CN117535653A - Environment-friendly water-based treating agent for improving phosphating performance of high-strength steel - Google Patents
Environment-friendly water-based treating agent for improving phosphating performance of high-strength steel Download PDFInfo
- Publication number
- CN117535653A CN117535653A CN202210919224.7A CN202210919224A CN117535653A CN 117535653 A CN117535653 A CN 117535653A CN 202210919224 A CN202210919224 A CN 202210919224A CN 117535653 A CN117535653 A CN 117535653A
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- China
- Prior art keywords
- treating agent
- strength steel
- phosphating
- improving
- based treating
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 57
- 239000010959 steel Substances 0.000 title claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000012736 aqueous medium Substances 0.000 claims abstract description 3
- 150000007524 organic acids Chemical class 0.000 claims abstract description 3
- 235000005985 organic acids Nutrition 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- -1 organic acid compound Chemical class 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 239000010452 phosphate Substances 0.000 claims description 6
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 238000010924 continuous production Methods 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000001263 FEMA 3042 Substances 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000005097 cold rolling Methods 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 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 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 235000015523 tannic acid Nutrition 0.000 claims description 2
- 229940033123 tannic acid Drugs 0.000 claims description 2
- 229920002258 tannic acid Polymers 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 claims 2
- 239000011591 potassium Substances 0.000 claims 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000004381 surface treatment Methods 0.000 abstract description 6
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 23
- 239000000463 material Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005507 spraying Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000012756 surface treatment agent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000797 Ultra-high-strength steel Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007761 roller coating Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 201000009240 nasopharyngitis Diseases 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design 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
- 238000009713 electroplating Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
-
- 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
- C23C22/36—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 containing also phosphates
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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
- C23C22/36—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 containing also phosphates
- C23C22/361—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 containing also phosphates containing titanium, zirconium or hafnium compounds
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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
- C23C22/36—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 containing also phosphates
- C23C22/362—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 containing also phosphates containing also zinc cations
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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
- C23C22/36—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 containing also phosphates
- C23C22/364—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 containing also phosphates containing also manganese cations
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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
- C23C22/36—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 containing also phosphates
- C23C22/364—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 containing also phosphates containing also manganese cations
- C23C22/365—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 containing also phosphates containing also manganese cations containing also zinc and nickel cations
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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
- C23C22/46—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 oxalates
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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
- C23C22/46—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 oxalates
- C23C22/47—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 oxalates containing also phosphates
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Abstract
The invention belongs to the technical field of metal material surface treatment, and particularly relates to an environment-friendly water-based treating agent for improving phosphating performance of high-strength steel, which is prepared by dissolving or dispersing a composition in an aqueous medium, wherein the specific composition of the surface treating agent is as follows: A. a compound selected from the group consisting of fluoride-containing compounds; B. a metal ion compound selected from Cu, zn, mn, ni, fe-containing; C. a compound selected from organic acids; D. a compound selected from the group consisting of surfactants; the surface treating agent is diluted by adding 0-20 parts of water into 1 part of treating agent and then is applied. The treating agent can enable the surface of the high-strength steel plate to have excellent phosphating performance, and is mainly applied to the surface modification treatment of the high-strength steel plate.
Description
Technical Field
The invention relates to the technical field of metal material surface treatment, in particular to an environment-friendly water-based treating agent for the surface of high-strength coil steel, which can ensure that the surface of the high-strength steel plate has excellent phosphating performance and is mainly applied to the surface modification treatment of the high-strength steel.
Background
The phosphating process originates from the early 20 th century and is widely applied to the pretreatment process of the coating of automobiles/household appliances, and the technical development of the phosphating process for century gives a very mature technical system in the aspects of phosphating solution formulation, film forming mechanism and action mechanism. The main phosphating solution in phosphating treatment is contacted with the surface of the steel plate, the hydrogen ion content in the interface area is rapidly reduced through acid etching and corrosion and the oxidation action of the accelerator, and the phosphate radical is promoted to be gradually dissociated and form phosphate deposition on metal ions. Even and fine phosphating layer which completely covers the metal surface can effectively improve the adhesion of the coating and the corrosion performance under the film. The conventional car body is subjected to common cold rolling, and the galvanized material and the phosphating treatment have good and stable matching effect. At present, the phosphating application problem of the novel automobile material with the surface characteristics is more remarkable, and the novel automobile material is also a research hotspot of the industry.
In recent years, with the progress of steel material technology, ultra-high strength steel is increasingly widely applied, and particularly, in view of the remarkable effect of automobile high strength steel in the aspects of safety, environmental protection and light weight, the ultra-high strength steel material technology enters the stages of rapid development, popularization and application. Whereas ultra-high strength steels require the addition of more alloying elements, which directly changes the surface properties of the material. Researches show that the formed composition is enriched on the surface of the steel plate in a selective oxidation mode, so that the problems of coarse crystallization, poor coverage and the like frequently occur in the phosphating process, the phosphating performance is obviously reduced, and the application requirements of coating cannot be met. A plurality of technical researches for optimizing the phosphating performance of the high-strength steel surface are carried out on main steel suppliers at home and abroad. Most of the components are focused on the aspects of controlling the selective oxidation of Mn, si, cr and other elements on the surface of the steel plate (such as CN102834531, CN102482728, CN102534359 and CN 108368590). The technology of the patent needs to control the guarantee of the surface selective oxidation educts and effectively give consideration to the internal oxidation degree and the polar surface oxidation state, has narrow process window and great difficulty, and cannot be compatible with the process design of different component system materials which needs pertinence.
The technology for surface treatment of high-strength steel by good phosphating and modification mainly comprises the technology of removing an oxidation enriched layer by surface electrolytic pickling and the technology of covering the oxidation enriched layer by surface flash plating. The publication numbers CN104136644, CN103124799, CN104508155 and CN103305749 propose a method for removing an oxidation enriched layer affecting the phosphating performance on the surface of high-strength steel through an electrolytic pickling process on the surface of a cold-rolled sheet. The technology has strong operability, can be compatible with materials of different component systems, has the problems of high energy consumption and environmental protection, and is not suitable for a conventional high-strength steel manufacturing production line because of adding an acid washing process.
Publication No. CN104471115 proposes a method of plating zinc on the surface of a steel sheet by a flash plating method with a coverage rate of 60% or more to optimize the surface phosphating property and the mold sticking resistance. Meanwhile, a technology for manufacturing high-strength steel with good phosphating property by means of nickel and iron plating is also reported in the published literature. The technology can endow the surface of the high-strength steel material with novel stable characteristics through plating treatment, but has the disadvantages of overlarge energy consumption, environmental protection and inapplicability to the conventional high-strength steel manufacturing production line because of the need of adding an electroplating process.
The development of the environment-friendly water-based treating agent capable of realizing the optimal control of the surface phosphating performance of the high-strength steel has important significance for the high-efficiency application and popularization of the automobile high-strength steel technology.
Disclosure of Invention
The invention aims to provide an environment-friendly water-based treating agent which can be applied to the phosphating performance optimization modification of the surface of high-strength steel.
The invention finally determines the technical route of the environment-friendly water-based treating agent for nano modification of the good phosphating surface through theoretical analysis, a large amount of laboratory scientific researches and practical verification. The water-based treating agent is formed by combining the surface characteristics of typical high-strength steel to form one or more components of fluorine-containing compounds, metal ion compounds, organic acid compounds and surfactants. The treating agent can be applied to high-speed continuous production process of high-strength coiled steel and manufacturing process of workpieces, a specific treatment mode can form a wet film on the surface of a steel plate in a dipping, spraying, roller coating and other modes, and a surface modification layer with a plurality of nanometer thickness can be formed on the surface of the steel plate rapidly through blowing or drying. The modified treatment layer can form epitaxial active crystal nucleus points with the same orientation as that of phosphating crystals on the surface of the steel plate, so that the phosphating performance of the surface of the high-strength steel plate with high alloy elements (such as Mn, si, cr, mo and the like) is remarkably improved. Meanwhile, the processing performances such as molding, connection and the like are not affected.
The technical scheme of the invention is as follows:
the surface treating agent is prepared by dissolving or dispersing a composition in an aqueous medium, and the specific composition of the surface treating agent is as follows:
E. a compound selected from the group consisting of fluoride-containing compounds;
F. a metal ion compound selected from Cu, zn, mn, ni, fe-containing;
G. a compound selected from organic acids;
H. a compound selected from the group consisting of surfactants;
the invention relates to a surface treating agent application process, which can be applied after 1 part of treating agent is diluted by 0-20 parts of water. Can be directly applied without adding water.
The metal ions according to the present invention are not limited to specific valence states.
The aqueous treating agent of the present invention comprises a compound selected from fluoride-containing ions: ammonium fluorotitanate, ammonium fluorozirconate, potassium fluorotitanate, potassium fluorozirconate, and the like. The molar concentration of the F element in the solution is 0.3 to 1.8mol/L, preferably 0.6 to 1.1mol/L. The additive has the function of homogenizing surface etching, and titanium or zirconium can be deposited on the surface of the material in a punctiform manner to form active sites which are favorable for phosphating nucleation. When the content of F element is lower than 0.3mol/L, the film forming performance of the surface treating agent is poor, and the modification treatment effect is affected; when the F element content is higher than 1.8mol/L, the stability of the surface treatment agent tends to be significantly lowered.
The aqueous treating agent of the present invention is selected from one or more metal ion compounds containing Cu, zn, mn, ni, fe including: sulphate, carbonate, nitrate containing copper ions, sulphate, phosphate, formate, acetate containing Zn ions, phosphate, carbonate, nitrate containing Mn ions, nitrate containing Fe ions, oxalate, sulphate, nitrate containing Ni ions, carbonate. The molar concentration of the metal ion compound in the solution is 0.05 to 0.6mol/L, preferably 0.1 to 0.25mol/L. The additive is mainly used for further supplementing the isomorphous nucleation sites of the phosphating crystals. When the content is lower than 0.05mol/L, the effect of effectively supplementing the phosphorization nucleation point cannot be achieved, and when the content is higher than 0.6mol/L, the even passivation effect can be formed due to the excessive thickness of the modified film layer, and the coatability of the treated surface is directly affected.
The aqueous treating agent of the present invention comprises an organic acid compound selected from the group consisting of: organic acid compounds having complexing and chelating functions such as citric acid, oxalic acid, tannic acid, lactic acid, tartaric acid, and salicylic acid. The molar concentration of the organic acid compound in the solution is 0.03 to 0.4mol/L, preferably 0.05 to 0.2mol/L. The compound has a certain cleaning effect on the surface of the steel plate, and meanwhile, the formed reactant is partially adhered to the surface of the steel plate, so that the rapid nucleation growth of a phosphating film can be promoted. At levels below 0.03mol/L the surface cleaning effect is significantly reduced, and at levels above 0.4mol/L the stability of the treatment system is significantly affected.
The compound selected from the surface active agents in the surface treatment agent mainly comprises: sodium dodecyl sulfate, sodium dodecyl sulfonate, octadecyl amine, triethanolamine, etc., the molar concentration of the surfactant compound in the solution is 0.002-0.015mol/L, preferably 0.003-0.0.0.|mol/L. When the content is less than 0.002mol/L, the film forming performance of the treating agent is not obviously optimized; when the content is more than 0.015mol/L, the film forming quality of the treating agent is obviously influenced, and the phosphating performance optimizing effect is reduced after film forming.
The environment-friendly water-based treating agent with improved phosphating performance for high-strength steel can be applied to continuous production lines of pickling high-strength steel and cold-rolled high-strength steel, a wet film is formed on the surface of a steel plate in a dipping, spraying, roller coating and other modes, and a nanoscale surface modified layer can be formed on the surface of the steel plate by the treating agent in a blowing or drying mode. The effect of remarkably optimizing the surface phosphating performance of the high-strength steel is achieved.
The beneficial technical effects of the invention are as follows:
the environment-friendly water-based treating agent for improving the phosphating performance of the high-strength steel provided by the invention ensures that the surface of the high-strength steel plate has excellent phosphating performance. The water-based treating agent can meet the application of high-speed continuous production process and workpiece manufacturing process of high-strength coil steel; meanwhile, the processing performances such as forming, connection and the like are not affected, and the environment-friendly water-based treating agent is also provided.
Detailed Description
For a better understanding of the present invention, the present invention will be specifically described by way of examples and comparative examples, but the scope of the present invention is not limited by these examples, and the following description will be made on the type of surface treatment agent composition and treated steel sheet used:
(1) Test panel:
the materials used in the examples are typical 80 kg grade ultra-high strength steel, specification 1.2mm, composition as shown in Table 1
Table 1 composition information of the common cold steel sheet used in the examples
(2) The sample plate processing and cleaning method comprises the following steps:
the material is processed into a sample wafer with the thickness of 30 mm by shearing, and is subjected to spray cleaning by using an alkalinity degreasing agent (pH=11-12) to remove dirt and oil adhered on the surface, then is cleaned by using pure water to remove residual alkaline components on the surface, and is dried by cold air for later use.
(3) Composition of water-based surface treatment agent
The composition ratios and treatment methods of the environment-friendly aqueous surface treatment agents used in the examples are shown in table 2.
Wherein comparative example 4 is a raw surface material subjected to surface treatment without the treatment
Table 2 examples and surface treatment composition used
The surface treatment panels obtained in the examples and comparative examples were subjected to 1000mg/m2 of rust preventive oil coating treatment, and after one week of leaving, the phosphating performance evaluation before coating was performed. Laboratory simulation by referring to the pretreatment process flow before coating in an automobile factory mainly comprises degreasing, surfacing and phosphating procedures. The related treating agent is a commercial product of the Paka-rice-flour noodles, and the specific technological parameters are shown in Table 3.
TABLE 3 phosphating process parameters
| Working procedure | Degreasing | Washing with water | Watch tone | Phosphating | Washing with water | Pure water washing | Drying |
| Treatment mode | Soaking | Spraying | Soaking | Soaking | Spraying | Spraying | Drying |
| Treatment temperature | 40℃ | Room temperature | Room temperature | 35℃ | Room temperature | Room temperature | 90℃ |
| Processing time | 90s | 20s | 30s | 120s | 20s | 20s |
After the sample plate is processed in the mode, the coverage rate and the crystal size of the phosphating crystals are observed in a microscopic mode by utilizing a scanning electron microscope, and the retest of the phosphating films is carried out by a chemical solution method. The specific method comprises the following steps:
(1) Phosphating crystallization coverage assessment
1000 times of observation is carried out on the phosphated surface of the sample wafer by using a scanning electron microscope (equipment: zeiss scanning electron microscope SIGMA 500), and evaluation is carried out by the proportion of the coverage area of the phosphated film
And (3) the following materials: phosphating film coverage = 100%
O: the coverage rate of the phosphating film is more than or equal to 80 percent and less than 100 percent
Delta: the coverage rate of the phosphating film is more than or equal to 60 percent and less than 80 percent
X: the coverage rate of the phosphating film is less than 60 percent
(2) Size test of phosphated crystals
2000 times observation is carried out on the phosphated surface of the sample wafer by utilizing a scanning electron microscope (equipment: zeiss scanning electron microscope SIGMA 500), and the average value is obtained by measuring the length dimension of random 5 phosphated crystals by a scale
(3) Phosphated film weight test
First, a 30 x 70mm phosphorylation sample plate was weighed (Metler MS-TS analytical balance) and recorded for W 0 Then immersing the sample into a phosphating film stripping solution (solution: 50g/L of anhydrous chromic acid, temperature: 75 ℃) for 15min, taking out, washing with deionized water for 40s, drying with cold air, and weighing for the second time to record W 1 。
The phosphated film weight W was calculated.
W＝(W 0 -W 1 )/S Surface area of template
From the effect of the examples (as shown in Table 4), examples 1 to 6 showed good phosphating properties in each evaluation item, and in particular, examples 1, 2, 3, 4 and 6 were excellent in combination. Comparison of examples and comparative example 4 shows a significant improvement in phosphating performance of the surface treated materials with the treating agent. As can be seen from the comparison of example 6 and comparative example 1, effective improvement of phosphating performance of the surface of the treatment template cannot be achieved when the content of the treating agent component is insufficient. Examples 1, 2 and comparative example 2 show that the addition of an appropriate amount of the F-containing compound and the metal salt can optimize the phosphating performance of the surface of the sample, but the excessive addition is affected by the increase of the film thickness, which is unfavorable for the rapid growth of the phosphating film, and further the degradation of the phosphating performance occurs. Example 4 and comparative example 3 show that the addition of excessive surfactant affects the film forming effect of the treating agent and further significantly reduces the effect of optimizing the phosphating performance of the surface of the treating panel. Examples 3, 4 and 5 show that the treating agent can adapt to typical coating treatment modes of spraying, dipping and roller coating, and has wider process suitability.
Table 4 example performance
It will of course be appreciated by those skilled in the art that the above-described embodiments are provided for illustration only and not as limitations of the present invention, and that variations and modifications of the above-described embodiments will fall within the scope of the appended claims.
Claims (10)
1. The environment-friendly water-based treating agent for improving the phosphating performance of high-strength steel is characterized in that the surface treating agent is prepared by dissolving or dispersing a composition in an aqueous medium, and the specific composition of the surface treating agent is as follows:
A. a compound selected from the group consisting of fluoride-containing compounds;
B. a metal ion compound selected from Cu, zn, mn, ni, fe-containing;
C. a compound selected from organic acids;
D. a compound selected from the group consisting of surfactants;
the surface treating agent is diluted by adding 0-20 parts of water into 1 part of treating agent and then is applied.
2. The environment-friendly water-based treating agent for improving phosphating performance of high-strength steel according to claim 1, wherein the fluoride ion-containing compound is one or more selected from ammonium fluotitanate, ammonium fluozirconate, potassium fluotitanate and potassium fluozirconate.
3. The environmentally friendly surface modified water-based treating agent for high-strength steel products with good phosphating effect according to claim 1, wherein the molar concentration of F element in the modified water-based treating agent solution is 0.3-1.8mol/L, preferably 0.6-1.1mol/L.
4. An environmentally friendly water-based treating agent for improving phosphating properties of high strength steel according to claim 1, wherein said metal ion compound containing Cu, zn, mn, ni, fe comprises: sulphate, carbonate, nitrate containing copper ions, sulphate, phosphate, formate, acetate containing Zn ions, phosphate, carbonate, nitrate containing Mn ions, nitrate containing Fe ions, oxalate, sulphate, nitrate containing Ni ions, carbonate.
5. An environmentally friendly water-based treating agent for improving the phosphating performance of high strength steel according to claim 1, wherein the molar concentration of the metal ion compound in the modified water-based treating agent solution is 0.05-0.6mol/L, preferably 0.1-0.25mol/L.
6. An environmentally friendly water-based treating agent for improving phosphating properties of high strength steel according to claim 1, wherein said organic acid compound comprises: organic acid compounds having complexing and chelating functions such as citric acid, oxalic acid, tannic acid, lactic acid, tartaric acid, and salicylic acid.
7. An environmentally friendly water-based treating agent for improving the phosphating performance of high strength steel according to claim 1, wherein the molar concentration of the organic acid compound in the modified water-based treating agent solution is 0.03 to 0.4mol/L, preferably 0.05 to 0.2mol/L.
8. An environmentally friendly water-based treating agent for improving phosphating properties of high strength steel according to claim 1, wherein the compound selected from the group consisting of surfactants in the surface treating agent mainly comprises: sodium dodecyl sulfate, sodium dodecyl sulfonate, octadecyl amine, and triethanolamine.
9. An environmentally friendly water-based treating agent for improving phosphating performance of high strength steel according to claim 1, wherein the molar concentration of the compound of the surfactant in the modified water-based treating agent solution is 0.002-0.015mol/L, preferably 0.003-0.01mol/L.
10. Use of an environmentally friendly water-based treatment agent for improving phosphating properties of high strength steel according to any one of claims 1 to 9 in continuous production lines for pickling high strength steel and cold rolling high strength steel.
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| PCT/CN2023/110360 WO2024027666A1 (en) | 2022-08-01 | 2023-07-31 | Environment-friendly water-based treatment agent for improving phosphatability of high-strength steel |
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