CN112481574A - 一种高耐蚀热镀锌钝化液及其制备方法 - Google Patents
一种高耐蚀热镀锌钝化液及其制备方法 Download PDFInfo
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- CN112481574A CN112481574A CN202011367700.6A CN202011367700A CN112481574A CN 112481574 A CN112481574 A CN 112481574A CN 202011367700 A CN202011367700 A CN 202011367700A CN 112481574 A CN112481574 A CN 112481574A
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- parts
- corrosion
- hot galvanizing
- passivation solution
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- 238000002161 passivation Methods 0.000 title claims abstract description 66
- 238000005246 galvanizing Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims abstract description 58
- 238000005260 corrosion Methods 0.000 claims abstract description 58
- 239000000839 emulsion Substances 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- 239000003112 inhibitor Substances 0.000 claims abstract description 25
- 239000002738 chelating agent Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims description 56
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 7
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- QZDMLRALZVFUOK-UHFFFAOYSA-N 1H-imidazole thiourea Chemical compound NC(=S)N.N1C=NC=C1 QZDMLRALZVFUOK-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001715 Ammonium malate Substances 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- KGECWXXIGSTYSQ-UHFFFAOYSA-N ammonium malate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)CC([O-])=O KGECWXXIGSTYSQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019292 ammonium malate Nutrition 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims description 2
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 claims description 2
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 claims description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 2
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 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
- 229960001484 edetic acid Drugs 0.000 claims 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052804 chromium Inorganic materials 0.000 abstract description 9
- 239000011651 chromium Substances 0.000 abstract description 9
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 7
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 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
- 238000001035 drying Methods 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical group OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- 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
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Abstract
本发明公开了一种高耐蚀热镀锌钝化液,属于热镀锌技术领域。本发明包括以下重量份的组分:5~15份三价铬化合物、2~10份辅助成膜剂、0.1~1份含钛化合物、5~15份树脂乳液、2~6份缓蚀剂以及1~10份螯合剂。该产品以三价铬化合物作为铬源,不含剧毒的铬酸盐;该产品成膜速度快且操作温度范围宽,得到的钝化膜颜色鲜艳且耐腐蚀、耐杂质性能优秀。本发明还提供了所述高耐蚀热镀锌钝化液的制备方法,所述方法操作步骤简单,可实现大规模工业化生产。
Description
技术领域
本发明涉及热镀锌技术领域,具体涉及一种热镀锌钝化液及其制备方法。
背景技术
热镀锌也叫热浸锌或者热浸镀锌,热镀锌具有防腐蚀性能好、成本低、镀层较美观等特点。锌资源丰富,因此价格低廉,另外锌的电极电位较铁为负,对钢铁基体来说它是阳极性镀层,能起到电化学保护作用,因此,在建筑、机电、五金、农机和国防等工业得到了广泛的应用,镀锌后如果不进行后续的后处理,镀锌很快氧化出现黑点,并相继出现白色腐蚀产物。为了降低锌的化学活性,镀锌后需要经过铬酸盐处理,以便在锌上覆盖一层化学转化膜,使活泼的金属处于钝态,铬酸盐处理是抑制锌层产生白锈廉价而有效的方法,具有钝化液稳定、膜结合力好、耐蚀性好等优点,因为被广泛用于镀锌的制品上,然而铬酸盐溶液含有毒性的六价铬化合物,在生产过程中的处理液和清洗含铬废水均可对环境及人造成严重污染,现全世界范围内都已经禁止含有六价铬的钝化液的使用,三价铬毒性低,在许多方面有类似于六价铬的特性,目前三价铬钝化液已被广泛使用现在市场,其毒性相对于六价铬小,外观、耐蚀性及膜结合力都比较优异,基本满足于市场的需求,但总体外观及耐蚀性都较六价铬有一定的差距,需要进一步提升,以满足市场的多样性的需求。
现行的三价铬钝化液,形成的钝化膜在外观、耐蚀性及膜结合力等方面都比较优异,但还是需要一定的提升以满足市场的发展需求,仍具有如下明显的缺陷:(1)成膜速度慢,目前三价铬钝化时间大概在30~60s,时间较长,增加了企业成本和劳动强度;(2)耐腐蚀性能一般,热浸锌后配合后处理中性盐雾时间白锈最高只能做到48h左右,红锈时间不超过120h,难以满足要求更高的产品耐蚀性需求;(3)耐杂质性低,钝化液在渗入一定的重金属杂质后,钝化膜颜色不够鲜艳,耐蚀性能大幅下降,满足不了客户的需求。
发明内容
基于现有技术的不足,本发明的目的在于提供一种具有不含六价铬、成膜速度快、外观靓丽且钝化时间短,钝化膜耐蚀性、耐杂质性高等优点的热镀锌钝化液。
为了达到上述目的,本发明采取的技术方案为:
一种高耐蚀热镀锌钝化液,包括以下重量份的组分:5~15份三价铬化合物、2~10份辅助成膜剂、0.1~1份含钛化合物、5~15份树脂乳液、2~6份缓蚀剂以及1~10份螯合剂。
本发明所提供的高耐蚀热镀锌钝化液以三价铬化合物作为铬源,不含剧毒的铬酸盐,配合含钛化合物及螯合物和树脂,制备得到热镀锌钝化液操作温度范围宽,整体液态稳定,具有成膜速度快且膜层外观靓丽、耐腐蚀性强以及耐杂质性优异的特点。
优选地,所述三价铬化合物包括氯化铬、硝酸铬、硫酸铬、磷酸铬、草酸铬、碳酸铬中的至少一种。
优选地,所述缓蚀剂包括油酸基咪唑啉、松香基咪唑啉、硫脲基咪唑、喹啉和吡啶中的至少一种。缓蚀剂具有保护基体的作用,缓解基体被腐蚀。上述种类的缓蚀剂具有溶解度较好、性质稳定、不易分解的特点,缓蚀性能优秀,能较长时间保护基体不被腐蚀。
优选地,所述含钛化合物包括氟钛酸铵、氟钛酸钾、溴化钛、氟化钛、三氯化钛、钛酸铵、钛酸钾中的至少一种。所述含钛化合物在热镀锌表面发生氧化还原作用,生成的产物可均匀沉积在热镀锌表面,稳定性高,并且在机械损伤后可实现快速自修复,具有优良的耐腐蚀性能。本发明所述热镀锌钝化液中,若含钛化合物过多会使其溶解性不好,同时在镀锌层上形成的钝化膜光泽和结合力较差;含量过少则会导致镀锌层上面形成的钝化膜较薄,耐蚀性较差。
优选地,所述树脂乳液包括水性聚氨酯树脂乳液、阴离子乙烯基树脂乳液、阳离子丙烯酸树脂乳液、阴离子丙烯酸树脂乳液、改性环氧树脂乳液中的至少一种。
优选地,所述辅助成膜剂包括四烷氧基硅烷、硫酸铝、硅烷醇、明胶中的至少一种。所述种类的辅助成膜剂具有成膜速度快且结合力良好的优点,可使生成的钝化膜细腻致密,均匀透明,具有良好的耐蚀性能。
优选地,所述螯合剂包括三乙酸、乙二胺四乙酸、乙二胺四乙酸钠、二乙醇胺、二乙烯三胺五甲叉膦酸盐、酒石酸铵、苹果酸铵、柠檬酸铵、氨基羧酸盐、单乙醇胺、三亚乙基四胺、四亚乙基四胺中的至少一种。所述种类的螯合剂具有螯合能力强,性质稳定的特点,使用过程中不易产生沉淀,保证产品的储存及使用。
优选地,所述高耐蚀热镀锌钝化液的组分还包括80~120份蒸馏水。
优选地,所述高耐蚀热镀锌钝化液,包括以下重量份的组分:100份蒸馏水、12份三价铬化合物、0.5份含钛化合物、6份辅助成膜剂、8份树脂乳液、4份缓蚀剂及6份螯合剂。所述含量下的三价铬化合物能在镀锌层上形成颜色鲜艳的钝化膜,随着含钛化合物和辅助成膜剂的加入,能进一步加快钝化膜的形成,缩短钝化时间,同时使钝化膜具有细腻均匀、透明致密及结合力优秀的优点;特定螯合剂的加入能有效络合钝化液中的重金属杂质,使钝化液稳定;树脂乳液在干燥过程中分子间能相互交联强化成一层均匀玻璃态的保护层,填充在钝化膜空隙中,使其致密且孔隙率低,协同缓蚀剂的缓蚀作用使钝化膜耐腐蚀性能优秀。
本发明的另一目的还在于提供所述高耐蚀热镀锌钝化液的制备方法,包括以下步骤:
(1)将三价铬化合物加入蒸馏水中加热并进行反应,得混合液A;
(2)在步骤(1)所得混合液A中加入含钛化合物并搅拌混合后,加入辅助成膜剂,得混合液B;
(3)将步骤(2)所得混合液B在搅拌下依次缓慢加入树脂乳液和缓蚀剂并混合均匀后,加入螯合剂并搅拌25~35min,即得所述高耐蚀热镀锌钝化液。
本发明所提供的高耐蚀热镀锌钝化液的制备方法操作步骤简单,可实现大规模工业化生产。
优选地,步骤(1)所述加热的温度为45~55℃,反应的时间为15~25min。
优选地,步骤(2)所述搅拌混合的时间为10~20min。
所述优选的技术参数下各组分混合及反应更加充分均匀。
本发明的有益效果在于:本发明提供了高耐蚀热镀锌钝化液,该产品以三价铬化合物作为铬源,不含剧毒的铬酸盐;该产品成膜速度快且操作温度范围宽,得到的钝化膜颜色鲜艳且耐腐蚀、耐杂质性能优秀。本发明还提供了所述高耐蚀热镀锌钝化液的制备方法,所述方法操作步骤简单,可实现大规模工业化生产。
具体实施方式
为了更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明,其目的在于详细地理解本发明的内容,而不是对本发明的限制。
实施例1
本发明所述高耐蚀热镀锌钝化液的一种实施例,本实施例所述一种高耐蚀热镀锌钝化液,包括以下重量份的组分:12份三价铬化合物、0.5份含钛化合物、6份辅助成膜剂、8份树脂乳液、4份缓蚀剂及6份螯合剂;所述三价铬化合物为氯化铬;所述缓蚀剂为油酸基咪唑啉;所述含钛化合物为三氯化钛;所述树脂乳液为水性聚氨酯树脂乳液;所述辅助成膜剂为四烷氧基硅烷;所述螯合剂为氨三乙酸;所述高耐蚀热镀锌钝化液的组分还包括100份蒸馏水。
本实施例所述高耐蚀热镀锌钝化液的制备方法,包括以下步骤:
(1)将三价铬化合物加入蒸馏水中加热至50℃并进行反应20min,得混合液A;
(2)在步骤(1)所得混合液A中加入含钛化合物并搅拌混合15min后,加入辅助成膜剂,得混合液B;
(3)将步骤(2)所得混合液B在搅拌下依次缓慢加入树脂乳液和缓蚀剂并混合均匀,保温10min后,加入螯合剂并搅拌30min,即得所述高耐蚀热镀锌钝化液。
实施例2
本实施例与实施例的差别仅在于,本实施例所述一种高耐蚀热镀锌钝化液,包括以下重量份的组分:15份三价铬化合物、3份辅助成膜剂、1份含钛化合物、12份树脂乳液、6份缓蚀剂以及2份螯合剂;所述三价铬化合物为硝酸铬;所述缓蚀剂为松香基咪唑啉;所述含钛化合物为溴化钛;所述树脂乳液为阳离子乙烯基树脂乳液;所述辅助成膜剂为硫酸铝;所述螯合剂为乙二胺四乙酸。
实施例3
本实施例与实施例的差别仅在于,本实施例所述一种高耐蚀热镀锌钝化液,包括以下重量份的组分:8份三价铬化合物、8份辅助成膜剂、0.1份含钛化合物、5份树脂乳液、2份缓蚀剂以及10份螯合剂;所述三价铬化合物为硫酸铬;所述缓蚀剂为硫脲基咪唑啉;所述含钛化合物为钛酸铵;所述树脂乳液为阳离子丙烯酸树脂乳液;所述辅助成膜剂为硫酸铝;所述螯合剂为二乙醇胺。
对比例1
本对比例与实施例的差别仅在于,本对比例所述高耐蚀热镀锌钝化液,包括以下重量份的组分:12份三价铬化合物、0.05份含钛化合物、6份辅助成膜剂、8份树脂乳液、4份缓蚀剂及6份螯合剂。
对比例2
本对比例与实施例的差别仅在于,本对比例所述高耐蚀热镀锌钝化液,包括以下重量份的组分:12份三价铬化合物、1.5份含钛化合物、6份辅助成膜剂、8份树脂乳液、4份缓蚀剂及6份螯合剂。
对比例3
本对比例与实施例的差别仅在于,本对比例所述高耐蚀热镀锌钝化液,包括以下重量份的组分:12份三价铬化合物、0.5份含钛化合物、1份辅助成膜剂、8份树脂乳液、4份缓蚀剂及6份螯合剂。
对比例4
本对比例与实施例的差别仅在于,本对比例所述高耐蚀热镀锌钝化液,包括以下重量份的组分:12份三价铬化合物、0.5份含钛化合物、11份辅助成膜剂、8份树脂乳液、4份缓蚀剂及6份螯合剂。
对比例5
本对比例与实施例的差别仅在于,本对比例所述高耐蚀热镀锌钝化液,包括以下重量份的组分:12份三价铬化合物、0.5份含钛化合物、6份辅助成膜剂、8份树脂乳液、1份缓蚀剂及6份螯合剂。
对比例6
本对比例与实施例的差别仅在于,本对比例所述高耐蚀热镀锌钝化液,包括以下重量份的组分:12份三价铬化合物、0.5份含钛化合物、6份辅助成膜剂、8份树脂乳液、4份缓蚀剂及0.5份螯合剂。
对比例7
本对比例与实施例的差别仅在于,本对比例所述高耐蚀热镀锌钝化液的组分中,三氯化钛使用氯化钒代替。
对比例8
本对比例与实施例的差别仅在于,本对比例所述高耐蚀热镀锌钝化液的组分中,四烷氧基硅烷使用硫酸代替。
为验证本发明所述热镀锌钝化液的使用性能,将实施例1~3所得高耐蚀热镀锌钝化液以及对比例1~8所得产品进行钝化测试及盐水喷雾实验测试,所述钝化测试为将产品在25℃下进行涂覆,所述涂覆的厚度为10μm,记录钝化膜层形成时间,所述测试结果如表1所示;所述盐水喷雾实验测试使用GB/T10125-2012标准测试方法,所述测试结果如表2所示。
表1
表2
从表1及表2可知,本发明所提供的高耐蚀热镀锌钝化液相比于对比例1~8所得产品具有更快的钝化膜形成速率以及更好的耐蚀性,所述产品出现红锈的时间大于600h,且未出现白锈,其性能远优于现有钝化液产品。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种高耐蚀热镀锌钝化液,其特征在于,包括以下重量份的组分:5~15份三价铬化合物、2~10份辅助成膜剂、0.1~1份含钛化合物、5~15份树脂乳液、2~6份缓蚀剂以及1~10份螯合剂。
2.如权利要求1所述的高耐蚀热镀锌钝化液,其特征在于,所述三价铬化合物包括氯化铬、硝酸铬、硫酸铬、磷酸铬、草酸铬、碳酸铬中的至少一种。
3.如权利要求1所述的高耐蚀热镀锌钝化液,其特征在于,所述缓蚀剂包括油酸基咪唑啉、松香基咪唑啉、硫脲基咪唑、喹啉、吡啶中的至少一种。
4.如权利要求1所述的高耐蚀热镀锌钝化液,其特征在于,所述含钛化合物包括氟钛酸铵、氟钛酸钾、溴化钛、氟化钛、三氯化钛、钛酸铵、钛酸钾中的至少一种。
5.如权利要求1所述的高耐蚀热镀锌钝化液,其特征在于,所述树脂乳液包括水性聚氨酯树脂乳液、阴离子乙烯基树脂乳液、阳离子丙烯酸树脂乳液、阴离子丙烯酸树脂乳液、改性环氧树脂乳液中的至少一种。
6.如权利要求1所述的高耐蚀热镀锌钝化液,其特征在于,所述辅助成膜剂包括四烷氧基硅烷、硫酸铝、硅烷醇、明胶中的至少一种。
7.如权利要求1所述的高耐蚀热镀锌钝化液,其特征在于,所述螯合剂包括三乙酸、乙二胺四乙酸、乙二胺四乙酸钠、二乙醇胺、二乙烯三胺五甲叉膦酸盐、酒石酸铵、苹果酸铵、柠檬酸铵、氨基羧酸盐、单乙醇胺、三亚乙基四胺、四亚乙基四胺中的至少一种。
8.如权利要求1所述的高耐蚀热镀锌钝化液,其特征在于,所述高耐蚀热镀锌钝化液,包括以下重量份的组分:100份蒸馏水、12份三价铬化合物、0.5份含钛化合物、6份辅助成膜剂、8份树脂乳液、4份缓蚀剂及6份螯合剂。
9.如权利要求1~8任一项所述的高耐蚀热镀锌钝化液的制备方法,其特征在于,包括以下步骤:
(1)将三价铬化合物加入蒸馏水中加热并进行反应,得混合液A;
(2)在步骤(1)所得混合液A中加入含钛化合物并搅拌混合后,加入辅助成膜剂,得混合液B;
(3)将步骤(2)所得混合液B在搅拌下依次缓慢加入树脂乳液和缓蚀剂并混合均匀后,加入螯合剂并搅拌25~35min,即得所述高耐蚀热镀锌钝化液。
10.如权利要求9所述的高耐蚀热镀锌钝化液的制备方法,其特征在于,步骤(1)所述加热的温度为45~55℃,反应的时间为15~25min;步骤(2)所述搅拌混合的时间为10~20min。
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