处理镀锌热轧钢板成膜工艺示意图。
具体实施方式
以下结合实施例和附图对本申请作进一步详细说明。
本具体实施例仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改和替换，但只要在本申请的权利要求范围内都受到专利法的保护。
本申请实施例及对比例的原料除特殊说明以外均为普通市售。
实施例
实施例1
本实施例的金属表面环保铁系无磷皮膜处理组合物，由如下重量的原料组成：柠檬酸亚铁5kg、柠檬酸铁3kg、硫酸亚铁铵2kg、丁二酸2kg、聚丙烯酸1kg、硝酸钠3kg、硝基胍0.2kg、Op-10表面活性剂3kg、钼酸钠1kg、乙酸锌0.5kg。
本实施例的金属表面环保铁系无磷皮膜处理剂，包括如下质量百分比的组分：柠檬酸亚铁5％、柠檬酸铁3％、硫酸亚铁铵2％、丁二酸2％、聚丙烯酸1％、硝酸钠3％、硝基胍0.2％、Op-10表面活性剂3％、钼酸钠1％、乙酸锌0.5％、余量为水。
本实施例的金属表面环保铁系无磷皮膜处理剂的制备方法，包括如下的步骤：
S1：将配方量的柠檬酸亚铁、柠檬酸铁、硫酸亚铁铵、丁二酸、聚丙烯酸、硝酸钠、硝基胍、Op-10表面活性剂、钼酸钠、乙酸锌、水混合均匀制得浓缩液；
S2：将浓缩液加热成透明溶液，稀释10倍后用氢氧化钠调节pH值为3后即得。
本实施例的金属表面环保铁系无磷皮膜处理剂的应用，包括如下步骤：I、将冷轧钢板进行表面除油、水洗后待用；
II、将上述的金属表面环保铁系无磷皮膜处理剂加热至40℃，然后采用喷淋的方式后对冷轧钢板表面进行处理，成膜后水洗处理即可。
实施例2
本实施例的金属表面环保铁系无磷皮膜处理组合物，由如下重量的原料组成：柠檬酸铁铵7kg、柠檬酸5kg、硝酸钠3kg、Op-10表面活性剂3kg。
本实施例的金属表面环保铁系无磷皮膜处理剂，包括如下质量百分比的组分：柠檬酸铁铵7％、柠檬酸5％、硝酸钠3％、Op-10表面活性剂3％、余量为水。
本实施例的金属表面环保铁系无磷皮膜处理剂的制备方法，包括如下步骤：
S1：将配方量的柠檬酸亚铁、柠檬酸、硝酸钠、Op-10表面活性剂、水混合均匀制得浓缩液；S2：将浓缩液用氢氧化钠调节pH值为3后即得。
本实施例的金属表面环保铁系无磷皮膜处理剂的应用，包括如下的步骤：I、将冷轧钢板进行表面除油、水洗后待用；
II、在上述的金属表面环保铁系无磷皮膜处理剂内加入0.02g亚硝酸钠，混合均匀，然后采用槽浸的方式后对镀锌板表面进行处理，成膜后水洗处理即可。
实施例3
本实施例的金属表面环保铁系无磷皮膜处理组合物，由如下重量的原料组成：硝酸铁5kg、硫酸亚铁4kg、硫酸亚铁铵2kg、丁二酸2kg、柠檬酸3kg、聚乙二醇1kg、硝酸钠3kg、X-100表面活性剂3kg、硫酸羟胺1kg、乙酸锌0.5kg、乙酸镍0.1kg。
本实施例的金属表面环保铁系无磷皮膜处理剂，包括如下质量百分比的组分：硝酸铁5％、硫酸亚铁4％、硫酸亚铁铵2％、丁二酸2％、柠檬酸3％、聚乙二醇1％、硝酸钠3％、X-100表面活性剂3％、硫酸羟胺1％、乙酸锌0.5％、乙酸镍0.1％、余量为水。
本实施例的金属表面环保铁系无磷皮膜处理剂的制备方法，包括如下的步骤：
S1：将配方量的硝酸铁、硫酸亚铁、硫酸亚铁铵、丁二酸、柠檬酸、聚乙二醇、硝酸钠、X-100表面活性剂、硫酸羟胺、乙酸锌、乙酸镍、乙酸锌、水混合均匀制得浓缩液；
S2：将浓缩液加热成透明溶液，稀释10倍，用氢氧化钠调节pH值为3后即得。
本实施例的金属表面环保铁系无磷皮膜处理剂的应用，包括如下的步骤：I、将镀锌板进行表面除油、水洗后待用；
II、将上述的金属表面环保铁系无磷皮膜处理剂在常温下使用，采用喷淋的方式后对镀锌板表面进行处理，成膜后水洗处理即可。
实施例4-8
实施例4-8中的金属表面环保铁系无磷皮膜处理剂中各主要组分含量(％)，余量为水，如表1所示。
表1实施例4-8中金属表面环保铁系无磷皮膜处理剂中主要组分含量
实施例4-8的金属表面环保铁系无磷皮膜处理剂的制备方法与实施例1的不同之处在于：步骤S2中，调节pH值为0后即得。
实施例4-8的金属表面环保铁系无磷皮膜处理剂的应用与实施例1相同。
实施例9-13
实施例9-13中的金属表面环保铁系无磷皮膜处理剂中各主要组分含量(％)，余量为水，如表2所示。
表2实施例9-13中金属表面环保铁系无磷皮膜处理剂中主要组分含量
实施例9-13的金属表面环保铁系无磷皮膜处理剂的制备方法与实施例1的不同之处在于：步骤S2中，用氢氧化钠调节pH值为6后即得。
实施例9-13的金属表面环保铁系无磷皮膜处理剂的应用与实施例1相同。
实施例14-18
实施例14-18中的金属表面环保铁系无磷皮膜处理剂中各主要组分含量(％)，余量为水，如表3所示。
表3实施例14-18中金属表面环保铁系无磷皮膜处理剂中主要组分含量
实施例14-18的金属表面环保铁系无磷皮膜处理剂的制备方法与实施例1相同。
实施例14-18的金属表面环保铁系无磷皮膜处理剂的应用与实施例1相同。
实施例19-23
实施例19-23中的金属表面环保铁系无磷皮膜处理剂中各主要组分含量(％)，余量为水，如表4所示。
表4实施例19-23中金属表面环保铁系无磷皮膜处理剂中主要组分含量
实施例19-23的金属表面环保铁系无磷皮膜处理剂的制备方法与实施例1相同。
实施例19-23的金属表面环保铁系无磷皮膜处理剂的应用与实施例1相同。
实施例24-28
实施例24-28中的金属表面环保铁系无磷皮膜处理剂中各主要组分含量(％)，余量为水，如表5所示。
表5实施例24-28中金属表面环保铁系无磷皮膜处理剂中主要组分含量
实施例24-28的金属表面环保铁系无磷皮膜处理剂的制备方法与实施例1相同。
实施例24-28的金属表面环保铁系无磷皮膜处理剂的应用与实施例1相同。
对比例
对比例1
本对比例的无磷皮膜剂，包括如下质量百分比的组分：氟锆酸2％、聚乙二醇(12000)2％、氟化钠0.6％、丙烯酸1.5％、0P-100 1％、余量为水。
本对比例的无磷皮膜剂的制备方法，包括如下步骤：将配方量的氟锆酸、聚乙二醇(12000)、氟化钠、丙烯酸、0P-100、水混匀即得。
本对比例的金属表面环保铁系无磷皮膜处理剂的应用，包括如下步骤：将上述的无磷皮膜剂加热至35℃，然后在钢板上膜，上膜时间为1.5-2.5min，膜厚0.2μm。
对比例2
本对比例的金属表面环保铁系无磷皮膜处理剂，包括如下质量百分比的组分：柠檬酸亚铁35％、柠檬酸铁15％、硫酸亚铁铵10％、丁二酸2％、聚丙烯酸1％、硝酸钠3％、硝基胍0.2％、Op-10表面活性剂3％、钼酸钠1％、乙酸锌0.5％、余量为水。
本对比例的金属表面环保铁系无磷皮膜处理剂的制备方法与实施例1相同。
本对比例的金属表面环保铁系无磷皮膜处理剂的应用与实施例1相同。
性能检测试验
检测方法
取实施例1上膜后的金属工件，观察金属工件表面的成膜情况，相关测试结果如图1所示。
取实施例1上膜后的金属工件，采用电子显微成型技术观察金属工件表面的成膜情况，相关测试结构如图2所示。
取实施例2以及对比例1上膜后的金属工件，观察成膜外观情况，相关测试结果如图3所示。
取实施例3以及对比例1上膜后的金属工件，采用市售静电粉末对金属工件表面进行喷粉，喷粉厚度为60-80μm，喷粉后在200℃条件下固化15min形成漆膜。测试成膜后漆膜结合力及耐腐蚀性能，测试结果如图4所示。
结果分析
分析实施例1并结合图1可以看出，冷轧钢板经过环保铁盐系无磷皮膜处理剂处理后能够在表面形成一层致密的钝化膜，外观光亮均匀细密，防锈性能良好。
分析实施例2并结合图2可以看出，采用电子显微成像技术观察成膜状态，可以看出钝化膜非常致密均匀，没有任何空洞和裂隙，能够对金属工件表面形成良好的防护。
分析实施例3、对比例1-2并结合图3可以看出，本申请的环保铁盐系无磷皮膜处理剂形成的钝化膜相较于常规锆化液皮膜剂所形成的钝化膜更加致密均匀，成膜状态更好。而对比例2中的处理剂中添加了过多的铁源，成膜后形成的钝化膜不够致密，容易脱落，因此选择合适浓度的铁源是非常重要的。
分析实施例3、对比例1并结合图4，a代表实施例3中采用金属表面环保铁系无磷皮膜处理剂处理后的镀锌板漆膜百格测试结果，b代表对比例1中采用金属表面环保铁系无磷皮膜处理剂处理后的镀锌板漆膜百格测试结果，可以看出，漆膜被划开后，在质量分数为3.5％的氯化钠盐水中煮沸15min并折弯后，采用锆化液处理工艺的镀锌板表面的漆膜完全脱落。而本申请环保铁盐系无磷皮膜处理剂处理的镀锌板，能够在质量分数为3.5％的氯化钠盐水中煮沸长达5h，折弯后漆膜没有任何脱落，成膜后的漆膜结合力非常强，耐腐蚀性能优异。
Claims (10)
1.一种金属表面环保铁系无磷皮膜处理组合物，其特征在于，包括如下重量份数的原料：
铁源：1-200份；
络合缓冲剂：5-300份；
成膜促进剂：0.1-100份；
表面活性剂：2-150份；
所述铁源为有机酸铁盐、无机酸铁盐、铁氧化物、铁氢氧化物、高分子聚合铁中的一种或多种。
2.一种金属表面环保铁系无磷皮膜处理剂，其特征在于，包括溶剂，每升处理剂中包含有如下重量的组分：
铁源：1g-200g；
络合缓冲剂：5g-300g；
成膜促进剂：0.1g-100g；
表面活性剂：2g-150g；
所述铁源为有机酸铁盐、无机酸铁盐、铁氧化物、铁氢氧化物、高分子聚合铁中的一种或多种；所述处理剂的pH值范围为0-6。
3.根据权利要求2所述的一种金属表面环保铁系无磷皮膜处理剂，其特征在于，所述有机酸铁盐为柠檬酸铁盐、甲酸铁盐、乙酸铁盐、酒石酸铁盐、苹果酸铁盐、丙二酸铁盐、丁二酸铁盐中的一种或多种。
4.根据权利要求2所述的一种金属表面环保铁系无磷皮膜处理剂，其特征在于，所述无机酸铁盐为盐酸铁盐、硫酸铁盐、氨基磺酸铁盐、硝酸铁盐中的一种或多种。
5.根据权利要求2所述的一种金属表面环保铁系无磷皮膜处理剂，其特征在于，所述络合缓冲剂为有机酸、有机碱、无机酸、无机碱、有机酸盐、无机酸盐中的一种或多种；所述有机酸为柠檬酸、酒石酸、乙酸、乙二酸、丙二酸、丁二酸、苹果酸、邻苯二甲酸中的一种或多种。
6.根据权利要求2所述的一种金属表面环保铁系无磷皮膜处理剂，其特征在于，所述促进剂为硝酸、亚硝酸、硝酸盐、亚硝酸盐、钼酸盐、胍基化合物、硝基苯磺酸盐、硝基苯酚、硫酸羟胺、盐酸羟胺、氯酸盐、过硫酸盐中的一种或多种。
7.根据权利要求6所述的一种金属表面环保铁系无磷皮膜处理剂，其特征在于，所述胍基化合物为硝基胍、1-甲基-3-硝基胍中的至少一种。
8.根据权利要求2所述的一种金属表面环保铁系无磷皮膜处理剂，其特征在于，每升处理剂中还包括有0.1g-100g的添加剂，所述添加剂为金属硝酸盐、金属硫酸盐、乙酸盐、氟锆酸、氟钛酸、氨水、铵盐、金属氟锆酸盐、金属氟钛酸盐、氧化锌、聚乙二醇、聚丙烯酰胺、聚丙烯酸、聚乙烯醇、羟基纤维素盐中的一种或多种。
9.一种如权利要求2-7任一所述的金属表面环保铁系无磷皮膜处理剂的制备方法，其特征在于，包括如下步骤：
S1：将配方量的铁源、络合缓冲剂、促进剂、表面活性剂、添加剂、溶剂混合均匀制得浓缩液；
S2：调节浓缩液的pH值范围为0-6后即得。
10.一种金属表面环保铁系无磷皮膜处理剂的应用，其特征在于，包括如下步骤：
I、将权利要求2-8任一所述的金属表面环保铁系无磷皮膜处理剂对金属工件表面进行化学转化膜处理；
II、成膜后水洗处理即可。
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