CN114836706B - Preparation method of batch hot dip galvanized steel ultrathin galvanized layer - Google Patents
Preparation method of batch hot dip galvanized steel ultrathin galvanized layer Download PDFInfo
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- CN114836706B CN114836706B CN202210502136.7A CN202210502136A CN114836706B CN 114836706 B CN114836706 B CN 114836706B CN 202210502136 A CN202210502136 A CN 202210502136A CN 114836706 B CN114836706 B CN 114836706B
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- zinc
- iron
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- gadolinium
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 76
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 560
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 508
- 239000011701 zinc Substances 0.000 claims abstract description 508
- 239000007788 liquid Substances 0.000 claims abstract description 445
- 238000007747 plating Methods 0.000 claims abstract description 301
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 209
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 148
- 239000010959 steel Substances 0.000 claims abstract description 148
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 136
- 238000005246 galvanizing Methods 0.000 claims abstract description 106
- 229910052742 iron Inorganic materials 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 74
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 74
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 67
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 65
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 42
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 181
- 239000000956 alloy Substances 0.000 claims description 181
- -1 zinc-aluminum-vanadium Chemical compound 0.000 claims description 172
- 229910000756 V alloy Inorganic materials 0.000 claims description 118
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 99
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 90
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 68
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 68
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 41
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 38
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 35
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 35
- 239000001119 stannous chloride Substances 0.000 claims description 35
- 235000011150 stannous chloride Nutrition 0.000 claims description 35
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 34
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical group Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 34
- 235000019270 ammonium chloride Nutrition 0.000 claims description 34
- 235000005074 zinc chloride Nutrition 0.000 claims description 34
- 239000011592 zinc chloride Substances 0.000 claims description 34
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 32
- 238000002844 melting Methods 0.000 claims description 31
- 230000008018 melting Effects 0.000 claims description 31
- HIMLGVIQSDVUJQ-UHFFFAOYSA-N aluminum vanadium Chemical compound [Al].[V] HIMLGVIQSDVUJQ-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 28
- 239000001103 potassium chloride Substances 0.000 claims description 28
- 235000011164 potassium chloride Nutrition 0.000 claims description 28
- ZSOJHTHUCUGDHS-UHFFFAOYSA-N gadolinium iron Chemical compound [Fe].[Gd] ZSOJHTHUCUGDHS-UHFFFAOYSA-N 0.000 claims description 22
- 238000005266 casting Methods 0.000 claims description 21
- 239000008139 complexing agent Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 239000004471 Glycine Substances 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 17
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 claims description 16
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000011550 stock solution Substances 0.000 claims description 7
- 229940107816 ammonium iodide Drugs 0.000 claims description 4
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 39
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 229910000976 Electrical steel Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 description 48
- 238000003756 stirring Methods 0.000 description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- 239000002893 slag Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 230000006698 induction Effects 0.000 description 19
- 230000008569 process Effects 0.000 description 17
- 229910052759 nickel Inorganic materials 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 11
- 229910001431 copper ion Inorganic materials 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 238000002791 soaking Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229910001432 tin ion Inorganic materials 0.000 description 8
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical class [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002500 ions Chemical group 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 229940123973 Oxygen scavenger Drugs 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 2
- QOVZZLFSTROUML-UHFFFAOYSA-M [Cl-].[Zn+].[Cl-].[NH4+] Chemical compound [Cl-].[Zn+].[Cl-].[NH4+] QOVZZLFSTROUML-UHFFFAOYSA-M 0.000 description 2
- RFIJBZKUGCJPOE-UHFFFAOYSA-N [Fe].[Ni].[Zn] Chemical compound [Fe].[Ni].[Zn] RFIJBZKUGCJPOE-UHFFFAOYSA-N 0.000 description 2
- 239000004063 acid-resistant material Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 2
- 235000010210 aluminium Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910005883 NiSi Inorganic materials 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- KMVJYZPWGWEBIK-UHFFFAOYSA-L zinc azane dichloride Chemical compound N.[Cl-].[Cl-].[Zn+2] KMVJYZPWGWEBIK-UHFFFAOYSA-L 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- C23C2/04—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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention relates to the technical field of hot galvanizing, and provides a preparation method of an ultrathin galvanized layer of batch hot galvanized steel. The invention sequentially carries out acid washing, water washing, plating assistance and hot galvanizing on the steel to obtain the hot galvanized steel, wherein the thickness of a galvanized layer is 35-48 mu m. The plating assistant agent provided by the invention not only can be matched with higher aluminum content in zinc liquid, so that no plating leakage occurs during zinc plating, but also is easy to decompose, the zinc plating time can be shortened, and the thickness of a zinc plating layer can be reduced; the iron content in the zinc liquid is greatly reduced, the fluidity of the zinc liquid is improved, and the thickness of a galvanized layer is reduced by a method of removing iron through a temperature difference method and adding gadolinium element into the zinc liquid; by adding vanadium element into the zinc liquid, the eride effect is inhibited, the iron-zinc reaction is slowed down, the thickness of the galvanized layer is further reduced, and the ultra-thin galvanized layer can be obtained when various steel products including high silicon steel are galvanized. The preparation method provided by the invention can efficiently reduce the thickness of the galvanized layer and ensure that the surface quality of the galvanized layer is good.
Description
Technical Field
The invention relates to the technical field of hot galvanizing, in particular to a preparation method of an ultrathin galvanized layer of batch hot galvanized steel.
Background
The galvanization is a surface treatment technology which covers a continuous metal zinc film on the surface of steel to improve the corrosion resistance of the steel, prolong the service life of the steel and have the decorative effect. There are two modes of galvanization of steel currently in common use, namely electro-galvanization and hot galvanizing. Wherein, the hot galvanizing is to soak the steel in high temperature liquid zinc, and the iron on the surface of the steel reacts with the zinc liquid to generate iron-zinc compound, so that the galvanized layer is firmly fixed on the surface of the steel and is not easy to peel off. The atoms of the hot dip galvanizing layer are tightly combined to form chemical bonds or metal bonds, pores cannot appear in the galvanized layer, the compactness is good, and the good corrosion resistance of the hot dip galvanizing layer is ensured. In the prior art, zinc with low melting point (419 ℃) is heated and melted by natural gas, and the temperature is raised to 440-450 ℃ for galvanizing. On the premise of obtaining the galvanized layer with the same thickness, the energy (added with the heat absorbed by the steel) required by hot galvanizing is about half of that of the electrogalvanizing, and the comprehensive cost is reduced by more than 30 percent compared with that of the electrogalvanizing.
Hot galvanizing is divided into continuous hot galvanizing and batch hot galvanizing. The continuous hot galvanizing is mainly suitable for galvanizing strip steel with simple structure such as steel plates, steel strips and the like, and the galvanizing process is different from batch hot galvanizing. The continuous hot galvanizing process is to remove oil by high temperature oxidation under vacuum condition; then, the rust on the surface of the steel is reduced into simple substance iron and water vapor by hydrogen under vacuum, so as to achieve the purpose of removing the rust on the surface of the steel. Because continuous hot galvanizing is carried out under vacuum condition, the workpiece is not contacted with air, and secondary rust can not occur, so that no plating assistant agent is needed, and the process of thermal decomposition of the plating assistant agent is avoided. The galvanizing time can be controlled to be 3-10 s, the iron-zinc compound layer formed by the iron-zinc reaction is very thin, and the galvanized layer is mainly a pure zinc layer. In addition, the steel material adopting continuous galvanization is long-strip, the free zinc layer on the steel material can be scraped off by adopting an air knife (namely compressed air blowing), and the thickness of the galvanization layer can be controlled to be 10-20 mu m.
However, continuous hot dip galvanizing can only be used for steel structural members with regular shapes, and for steel structural members with irregular shapes, galvanizing can only be performed by adopting a batch hot dip galvanizing mode. Batch hot galvanizing is also called as "hanging plating", and is an intermittent production mode of hanging a certain amount of steel structural members into a zinc pot containing zinc liquid for galvanizing each time. Because the structural member is generally used outdoors and is exposed to sunlight and rain, if the structural member is used in cities or coastal areas, the structural member is also corroded by sulfur dioxide and chloride in the air, the corrosion environment is worse, and the loss speed of a galvanized layer is higher. Therefore, the galvanized layer thickness index of the batch hot dip galvanized product is thicker than that of the continuous galvanized product, and according to the different thickness, application and use environmental conditions of the steel, the galvanized layer thickness of the steel is specified in the national standard 'technical requirement of hot dip galvanized layer of hot dip galvanized steel sheet of metal coating steel and test method of GB/T13912-2020': four grades of 45 μm, 55 μm, 70 μm, 85 μm. At present, the galvanized layer of the existing batch hot dip galvanized product is generally thicker, the galvanized layer with the thickness of about 100 mu m is quite common, sometimes even reaching more than 200 mu m, and is far higher than the national standard, so that a great amount of zinc resources are wasted. The thickness superscalar of the zinc coating is generally affected by several factors: (1) The silicon content of the steel, when the silicon content is lower than 0.05%, the galvanization reaction is normal; when the silicon content in the steel is 0.05-0.20%, the reaction of iron and zinc is extremely rapid in the galvanizing process, so that the galvanized layer is seriously and super-thick, and the phenomenon is called as the Style effect; (2) iron content in zinc liquid: in the galvanizing process, iron and zinc compounds in a galvanized layer on the surface of steel can be partially dissolved in zinc liquid, and the zinc liquid can corrode the surface of a zinc pot made of iron, so that the content of iron element in the zinc liquid is increased. The iron element has certain solubility in the zinc liquid, and the saturated iron content in the zinc liquid is about 0.03 percent at 445 ℃. When the iron content in the zinc liquid exceeds the saturated iron content, the iron exceeding the saturated content can form solid-state iron-zinc compounds insoluble in the zinc liquid, so that large-particle iron-zinc compounds are formed, and the large-particle iron-zinc compounds are settled to the bottom of the zinc pot due to the fact that the specific gravity is larger than that of the zinc liquid, so that zinc slag is formed. The small-particle iron-zinc compound is suspended in the zinc liquid, and is a macromolecule formed by combining 1 iron atom with more than 10 zinc atoms, and the macromolecules interact to form a net structure in the zinc liquid to block the normal flow of the zinc liquid, so that the viscosity of the zinc liquid is increased. The viscosity of the zinc liquid is increased, the fluidity is deteriorated, and in the galvanizing process, when a workpiece is lifted from the zinc liquid, the free zinc layer on the surface of the zinc coating is difficult to flow downwards, so that the free zinc layer is thicker, and the overall thickness of the zinc coating is increased; (3) aluminum element content in zinc liquid: the chemical activity of aluminum is higher than that of zinc, and the aluminum reacts with the surface of steel to form iron-aluminum compound in preference to zinc in the galvanizing process, so that the iron-zinc reaction is prevented, the aluminum content is improved, and the thickness of a galvanized layer can be reduced. In actual production, the aluminum content in the zinc liquid is generally controlled to be between 0.006% and 0.008%, so that the low aluminum content has little effect on reducing the thickness of the galvanized layer. The effect of reducing the thickness of the galvanized layer is more obvious only when the aluminum content in the zinc liquid exceeds 0.020%, but the phenomenon of 'miss-plating' (that is, no galvanized layer is formed at certain parts of the surface of the steel) is more serious as the aluminum content is increased. Meanwhile, with the increase of the aluminum content, the surface quality of the galvanized layer is poor, and a particle or orange peel galvanized layer appears; (4) Effect of plating aid composition: the conventional zinc chloride-ammonia chloride plating assistant has a certain influence on the thickness of a galvanized layer, and the higher the total concentration of the plating assistant is, the more salt is adsorbed on the surface of steel, and the longer the salt needs to be decomposed in the galvanizing process and leaves the surface of the steel, so that the galvanized layer becomes thicker; (5) effect of galvanization time: the iron element on the surface of the steel reacts with zinc in the zinc liquid in the galvanizing process to form iron-zinc compounds, and the longer the galvanizing time is, the more the generated iron-zinc compounds are, the thicker the galvanized layer is; (6) influence of steel thickness: the greater the thickness of the steel, the longer the time for the heat transfer between the steel and the zinc bath to reach equilibrium, the longer the zinc plating time is required, and the thicker the zinc plating layer.
In order to reduce the thickness of the galvanized layer, the prior art mainly solves the problem of the ultra-thick galvanized layer by the following ways: (1) Lanthanum and cerium are added into the zinc liquid, so that the surface tension of the zinc liquid is reduced, and the fluidity of the zinc liquid is improved. However, in actual production, as the density of the two elements is smaller and the elements are active metals, the elements are easy to enrich the surface of the zinc liquid and are lost by air oxidation, and the application effect is not obvious; (2) Nickel is added to the zinc bath to control the "san. Delin effect" caused by the silicon element in the steel. In the zinc plating process, nickel element reacts with iron and zinc to form a nickel-iron-zinc ternary compound, the nickel-iron-zinc ternary compound is adhered between a zeta phase and a eta phase of a zinc plating layer, a liquid phase channel formed by the zeta phase is damaged by silicon element, and the delta phase is prevented from being directly corroded by zinc liquid, so that zinc and iron elements can only diffuse into each other through the formed zinc plating layer according to a normal way, the san-delin effect can be slowed down, at present, a certain amount of nickel element is added into the zinc liquid by batch hot dip galvanizing manufacturers, the san-delin effect is restrained, a certain effect is obtained, and the thickness of the zinc plating layer of the san-delin steel can be controlled to be 80-100 mu m. However, when the user requires a lower galvanized layer thickness, the method of adding nickel into the zinc liquid cannot be solved; (3) More than 0.02% of aluminum is added into the zinc liquid, a barrier layer is formed on the surface of the steel, and the iron-zinc reaction is delayed. Aluminum has higher chemical activity than zinc and can react with iron to form Fe in preference to zinc 2 Al 5 The compound adheres to the surface of steel material and prevents the smooth progress of iron-zinc reaction, thereby reducing the thickness of the galvanized layer. However, this method causes two major problems in mass hot dip galvanizing production: (1) a large amount of missing plating, namely that the galvanized layer cannot completely cover the surface of the steel, a plurality of small blocks without being covered by the galvanized layer appear, so that the rust prevention function of the galvanized layer is affected, the appearance is also affected, and when the aluminum content in the zinc liquid exceeds 0.01%, the problem begins to appear. The reason for this is that aluminium reacts with zinc chloride or ammonium chloride to form aluminium trichloride,the adhesive is adhered to the surface of steel, so that the normal iron-zinc reaction is prevented; the aluminum reacts with the plating assistant agent, and the plating assistant agent is consumed, so that the plating assistant effect is reduced; (2) the surface quality of the galvanized layer is seriously reduced, the surface is not smooth, orange peel-shaped, and even a plurality of particles with different sizes grow. The reason is that when the aluminum content in the zinc liquid reaches more than 0.02%, the aluminum in the zinc liquid on the surface of the galvanized layer is consumed too quickly due to rapid iron-aluminum reaction, aluminum elements in the nearby zinc liquid are not diffused to be supplemented, the local aluminum concentration is suddenly reduced, and Fe cannot be further formed 2 Al 5 A compound. As the iron-aluminum reaction is an exothermic reaction, the local temperature can be raised, which is favorable for the iron-zinc reaction and accelerates the Fe of the zinc liquid 2 Al 5 Erosion of the compound, fe occurs rapidly 2 Al 5 The blocking layer is locally broken, a severe iron-zinc reaction occurs at the broken position, and the galvanized layer is explosive-grown, so that the phenomena of particles and orange peel on the surface appear.
In conclusion, the problem that the batch hot galvanizing zinc coating is thicker cannot be effectively solved in the prior art.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a batch hot dip galvanized steel ultrathin galvanized layer. The method provided by the invention can effectively reduce the galvanized layer on the surface of the steel during batch hot galvanizing, and improve the surface quality of the galvanized layer.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of an ultrathin galvanized layer of batch hot galvanized steel comprises the following steps:
sequentially carrying out acid washing, water washing, plating assistance and hot galvanizing on the steel to obtain hot galvanized steel;
the plating assistant agent for plating assistant comprises the following components: zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent, a plating assistant thickness control agent, hydrochloric acid and water; the total mass concentration of zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, deoxidizer, complexing agent and plating assistant film thickness control agent in the plating assistant agent is less than 170g/L, and the pH value of the plating assistant agent is 1.0-2.0;
The preparation method of the alloy liquid for hot galvanizing comprises the following steps: carrying out temperature difference method iron removal on the conventional zinc liquid to obtain primary iron-removed zinc liquid; adding gadolinium element into the primarily iron-removed zinc liquid to further remove iron, so as to obtain low-iron zinc liquid; adding zinc-aluminum-vanadium alloy into the low-iron zinc liquid to obtain alloy zinc liquid; the conventional zinc liquid consists of the following components in percentage by mass: zinc is more than or equal to 99.95 percent, iron is 0.030 percent to 0.035 percent, aluminum is 0.006 percent to 0.008 percent, and impurities are less than 0.005 percent;
the alloy zinc liquid for hot galvanizing comprises the following components in percentage by mass: iron is less than or equal to 0.013%, gadolinium is 0.0010-0.0015%, vanadium is 0.004-0.008%, aluminum is 0.038-0.050%, impurities are less than 0.005%, and the balance is zinc;
the thickness of the galvanized layer of the hot dip galvanizing is 35-48 mu m.
Preferably, the method for removing iron by the temperature difference method comprises the following steps: heating the conventional zinc liquid from 440-445 ℃ to 450-455 ℃, preserving heat for 0.5-1 h after the heating, naturally cooling to 430-435 ℃, and preserving heat for 1-2 h after the cooling, thus obtaining the preliminary iron-removing zinc liquid.
Preferably, the gadolinium element is added in a zinc-gadolinium-iron alloy mode, and the mass of the effective gadolinium element in the zinc-gadolinium-iron alloy is 0.0050% -0.0062% of the total mass of the preliminary iron-removing zinc liquid.
Preferably, the zinc-gadolinium-iron alloy is in the form of zinc-gadolinium-iron alloy ingot, and the preparation method of the zinc-gadolinium-iron alloy ingot comprises the following steps: melting a zinc ingot, adding gadolinium-iron alloy, heating to 750-800 ℃ and preserving heat for 30-60 min to obtain zinc-gadolinium-iron alloy liquid, and casting the zinc-gadolinium-iron alloy liquid to obtain the zinc-gadolinium-iron alloy ingot, wherein the effective gadolinium element content of the zinc-gadolinium-iron alloy ingot is 1.00-1.25 wt%; the zinc ingot is a 0# zinc ingot, and the melting temperature of the zinc ingot is 500-550 ℃; the mass ratio of the zinc ingot to the gadolinium-iron alloy is 64.5-81.5:1; the gadolinium content of the gadolinium-iron alloy is 86.6wt%, and the effective gadolinium content of the gadolinium-iron alloy is 82.4wt%.
Preferably, the zinc-aluminum-vanadium alloy is in the form of zinc-aluminum-vanadium alloy ingot, and the preparation method of the zinc-aluminum-vanadium alloy ingot comprises the following steps: melting a zinc ingot, adding aluminum-vanadium alloy, heating to 700-750 ℃ and preserving heat for 30-60 min to obtain zinc-aluminum-vanadium alloy liquid, and casting the zinc-aluminum-vanadium alloy liquid to obtain the zinc-aluminum-vanadium alloy ingot, wherein the aluminum content of the zinc-aluminum-vanadium alloy ingot is 4.5-5.4 wt% and the vanadium content is 0.50-0.60 wt%; the zinc ingot is a 0# zinc ingot, and the melting temperature of the zinc ingot is 450-500 ℃; the mass ratio of the zinc ingot to the aluminum-vanadium alloy is 15.8-19:1; the content of vanadium element in the aluminum-vanadium alloy is 10wt%.
Preferably, the temperature of the hot dip galvanizing is 440-445 ℃, and the time of the hot dip galvanizing is 130-160 s.
Preferably, the deoxidizer is hydroxylamine hydrochloride, the complexing agent is glycine, and the plating assistant film thickness control agent is perfluorobutyl trimethyl quaternary ammonium iodine; the plating assistant has zinc chloride in 60-80 g/L, ammonium chloride in 20-30 g/L, potassium chloride in 10-20 g/L, nickel fluoride in 5-10 g/L, stannous chloride in 5-20 g/L, copper chloride in 0.5-1.5 g/L, gemini-12-2-12 in 0.05-0.15 g/L, hydroxylamine hydrochloride in 0.5-2.0 g/L, glycine in 1.0-2.0 g/L and perfluorobutyl trimethyl quaternary ammonium iodide in 0.2-1.0 g/L.
Preferably, the preparation method of the plating assistant comprises the following steps: and mixing the zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent, a plating assistant film thickness control agent, hydrochloric acid and water to obtain the plating assistant agent.
Preferably, the mixing comprises the steps of:
firstly mixing part of water with zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent and a plating assistant film thickness control agent to obtain a first mixed solution, wherein the mass of the part of water accounts for 60% -80% of the total mass of the water;
Performing second mixing on the first mixed solution and hydrochloric acid to obtain plating assistant agent stock solution;
and thirdly mixing the plating assistant agent stock solution and the rest of water to obtain the plating assistant solution.
Preferably, the plating assisting temperature is 65-85 ℃, and the plating assisting time is 30-60 s; and the plating assistant is further subjected to natural drying, wherein the natural drying temperature is room temperature, and the natural drying time is 3-5 min.
The invention provides a preparation method of an ultrathin galvanized layer of batch hot dip galvanized steel, which comprises the following steps: sequentially carrying out acid washing, water washing, plating assistance and hot galvanizing on the steel to obtain hot galvanized steel; the plating assistant agent for plating assistant comprises the following components: zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent, a plating assistant thickness control agent, hydrochloric acid and water; the total mass concentration of zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, deoxidizer, complexing agent and plating assistant film thickness control agent in the plating assistant agent is less than 170g/L, and the pH value of the plating assistant agent is 1.0-2.0; the preparation method of the alloy liquid for hot galvanizing comprises the following steps: carrying out temperature difference method iron removal on the conventional zinc liquid to obtain primary iron-removed zinc liquid; adding gadolinium element into the primarily iron-removed zinc liquid to further remove iron, so as to obtain low-iron zinc liquid; adding zinc-aluminum-vanadium alloy into the low-iron zinc liquid to obtain alloy zinc liquid; the conventional zinc liquid consists of the following components in percentage by mass: zinc is more than or equal to 99.95 percent, iron is 0.030 percent to 0.035 percent, aluminum is 0.006 percent to 0.008 percent, and impurities are less than 0.005 percent; the alloy zinc liquid for hot galvanizing comprises the following components in percentage by mass: iron is less than or equal to 0.013%, gadolinium is 0.0010-0.0015%, vanadium is 0.004-0.008%, aluminum is 0.038-0.050%, impurities are less than 0.005%, and the balance is zinc; the thickness of the galvanized layer of the hot dip galvanizing is 35-48 mu m.
In the invention, the plating assistant film formed by the plating assistant agent contains nickel fluoride, the nickel fluoride plays two roles in the subsequent hot galvanizing process, firstly, fluoride ions in the nickel fluoride can react with an aluminum oxide film on the surface of liquid zinc in hot galvanizing to form hexafluoroaluminate, so that the film is broken, and the wetting effect of the liquid zinc on a steel substrate is not blocked; secondly, nickel ions are provided, zinc in hot galvanizing liquid is reduced into elemental nickel, nickel-zinc compounds are adsorbed between zeta phase and eta phase of a galvanized layer, interdiffusion of zinc and iron atoms is hindered, iron-zinc reaction is slowed down, gemini-12-2-12 is used as a double quaternary ammonium salt and can form chelation type adsorption with negatively charged iron base, under the action of chemical bonds of intermediate connecting groups, the problem of mutual electrostatic repulsion between molecules when single quaternary ammonium salt is adopted is avoided, and tight arrangement among adsorption molecules is ensured, so that oxygen and aluminum trichloride gas can be effectively prevented from contacting with the surface of steel, the surface of the steel is prevented from being oxidized by oxygen in air, and aluminum trichloride gas is prevented from condensing on the surface of the steel, and the surface quality of a subsequent galvanized layer is affected; when stannous chloride and copper chloride can be attached to the surface of steel, tin ions and copper ions in the stannous chloride and copper ions are reduced to copper-tin compounds at the earliest after hot galvanizing begins, the tin ions and copper ions are rapidly spread on the surface of the steel, and a plating assistant agent is replaced so that zinc liquid contacts the steel as soon as possible, and the steel is prevented from being adhered with aluminum trichloride, aluminum oxide and other impurities under the condition that the steel is not galvanized for a long time, so that the problem of plating leakage is avoided, the aluminum content of the zinc liquid can be increased, the effect of reducing the thickness of a galvanized layer is improved, and meanwhile, the integrity of a galvanized film is ensured. In addition, the total concentration of other chemical substances except water and hydrochloric acid is lower than 170g/L, and is lower than that of a conventional plating assistant by more than 30%, and the actual plating assistant weight is lower than that of the conventional plating assistant by 50% under the interaction of the components. Meanwhile, the plating assistant provided by the invention is a low-smoke easy-to-decompose anti-leakage plating assistant, and the decomposition time is less than 30 seconds under the high-temperature action of hot galvanizing, and is reduced by more than 30 seconds compared with that of the conventional plating assistant, so that the galvanizing time can be reduced, and the thickness of a galvanized layer is reduced.
Furthermore, when the deoxidizer is hydroxylamine hydrochloride and the complexing agent is glycine, stannous chloride, cupric chloride, gemini-12-2-12, hydroxylamine hydrochloride and glycine can generate a synergistic effect, so that the problem of plating omission caused by the fact that the aluminum content in the zinc liquid is more than 0.02% is solved. Gemini-12-2-12 shape on steel surfaceForming a passivation layer, preventing air from oxidizing the surface of steel during galvanization, preventing aluminum trichloride formed by the reaction of aluminum, zinc chloride and ammonium chloride from condensing on the surface of steel, and respectively providing tin ions and copper ions by stannous chloride and cupric chloride, and glycine and Fe 2+ The ion forms complex, prevents the deposition of iron oxide on the surface of the steel matrix, and can react with Cu 2+ The ions form a complex, the content of free copper ions is controlled, so that copper ions and tin ions adsorbed on the surface of the steel have a more proper proportion, copper-tin compounds with a certain component proportion are generated more quickly during galvanization, the plating auxiliary agent on the surface of the steel is replaced, so that zinc liquid is contacted with the steel more quickly, the steel can be prevented from being adhered with impurities such as aluminum trichloride and aluminum oxide under the condition that the steel is not galvanized for a long time, and the anti-leakage plating effect is improved. The perfluoro butyl trimethyl quaternary ammonium iodine is an environment-friendly surfactant with low surface tension, is more beneficial to the reduction of the wetting angle of a plating assistant liquid film to steel, and reduces the thickness of a plating assistant film, thereby reducing the decomposition time of the plating assistant film during hot galvanizing, reducing the hot galvanizing time and further reducing the plating assistant time. The plating assistant agent provided by the invention can effectively reduce the thickness of the plating assistant agent film, reduce the decomposition time of the plating assistant agent film during hot galvanizing, and reduce the hot galvanizing time, thereby reducing the thickness of a galvanized layer, and meanwhile, the plating assistant agent can be matched with higher aluminum content (0.010-0.050 wt%) in alloy zinc liquid due to stannous chloride and copper chloride in the components, so that no plating leakage occurs during galvanizing.
The invention carries out preliminary iron removal on the conventional zinc liquid (iron content is 0.030 to 0.035 weight percent) by a temperature difference method to obtain preliminary iron removal zinc liquid so as to reduce the consumption of the follow-up iron removal agent; and by adding zinc-gadolinium-iron alloy into zinc liquid, gadolinium reacts with iron element in the zinc liquid to form Fe which is insoluble in the zinc liquid 17 Gd 2 The precipitation greatly reduces the content of iron element in the zinc liquid to obtain low-iron zinc liquid, thereby improving the fluidity of the zinc liquid, and enabling the free zinc liquid on the galvanized steel to flow back into the zinc pot more when the galvanized steel is lifted out of the zinc liquid, thereby achieving the effect of reducing the thickness of the galvanized layer. Meanwhile, the invention adds zinc-gadolinium-iron alloy and zinc-aluminum-vanadium alloy into zinc liquidThe alloy zinc liquid prepared by the gold not only can solve the problem that metal gadolinium and vanadium are very slowly dissolved in the zinc liquid due to the fact that the melting point is far higher than the hot galvanizing temperature, but also can adjust the weight proportion of various alloys added into the zinc liquid and the zinc ingot according to the actual content condition of various alloy components in the zinc liquid when the zinc liquid is continuously consumed and needs to be supplemented into the zinc liquid due to the zinc plating production in a zinc pot, and the content of gadolinium, aluminum and vanadium in the alloy zinc liquid is controlled within a proper range. In the alloy zinc liquid adopted by the invention, higher aluminum content can react with iron on the surface of steel, and a layer of Fe is formed on the surface of galvanized steel 2 Al 5 The inhibition layer film prevents the zinc liquid from reacting with iron elements on the surface of the steel, and improves the effect of reducing the thickness of the zinc coating; the gadolinium element can reduce the iron content in the alloy zinc liquid, reduce the iron content in the zinc liquid, reduce the viscosity of the zinc plating liquid, improve the fluidity of the zinc liquid, enable the free zinc which is not solidified on the surface to flow back into the zinc liquid when the zinc plating workpiece is lifted out of the zinc liquid, and reduce the thickness of the zinc plating layer; the vanadium element can react with silicon on the surface of the steel to generate Si 2 V, covering the surface between the zeta phase of the galvanized layer and the zinc liquid, controlling the 'san dielin effect', preventing the abnormal growth of the galvanized layer and reducing the thickness of the galvanized layer.
Detailed Description
The invention provides a preparation method of an ultrathin galvanized layer of batch hot dip galvanized steel, which comprises the following steps: sequentially carrying out acid washing, water washing, plating assistance and hot galvanizing on the steel to obtain hot galvanized steel; the plating assistant agent for plating assistant comprises the following components: zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent, a plating assistant thickness control agent, hydrochloric acid and water; the total mass concentration of zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, ge mini-12-2-12, deoxidizer, complexing agent and plating assistant film thickness control agent in the plating assistant agent is less than 170g/L, and the pH value of the plating assistant agent is 1.0-2.0; the preparation method of the alloy liquid for hot galvanizing comprises the following steps: carrying out temperature difference method iron removal on the conventional zinc liquid to obtain primary iron-removed zinc liquid; adding gadolinium element into the primarily iron-removed zinc liquid to further remove iron, so as to obtain low-iron zinc liquid; adding zinc-aluminum-vanadium alloy into the low-iron zinc liquid to obtain alloy zinc liquid; the conventional zinc liquid consists of the following components in percentage by mass: zinc is more than or equal to 99.95 percent, iron is 0.030 percent to 0.035 percent, aluminum is 0.006 percent to 0.008 percent, and impurities are less than 0.005 percent; the alloy zinc liquid for hot galvanizing comprises the following components in percentage by mass: iron is less than or equal to 0.013%, gadolinium is 0.0010-0.0015%, vanadium is 0.004-0.008%, aluminum is 0.038-0.050%, impurities are less than 0.005%, and the balance is zinc; the thickness of the galvanized layer of the hot dip galvanizing is 35-48 mu m.
In the invention, the plating assistant agent for plating assistant comprises the following components: zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent, a plating assistant thickness control agent, hydrochloric acid and water; the total mass concentration of zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, deoxidizer, complexing agent and plating-assisting film thickness control agent in the plating assisting agent is less than 170g/L, and the pH value of the plating assisting agent is 1.0-2.0.
The preparation raw materials used in the invention are all commercially available unless otherwise specified.
In the invention, the mass concentration of the zinc chloride in the plating assistant agent is preferably 60-80 g/L, more preferably 63-78 g/L, further preferably 65-75 g/L, and most preferably 70-72 g/L; the mass concentration of ammonium chloride is 20-30 g/L, more preferably 22-28 g/L, still more preferably 22-25 g/L, and most preferably 24-25 g/L; the mass concentration of potassium chloride is preferably 10 to 20g/L, more preferably 12 to 18g/L, still more preferably 14 to 17g/L, and most preferably 15 to 16g/L.
In the present invention, the mass concentration of nickel fluoride in the plating assistant is 5 to 10g/L, more preferably 6 to 9g/L, still more preferably 6 to 8g/L, and most preferably 7 to 8g/L. In the invention, nickel fluoride is an alumina dissolver and a galvanized layer thickness control agent, firstly, fluoride ions can react with alumina to form hexafluoroaluminate, so that a hard alumina film on the surface of liquid zinc is broken, and the wetting effect of the liquid zinc on a steel substrate is not blocked; secondly, nickel ions can be reduced into elemental nickel by zinc, nickel-zinc compounds are adsorbed between zeta and eta phases of the galvanized layer, interdiffusion of zinc and iron atoms is hindered, iron-zinc reaction is slowed down, and therefore the thickness of the galvanized layer is reduced.
In the invention, the mass concentration of stannous chloride in the plating assistant agent is 5-20 g/L, more preferably 8-18 g/L, further preferably 12-18 g/L, and most preferably 13-15 g/L; the mass concentration of copper chloride is 0.5 to 1.5g/L, more preferably 0.7 to 1.3g/L, still more preferably 0.8 to 1.2g/L, and most preferably 0.9 to 1.0g/L. In the invention, when tin chloride and copper chloride in the plating assistant agent can provide a certain amount of copper ions and tin ions to be adsorbed on the surface of steel after the steel is plated, a copper-tin compound is generated after the beginning of zinc plating, and is melted at the galvanizing temperature, and the plating assistant agent is quickly spread on the surface of the steel, so that zinc liquid is quickly contacted with the steel, the steel is prevented from being adhered with aluminum trichloride, aluminum oxide and other impurities under the condition that the steel is not plated with zinc for a long time, the occurrence of the problem of plating omission is avoided, the aluminum content of the zinc liquid is increased, the effect of reducing the thickness of a galvanized layer is improved, and meanwhile, the integrity of a galvanized film is ensured.
In the invention, the mass concentration of the Gemini-12-2-12 in the plating assistant agent is preferably 0.05-0.15 g/L, more preferably 0.06-0.13 g/L, even more preferably 0.08-0.12 g/L, and most preferably 0.10-0.11 g/L. In the invention, the molecular structure of the Gemini-12-2-12 is Cl - [C 12 H 25 (CH 3 ) 2 N + (CH 2 ) 2 N + (CH 3 ) 2 C 12 H 25 ]Cl - Is a quaternary ammonium salt cationic surfactant which is used as a passivating agent. The molecule of the zinc plating agent has two hydrophobic groups and two hydrophilic groups, the hydrophilic groups are connected by virtue of a connecting group through chemical bonds, the biquaternary ammonium salt and the negatively charged iron base form chelating adsorption, under the action of the chemical bonds of the intermediate connecting group, the problem of mutual electrostatic repulsion between molecules when the monoquaternary ammonium salt is adopted is avoided, the tight arrangement between adsorption molecules is ensured, thereby effectively preventing oxygen and aluminum trichloride gas from contacting with the surface of steel, avoiding the oxidation of the surface of the steel by oxygen in air, preventing the aluminum trichloride gas from condensing on the surface of the steel, and further improving the zinc platingSurface quality of the layer.
In the present invention, the oxygen scavenger is preferably hydroxylamine hydrochloride, and the mass concentration of the hydroxylamine hydrochloride in the plating assistant is preferably 0.5 to 2.0g/L, more preferably 0.7 to 1.8g/L, further preferably 0.9 to 1.5g/L, and most preferably 1.0 to 1.3g/L. In the invention, the deoxidizer can remove oxygen in the plating assistant agent, greatly reduce the oxygen content in the plating assistant agent film, prevent the steel from oxidizing and rusting during the plating assistant treatment, and decompose into a reducing atmosphere at the high temperature of galvanization, thereby preventing the high temperature oxidation of the steel matrix.
In the present invention, the complexing agent is preferably glycine, and the mass concentration of glycine in the plating assistant is preferably 1.0 to 2.0g/L, more preferably 1.2 to 1.8g/L, still more preferably 1.4 to 1.7g/L, and most preferably 1.5 to 1.6g/L.
In the present invention, the plating assistant thickness control agent is preferably perfluorobutyl trimethyl quaternary ammonium iodide, and the mass concentration of perfluorobutyl trimethyl quaternary ammonium iodide in the plating assistant agent is preferably 0.2 to 1.0g/L, more preferably 0.3 to 0.9g/L, still more preferably 0.4 to 0.7g/L, and most preferably 0.4 to 0.5g/L. In the invention, the perfluorobutyl trimethyl quaternary ammonium iodine is an environment-friendly surfactant with low surface tension, is more beneficial to the reduction of the wetting angle of a plating assistant liquid film on steel, and reduces the thickness of the plating assistant film, thereby reducing the decomposition time of the plating assistant film during hot galvanizing, reducing the hot galvanizing time and further reducing the plating assistant time.
In the invention, stannous chloride, copper chloride, gemini-12-2-12, hydroxylamine hydrochloride and glycine can generate synergistic effect, and the problem of plating omission caused by the fact that the aluminum content in the zinc liquid reaches more than 0.02% is solved. Wherein, gemini-12-2-12 forms a passivation layer on the surface of the steel, prevents aluminum trichloride formed by the reaction of aluminum, zinc chloride and ammonium chloride from condensing on the surface of the steel during the zinc plating, stannous chloride and cupric chloride respectively provide tin ions and copper ions, and glycine can react with Fe 2+ The ion forms complex, prevents the deposition of iron oxide on the surface of the steel matrix, and can react with Cu 2+ The ions form a complex, the content of free copper ions is controlled, so that the copper ions and tin ions adsorbed on the surface of the steel material have more proper proportion, and the copper ions and tin ions are adsorbed on the surface of the steel materialDuring galvanizing, copper-tin compounds are generated faster, and plating auxiliary agents are replaced by spreading on the surface of the steel, so that zinc liquid is contacted with the steel more quickly, the steel can be prevented from being adhered with aluminum trichloride, aluminum oxide and other impurities under the condition that the steel is not galvanized for a long time, and the anti-leakage plating effect is improved.
In the invention, the use amount of the hydrochloric acid is based on ensuring that the pH value of the plating assistant agent is 1.0-2.0. In the present invention, the pH of the plating assistant stock solution is 1.0 to 2.0, more preferably 1.2 to 1.8, and still more preferably 1.4 to 1.6. In the present invention, the hydrochloric acid is preferably 31% by mass of industrial hydrochloric acid, which is abbreviated as 31% industrial hydrochloric acid in the examples. In the invention, the pH value of the plating assistant agent is regulated to be in the above acid range, which is beneficial to preventing iron oxide from depositing on the surface of steel during use and strengthening the activation of the surface of steel by the plating assistant agent.
In the present invention, the total mass concentration of the chemical substances other than water and hydrochloric acid is less than 170g/L, more preferably 102.25 to 166.15g/L, still more preferably 113.96 to 156.93g/L. The total concentration of other chemical substances except water and hydrochloric acid of the plating assistant agent prepared by the invention is lower than 170g/L, which is lower than that of the conventional plating assistant agent by more than 30%, and the actual plating assistant weight is lower than that of the conventional plating assistant agent by 50% under the interaction of the components. Meanwhile, the plating assistant provided by the invention is a low-smoke easy-to-decompose anti-leakage plating assistant, and the decomposition time is less than 30 seconds under the high-temperature action of hot galvanizing, and is reduced by more than 30 seconds compared with that of the conventional plating assistant, so that the galvanizing time can be reduced, and the thickness of a galvanized layer is reduced.
In the invention, the preparation method of the plating assistant agent comprises the following steps: and mixing the zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent, a plating assistant film thickness control agent, hydrochloric acid and water to obtain the plating assistant agent.
In the present invention, the mixing comprises the steps of: firstly mixing part of water with zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent and a plating assistant film thickness control agent to obtain a first mixed solution, wherein the mass of the part of water accounts for 60-80% of the total mass of the water; and carrying out second mixing on the first mixed solution and hydrochloric acid to obtain a plating assistant agent stock solution, and carrying out third mixing on the plating assistant agent stock solution and the rest of water to obtain the plating assistant solution.
In the present invention, the mixing is preferably performed in a preparation tank or a stirring tank, and in the present invention, the first mixing is preferably performed by adding part of water to the preparation tank or the stirring tank, stirring is preferably performed at a stirring speed of 30-100 rpm, and then adding the zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an oxygen scavenger, a complexing agent and a plating assistant film thickness controlling agent under stirring conditions. In the present invention, the second mixing and the third mixing are preferably performed under stirring, and the stirring speed of the stirring and the stirring speed of the first mixing are kept uniform. In the present invention, the time of the first mixing is preferably 15 to 30 minutes, more preferably 20 to 30 minutes, still more preferably 20 to 25 minutes, and the time of the second mixing is preferably 30 to 60 minutes, more preferably 35 to 50 minutes, still more preferably 40 to 45 minutes. In the invention, the inner wall of the preparation tank or the stirring kettle is preferably made of acid-resistant materials, and the acid-resistant materials are preferably enamel, rubber, plastic or glass fiber reinforced plastic. In the present invention, the mass of the part of water is 60% to 80% of the total mass of the water, more preferably 65% to 75%, still more preferably 70%. In the invention, the second mixing can lead the components in the mixed solution to react with each other under proper concentration and acidity, so that the components in the plating assistant raw solution form a molecular state favorable for plating assistance, and the third mixing can dilute the effective components in the plating assistant solution to the optimal concentration suitable for plating assistance.
The present invention is not particularly limited to the type of steel material, which is known to those skilled in the art at the time of hot dip galvanizing. The present invention is not particularly limited to the acid washing and water washing, and is a technical means well known to those skilled in the art. In the present invention, the steel material after washing is immersed in the plating assistant agent to perform plating, wherein the plating assistant temperature is preferably 65 to 85 ℃, more preferably 68 to 82 ℃, still more preferably 70 to 78 ℃, most preferably 70 to 72 ℃, and the plating assistant time is preferably 30 to 60 seconds, more preferably 35 to 48 seconds, still more preferably 40 to 47 seconds, most preferably 42 to 45 seconds.
In the invention, natural drying is also included after plating assistance, the natural drying temperature is preferably room temperature, and the natural drying time is preferably 3-5 min, more preferably 4-5 min. In the present invention, the natural drying method is preferably to suspend the plating-assisted steel completely from the plating-assisted agent and dry it naturally in air.
In the invention, the preparation method of the alloy liquid for hot galvanizing comprises the following steps: carrying out temperature difference method iron removal on the conventional zinc liquid to obtain primary iron-removed zinc liquid; adding gadolinium element into the primarily iron-removed zinc liquid to further remove iron, so as to obtain low-iron zinc liquid; adding zinc-aluminum-vanadium alloy into the low-iron zinc liquid to obtain alloy zinc liquid; the conventional zinc liquid consists of the following components in percentage by mass: zinc is more than or equal to 99.95 percent, iron is 0.030 percent to 0.035 percent, aluminum is 0.006 percent to 0.008 percent, and impurities are less than 0.005 percent.
In the invention, the method for removing iron by the temperature difference method is preferably as follows: heating the conventional zinc liquid from 440-445 ℃ to 450-455 ℃, preserving heat for 0.5-1 h after the heating, naturally cooling to 430-435 ℃, and preserving heat for 1-2 h after the cooling, thus obtaining the preliminary iron-removing zinc liquid. In a specific embodiment of the invention, the normal production temperature is 440-445 ℃. In the invention, preferably, the fine iron-zinc compounds in the zinc liquid are dissolved in a heating mode, and then dissolved iron atoms in the zinc liquid are recombined into large-particle iron-zinc compounds in a cooling mode, namely: and meanwhile, the heating and cooling speed and the heat preservation time enable the generated zinc slag to have larger particle size and time for full sedimentation, thereby being beneficial to complete sedimentation of the zinc slag and reducing the iron content in the zinc liquid. The method can reduce the iron content in the zinc liquid from more than 0.03% to less than 0.023%.
After the preliminary iron-removing zinc liquid is obtained, gadolinium is added into the preliminary iron-removing zinc liquid to further remove iron, so that low-iron zinc liquid is obtained. In the present invention, the gadolinium element is preferably added as a zinc-gadolinium-iron alloy, and the mass of the effective gadolinium element in the zinc-gadolinium-iron alloy is preferably 0.0050% to 0.0062%, more preferably 0.005% of the total mass of the preliminary iron-removing zinc liquid. The temperature of the primarily iron-removed zinc liquid is preferably raised to 439-445 ℃ before the zinc-gadolinium-iron alloy is added. In the present invention, the zinc-gadolinium-iron alloy is preferably in the form of zinc-gadolinium-iron alloy ingot, and the preparation method of the zinc-gadolinium-iron alloy ingot preferably comprises the following steps: the zinc ingot is melted and then gadolinium-iron alloy is added, the temperature is raised to 750-800 ℃ and kept for 30-60 min to obtain zinc-gadolinium-iron alloy liquid, the zinc-gadolinium-iron alloy liquid is cast to obtain the zinc-gadolinium-iron alloy ingot, the effective gadolinium content of the zinc-gadolinium-iron alloy ingot is preferably 1.00-1.25 wt%, more preferably 1.05-1.20 wt%, even more preferably 1.10-1.15 wt%, and in a specific embodiment of the invention, the effective gadolinium content of the zinc-gadolinium-iron alloy ingot is preferably 1.00wt%, 1.07wt%, 1.10%, 1.11%, 1.14%, 1.22%, 1.23% or 1.25%. In the invention, the zinc ingot is preferably a 0# zinc ingot, and the melting temperature of the zinc ingot is preferably 500-550 ℃; the mass ratio of the zinc ingot to the gadolinium-iron alloy is preferably 64.5-81.5: 1, a step of; it is further preferred that the gadolinium content of the gadolinium-iron alloy is 86.6wt% and the effective gadolinium content of the gadolinium-iron alloy is 82.4wt%. In the present invention, since the iron element in the gadolinium-iron alloy and a part of the gadolinium element have formed intermetallic compound Fe 17 Gd 2 Can not be combined with iron element in zinc liquid any more, but can act as seed crystal in the iron removal process. Wherein the effective gadolinium is as follows: gadolinium which can be combined with iron element in zinc liquid has the content of 82.4wt%, and the gadolinium element can react with dissolved iron element in the zinc liquid to generate new Fe in the iron removal process of the zinc liquid 17 Gd 2 And (5) precipitation. Newly formed Fe 17 Gd 2 Attached to original Fe in alloy 17 Gd 2 On the seed crystal, fe is added 17 Gd 2 Particle size of (3) and promotion ofFeeding Fe into 17 Gd 2 Is deposited; the weight of the zinc-gadolinium-iron alloy ingot is preferably 10 kg/block. In a specific embodiment of the invention, the mass of the zinc ingot is preferably 500kg, the mass of the gadolinium-iron alloy is preferably 6.15 kg-7.70 kg, and the melting, heating and heat preservation are preferably carried out in a crucible of a coreless medium frequency induction furnace. In the invention, when the zinc-gadolinium-iron alloy is added into the preliminary iron-removing zinc liquid, the mass of the effective gadolinium element in the zinc-gadolinium-iron alloy is preferably 0.0050% -0.0062% of the total mass of the preliminary iron-removing zinc liquid, namely 500kg of the zinc-gadolinium-iron alloy is corresponding to every 100 tons of preliminary iron-removing zinc liquid, the content of the effective gadolinium element in the zinc-gadolinium-iron alloy is 1.00-1.25 wt%, and most of the added effective gadolinium element reacts with iron element to form Fe 17 Gd 2 The zinc slag is settled to the bottom of the zinc pot, a small part of gadolinium element is remained and dissolved in the zinc liquid to achieve dissolution balance with iron in the zinc liquid, and the content of the iron element and the gadolinium element in the obtained low-iron zinc liquid is greatly different from the content of the two elements in the initial stage of adding zinc-gadolinium-iron alloy. In a specific embodiment of the present invention, the mass of the effective gadolinium element in the zinc-gadolinium-iron alloy is preferably 0.0050%, 0.0053%, 0.0055%, 0.0057%, 0.0061% or 0.0062% of the total mass of the preliminary iron-removing zinc solution, and after the balance between the gadolinium element and the iron element content in the low-iron zinc solution is achieved, the gadolinium element content in the low-iron zinc solution is only 0.0010-0.0015%, and the iron element content is reduced to below 0.013%. When the galvanized steel is normally produced, the iron element on the surface of the galvanized steel is continuously dissolved into the alloy zinc liquid, so that the iron element content in the alloy zinc liquid is continuously increased, the viscosity of the alloy zinc liquid is synchronously increased, the thickness of a galvanized layer is correspondingly increased, zinc-gadolinium-iron alloy is required to be added according to the yield of the galvanized steel, so that the iron element and gadolinium element in the alloy zinc liquid form precipitation and precipitation, and the stability of the iron and gadolinium element content in the zinc liquid is maintained. The zinc-gadolinium-iron alloy was added to the alloy zinc bath once every 8 hours, and the amount of the zinc-gadolinium-iron alloy added was calculated on the yield of galvanized steel, and 10kg of the zinc-gadolinium-iron alloy was added to the alloy zinc bath every 1 ton of galvanized steel produced. In a specific embodiment of the invention, the zinc-gadolinium-iron The alloy adding method comprises the following steps: and (3) accommodating the zinc-gadolinium-iron alloy by using a basket, and moving back and forth along the length direction of the zinc pot at a position 0.2-0.5 m below the zinc liquid level until the zinc-gadolinium-iron alloy is completely dissolved at a moving speed of 0.2-0.3 m/s. Because the specific gravity of the metal gadolinium is 7.9 and is larger than that of the zinc liquid (6.88 at 440 ℃), in the downward sedimentation process, gadolinium reacts with suspended iron-zinc compounds and dissolved iron in the zinc liquid to form Fe with the specific gravity of about 7.8 17 Gd 2 Finally, the mixture is settled to the bottom of the zinc pot to form zinc slag. After the zinc-gadolinium-iron alloy is added, the method further comprises the steps of standing the zinc liquid and removing dross on the surface of the zinc liquid.
After the low-iron zinc liquid is obtained, zinc-aluminum-vanadium alloy is added into the low-iron zinc liquid to obtain the alloy zinc liquid. In the present invention, the zinc-aluminum-vanadium alloy is preferably in the form of zinc-aluminum-vanadium alloy ingot, and the preparation method of the zinc-aluminum-vanadium alloy ingot preferably comprises the following steps: melting a zinc ingot, adding aluminum-vanadium alloy, heating to 700-750 ℃ and preserving heat for 30-60 min to obtain zinc-aluminum-vanadium alloy liquid, and casting the zinc-aluminum-vanadium alloy liquid to obtain the zinc-aluminum-vanadium alloy ingot; the zinc ingot is preferably a 0# zinc ingot, and the melting temperature of the zinc ingot is preferably 450-500 ℃; the mass ratio of the zinc ingot to the aluminum-vanadium alloy is preferably 15.8-19:1, and in the specific embodiment of the invention, the mass ratio of the zinc ingot to the aluminum-vanadium alloy is preferably 15.8:1, 16.4:1, 17.0:1, 17.6:1 or 19.0:1, and the content of vanadium element in the aluminum-vanadium alloy is preferably 10wt%; the weight of the zinc-aluminum-vanadium alloy ingot is preferably 10 kg/block, the aluminum element content of the zinc-aluminum-vanadium alloy ingot is preferably 4.5-5.4 wt%, and the vanadium element content is preferably 0.50-0.60 wt%. In the specific embodiment of the invention, the weight of the zinc-aluminum-vanadium alloy ingot is preferably 10 kg/block, and the aluminum element content of the zinc-aluminum-vanadium alloy ingot is preferably 0.50wt%, 0.54wt%, 0.56wt%, 0.58wt% or 0.59wt%, and the corresponding vanadium element content is preferably 4.50wt%, 4.84wt%, 5.01wt%, 5.18wt% or 5.35wt%. In the specific embodiment of the invention, the mass of the zinc ingot is preferably 475kg, the mass of the aluminum-vanadium alloy is preferably 25-30 kg, the melting and the heating are preferably performed in a crucible of an intermediate frequency induction furnace, the aluminum-vanadium alloy is preferably added by pressing the aluminum-vanadium alloy to a position 50cm below the zinc liquid surface by a graphite bell jar, and the aluminum-vanadium alloy is fixed and is washed and dissolved by the stirred zinc liquid under the electromagnetic stirring action of the intermediate frequency induction furnace.
In the present invention, when the zinc-aluminum-vanadium alloy is added to the low-iron zinc liquid, the mass of the vanadium element in the zinc-aluminum-vanadium alloy is preferably 0.004% to 0.008%, more preferably 0.005% to 0.006%, of the total mass of the low-iron zinc liquid. In the present invention, when the zinc-aluminum-vanadium alloy is added to the low-iron zinc liquid, the temperature of the low-iron zinc liquid is preferably 439 to 445 ℃. In a specific embodiment of the invention, when the zinc-aluminum-vanadium alloy is added into the low-iron zinc liquid, namely, 1.00 ton of the zinc-aluminum-vanadium alloy is corresponding to each 100 tons of low-iron zinc liquid, the content of vanadium element in the zinc-aluminum-vanadium alloy is 0.50 to 0.60 weight percent, the content of aluminum element is 4.5 to 5.4 weight percent, and the content of vanadium in the obtained alloy zinc liquid is 0.005 to 0.006 weight percent. When hot galvanizing is carried out normally, the vanadium element in the alloy zinc liquid is continuously reacted with the silicon element on the surface of the steel to form and is consumed, and the aluminum element reacts with the iron element on the surface of the steel to form Fe 2 Al 5 The barrier layer is consumed, so that zinc-aluminum-vanadium alloy is continuously supplemented according to the production yield, and the content of vanadium and aluminum elements in the alloy zinc liquid is kept stable. The zinc-aluminum-vanadium alloy is added into the alloy zinc liquid every 8 hours, the addition amount of the zinc-aluminum-vanadium alloy is calculated according to the yield of galvanized steel, and 10kg of the zinc-aluminum-vanadium alloy is added into the alloy zinc liquid every 8-12 tons of galvanized steel is produced. In a specific embodiment of the invention, the zinc-aluminum-vanadium alloy adding method comprises the following steps: and (3) accommodating the zinc-aluminum-vanadium alloy by using a basket, and moving back and forth along the length direction of the zinc pot at a position 1.0 m-1.5 m below the zinc liquid level until the zinc-aluminum-vanadium alloy is completely dissolved, wherein the moving speed is 0.2 m/s-0.3 m/s. After the zinc-aluminum-vanadium alloy is added, the method further comprises the steps of standing the zinc liquid and removing dross on the surface of the zinc liquid.
In the present invention, the iron content in the alloy zinc liquid for hot dip galvanizing is not more than 0.013%, preferably 0.008% to 0.013%, more preferably 0.009% to 0.012%, and even more preferably 0.010% to 0.011% by mass. In the invention, because the iron content in the alloy zinc liquid is smaller than the saturated iron content in the alloy zinc liquid during hot galvanizing, the content of solid iron zinc compounds insoluble in the alloy zinc liquid is smaller, the viscosity of the alloy zinc liquid is reduced, the fluidity is improved, and free zinc which is not solidified on the surface can flow back into the zinc liquid when a galvanized workpiece is lifted out of the zinc liquid, thereby reducing the thickness of a galvanized layer.
In the present invention, the gadolinium content of the alloy zinc liquid for hot dip galvanizing is 0.0010% to 0.0015%, preferably 0.0012% to 0.0015%, and more preferably 0.0013% to 0.0014% by mass. In the invention, gadolinium can react with iron of steel dissolved in galvanization liquid to form stable Fe during hot galvanizing 17 Gd 2 And (3) precipitating to ensure that the iron content in the alloy zinc liquid is below 0.013%, so that the alloy zinc liquid has good fluidity.
In the present invention, the content of vanadium in the alloy zinc liquid for hot dip galvanizing is 0.004% to 0.008%, preferably 0.004% to 0.007%, more preferably 0.005% to 0.006% by mass. The inventors found that the effect of the vanadium (V) element in suppressing the "Style effect" is far superior to that of the nickel (Ni) element when the vanadium is present as Al 3 The V-shaped alloy is in the alloy zinc liquid, can effectively inhibit the iron-zinc reaction abnormal rapid caused by high silicon steel and the eride effect of the ultra-thick galvanized layer, and has the inhibition effect which is 5-8 times higher than that of the nickel element commonly used at present. This is because nickel reacts with silicon in the steel material to form Ni during the galvanization 2 Si and NiSi, the free energy of formation is-56 kJ/mol and-59 kJ/mol respectively; the vanadium element can react with silicon in the steel material to form Si in the galvanization process 2 V, the free energy of formation is-85 kJ/mol; it can be seen that vanadium reacts more readily with silicon on the surface of steel than nickel, so that needle-like elemental silicon is converted into fine-grained Si 2 V, adhere to the surface of zeta phase, can not merely avoid acicular elemental silicon to pierce zeta phase, can also block up the part that is pierced, prevent zinc liquid and delta phase of the inner layer from direct contact, slow down the iron zinc reaction, control "san dielin effect", prevent the zinc coating from growing excessively. In the hot galvanizing process, the alloy zinc liquidVanadium can react with aluminum to form Al 3 V and exists in this form, and the excess aluminum dissolves in the zinc bath to form aluminum atoms. When galvanization starts, atomic aluminum reacts with the steel surface rapidly to form Fe 2 Al 5 A barrier layer, the aluminum content in the alloy zinc liquid near the barrier layer is rapidly reduced, and the alloy zinc liquid contains Al 3 V has reactivity with iron smaller than that of aluminum, and Al after the aluminum content is reduced to a certain degree 3 V reacts with steel to form Fe 2 Al 5 And VZn 3 The former is adhered on the barrier layer, so that the barrier layer can continue to grow, and the problem that zinc liquid cannot be prevented from corroding the barrier layer due to partial aluminum deficiency near the barrier layer is solved. VZn (V-Zn) 3 Can react with silicon on the surface of steel to generate Si 2 V can well inhibit the Style effect, and besides, zinc slag generated when vanadium is added in the hot galvanizing process is less than nickel element.
In the present invention, the aluminum content of the alloy zinc liquid for hot dip galvanizing is 0.038% to 0.050%, preferably 0.038% to 0.048%, more preferably 0.040% to 0.045% by mass. In the present invention, the aluminum atoms react with the steel material to form Fe on the surface of the steel material 2 Al 5 The barrier layer reduces the zinc plating layer by more than 10 mu m. The present invention preferably controls the aluminum content within the above range, and can prevent problems of missing plating and poor surface quality of the zinc plating layer due to an excessively high aluminum content, when the plating assistant agent of the present invention is used in combination.
In the present invention, the impurity content in the alloy zinc liquid for hot dip galvanizing is < 0.005%, preferably 0.003% to 0.005%, more preferably 0.003% to 0.004% by mass. The impurity element content is too high, the surface quality and corrosion resistance of the galvanized layer are adversely affected, the impurity content is too low, and the raw material zinc ingot is difficult to meet the requirements.
In the invention, the zinc content in the hot dip galvanized alloy zinc liquid is preferably more than or equal to 99.92% in terms of mass fraction.
In the present invention, the temperature of the hot dip galvanizing is preferably 435 to 450 ℃, more preferably 438 to 446 ℃, still more preferably 440 to 445 ℃, and the time of the hot dip galvanizing is preferably 130 to 160 seconds, more preferably 136 to 158 seconds, still more preferably 141 to 154 seconds. In the present invention, the hot dip galvanizing method is preferably as follows: and (3) hanging the steel into the alloy zinc liquid for hot galvanizing until no obvious bubbles and scum in the alloy zinc liquid emerge, and hanging the steel out by taking off the alloy zinc liquid surface float by using an ash-spraying knife. In the present invention, the thickness of the zinc plating layer is preferably 35 to 48. Mu.m, more preferably 40 to 45. Mu.m.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
Example 1
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 60kg of zinc chloride, 30kg of ammonium chloride, 15kg of potassium chloride, 8kg of nickel fluoride, 15kg of stannous chloride, 1.0kg of copper chloride, 0.05kg of Gemini-12-2-12, 1.0kg of hydroxylamine hydrochloride, 1.0kg of glycine, 0.3kg of perfluorobutyl trimethyl quaternary ammonium iodine, the balance of hydrochloric acid and water, and the dosage of the hydrochloric acid is such that the pH value of the plating assistant is adjusted to 1.0. 1m 3 The preparation method of the plating assistant agent comprises the following steps: adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 15 minutes to completely dissolve the components, adding 31% industrial hydrochloric acid with calculated weight into the solution according to the pH value requirement of the final plating assistant, mixing for 60 minutes under a stirring state, and continuously adding water to ensure that the total amount of the solution is 1m 3 The pH value is 1.0, and the plating assistant agent A is obtained 1 . In the actual production process, the dosage of each component is multiplied according to the actual dosage of the plating assistant agent. In this example, plating assistant A 1 Heated to 70 ℃ for use.
2. Preparation of zinc-gadolinium-iron alloy: melting 500kg of No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 500 ℃, then adding 6.15kg of gadolinium-iron alloy containing 86.6wt% (wherein the content of effective gadolinium element is 82.4 wt%) of gadolinium into the zinc liquid, continuously heating to 750 ℃, and preserving heat for 30min to obtain zinc-gadolinium-iron alloy liquid. Casting the alloy liquid into zinc-gadolinium-iron alloy ingot B of 10 kg/block 1 Wherein the effective gadolinium content is 1.00wt%.
3. PreparationZinc-aluminum-vanadium alloy: melting 475kg No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 450 ℃, and then adding 25kg of aluminum-vanadium alloy containing 10wt% of vanadium into the zinc liquid, wherein the adding method comprises the following steps: the aluminum-vanadium alloy is pressed to a position 50cm below the liquid level of zinc by a graphite bell jar, and is fixed. Then the temperature of the zinc liquid is increased to 700 ℃, and the zinc-aluminum-vanadium alloy liquid is obtained after heat preservation for 30 min. Casting the alloy liquid into a zinc-aluminum-vanadium alloy ingot C with the weight of 10 kg/block 1 Wherein the aluminum content is 4.50wt% and the vanadium content is 0.50wt%;
4. preparing alloy zinc liquid: and (3) uniformly stacking 400 tons of No. 0 zinc ingots with the weight of 25 Kg/block in a zinc pot, indirectly heating the zinc ingots by using natural gas to melt the zinc ingots, controlling the temperature to be 440-445 ℃, and adding a certain amount of zinc-aluminum alloy to obtain the conventional zinc liquid. After the conventional zinc liquid is galvanized for a period of time, the conventional zinc liquid comprises the following main element components in percentage by mass: zinc is more than or equal to 99.95 percent, iron is 0.030 percent to 0.035 percent, aluminum is 0.006 percent to 0.008 percent, and impurities are less than 0.005 percent. The conventional zinc liquid is heated to 450 ℃ from the normal production temperature, kept for 1 hour, then naturally cooled to 435 ℃, and kept stand for 1.8 hours. Part of iron in the zinc liquid is FeZn 13 The zinc slag is formed by combining forms and is deposited at the bottom of a zinc pot, the zinc slag is fished out by a special tool, the zinc liquid with preliminary iron removal is obtained, and the temperature is raised to 442 ℃ for standby. The Fe content in the zinc liquid is reduced from more than 0.03% to less than 0.023%.
When the zinc-gadolinium-iron alloy ingot is added for the first time, 50 alloy ingots B are added according to the zinc liquid with preliminary iron removal per 100 tons 1 Is added with alloy ingot B in proportion of 1 The method comprises the steps of carrying out a first treatment on the surface of the After normal production, 1 block (10 kg/block) of alloy ingot B is added per 1 ton of galvanized steel 1 Added every 8 hours. The adding mode is as follows: 10 alloy ingots B are filled each time by using a hanging basket 1 Moving back and forth along the length direction of the zinc pot at a position 0.2-0.5 m below the zinc liquid level and at a moving speed of 0.2-0.3 m/s until the solution is complete, and then adding all alloy ingots B according to the method 1 Adding into zinc liquid. Standing to drag out dross on the surface of the zinc liquid to obtain low-iron zinc liquid D 1 。
To low iron zinc liquid D 1 Adding zinc-aluminum-vanadium alloy ingot C 1 Zinc-aluminium-vanadium alloy ingot C 1 The primary addition amount of (C) is low-iron zinc liquid D 1 1.0% by weightAfter normal production, 1 (10 kg/block) alloy ingot C is added per 10 tons of galvanized steel according to the weight of the galvanized steel 1 Added every 8 hours. Zinc-aluminum-vanadium alloy ingot C 1 The adding mode is that 2-3 alloy ingots C are filled each time by using a hanging basket 1 Moving back and forth along the length direction of the zinc pot at a position 1.0-1.5 m below the zinc liquid level and at a moving speed of 0.2-0.3 m/s until the solution is complete, and then adding all alloy ingots C according to the method 1 Adding into zinc liquid. Standing, and fishing out dross on the surface of the zinc liquid to obtain alloy zinc liquid E 1 E during hot galvanizing 1 The temperature of (2) was 441 ℃.
5. Hot galvanizing: after the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 70 DEG C 1 Soaking for 30s, lifting to air, and naturally drying for 5min. Then the steel is hung into alloy zinc liquid E with the temperature of 441 DEG C 1 Zinc plating is carried out until no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the zinc liquid surface float, the galvanized steel is lifted out, and the zinc plating time is 150s, thus obtaining the ultrathin galvanized layer steel F 1 。
Example 2
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 70kg of zinc chloride, 20kg of ammonium chloride, 20kg of potassium chloride, 5kg of nickel fluoride, 10kg of stannous chloride, 0.5kg of copper chloride, 0.10kg of Gemini-12-2-12, 0.5kg of hydroxylamine hydrochloride, 2.0kg of glycine, 0.2kg of perfluorobutyl trimethyl quaternary ammonium iodine, the balance of hydrochloric acid and water, and the dosage of the hydrochloric acid is used for adjusting the pH value of the plating assistant to 1.5. 1m 3 The preparation method of the plating assistant agent comprises the following steps: adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 25 minutes to completely dissolve the components, adding 31% industrial hydrochloric acid with calculated weight into the solution according to the pH value requirement of the final plating assistant, reacting for 45 minutes under the stirring state, and continuously adding water to ensure that the total amount of the solution is 1m 3 The pH value is 1.5, and the plating assistant agent A is obtained 2 . In the actual production process, the dosage of each component is multiplied according to the actual dosage of the plating assistant agent. In this example, plating assistant A 2 Heated to 75 ℃ for use.
2. Preparation of zinc-gadolinium-iron alloy: melting 500kg of No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 550 ℃, adding 6.8kg of gadolinium-iron alloy containing 86.6wt% (the effective gadolinium content is 82.4 wt%) of gadolinium into the zinc liquid, continuously heating to 760 ℃, and preserving heat for 60min to obtain zinc-gadolinium-iron alloy liquid. Casting the alloy liquid into zinc-gadolinium-iron alloy ingot B of 10 kg/block 2 Wherein the effective gadolinium content is 1.11wt%.
3. Preparation of zinc-aluminum-vanadium alloy: melting 475kg No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 500 ℃, and then adding 28kg of aluminum-vanadium alloy containing 10wt% of vanadium into the zinc liquid in the following manner: the aluminum-vanadium alloy is pressed to a position 50cm below the liquid level of zinc by a graphite bell jar, and is fixed. Then the temperature of the zinc liquid is increased to 720 ℃, and the zinc-aluminum-vanadium alloy liquid is obtained after heat preservation for 60 min. Casting the alloy liquid into a zinc-aluminum-vanadium alloy ingot C with the weight of 10 kg/block 2 Wherein the aluminum content is 5.01wt% and the vanadium content is 0.56wt%;
4. preparing alloy zinc liquid: the conventional zinc bath in example 1 was raised from the normal production temperature to 460 c, incubated for 0.5 hours, then naturally cooled to 430 c, and left to stand for 1.2 hours. Part of iron in the zinc liquid is FeZn 13 The zinc slag is formed by combining the forms and is deposited at the bottom of the zinc pot. And fishing out zinc slag by using a special tool. Heating to 445 ℃ for standby. The Fe content in the zinc liquid is reduced from more than 0.03% to less than 0.023%.
When zinc-gadolinium-iron alloy ingot is added for the first time, 50 alloy ingots B are added per 100 tons of zinc liquid 2 Is added with alloy ingot B in proportion of 2 The method comprises the steps of carrying out a first treatment on the surface of the After normal production, 1 block (10 kg/block) of alloy ingot B is added per 1 ton of galvanized steel 2 Added every 8 hours. Alloy ingot C 2 In the same manner as in example 1, all of the alloy ingots C 2 After the addition, standing and fishing out the scum on the surface of the zinc liquid to obtain low-iron zinc liquid D 2 。
To low iron zinc liquid D 2 Adding zinc-aluminum-vanadium alloy ingot C 2 Zinc-aluminium-vanadium alloy ingot C 2 The primary addition amount of (C) is low-iron zinc liquid D 2 1.0% of the mass, and 1 (10 kg/block) of alloy ingot C is added per 8 tons of galvanized steel according to the weight of the galvanized steel after normal production 2 Added every 8 hours. Zinc-aluminum-vanadium alloy ingot C 2 In the same manner as in example 1, all of the alloy ingots C 2 Adding into zinc liquid. Standing, and fishing out dross on the surface of the zinc liquid to obtain alloy zinc liquid E 2 E during hot galvanizing 2 The temperature of (2) was 443 ℃.
5. Hot galvanizing: after the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 75 DEG C 2 Soaking for 60s, lifting to air, and naturally drying for 5min. Then the steel is hung into alloy zinc liquid E with the temperature of 443 DEG C 2 Zinc plating is carried out until no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the zinc liquid surface float, the galvanized steel is lifted out, and the zinc plating time is 130s, thus obtaining the ultrathin galvanized layer steel F 2 。
Example 3
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 80kg of zinc chloride, 25kg of ammonium chloride, 10kg of potassium chloride, 10kg of nickel fluoride, 5kg of stannous chloride, 1.5kg of copper chloride, 0.15kg of Gemini-12-2-12, 1.5kg of hydroxylamine hydrochloride, 1.5kg of glycine, 0.5kg of perfluorobutyl trimethyl quaternary ammonium iodine, the balance of hydrochloric acid and water, and the dosage of the hydrochloric acid is such that the pH value of the plating assistant is adjusted to 2.0. 1m 3 The preparation method of the plating assistant agent comprises the following steps: adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 30 minutes to completely dissolve the components, adding 31% industrial hydrochloric acid with calculated weight into the solution according to the pH value requirement of the final plating assistant, reacting for 50 minutes under the stirring state, and continuously adding water to ensure that the total amount of the solution is 1m 3 The pH value is 2.0, and the plating assistant agent A is obtained 3 . In the actual production process, the dosage of each component is multiplied according to the actual dosage of the plating assistant agent. In this example, plating assistant A 3 Heated to 65℃for use.
2. Preparation of zinc-gadolinium-iron alloy: melting 500kg of No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 530 ℃, adding 7.5kg of gadolinium-iron alloy containing 86.6wt% (wherein the content of effective gadolinium element is 82.4 wt%) of gadolinium into the zinc liquid, continuously heating to 780 ℃, and preserving heat for 40min to obtain zinc-gadolinium-iron alloy liquid . Casting the alloy liquid into zinc-gadolinium-iron alloy ingot B of 10 kg/block 3 Wherein the effective gadolinium content is 1.22wt%.
3. Preparation of zinc-aluminum-vanadium alloy: melting 475kg No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 480 ℃, and then adding 30kg of aluminum-vanadium alloy containing 10wt% of vanadium into the zinc liquid in the following manner: the aluminum-vanadium alloy is pressed to a position 50cm below the liquid level of zinc by a graphite bell jar, and is fixed. Then the temperature of the zinc liquid is increased to 720 ℃, and the heat preservation is carried out for 40min, thus obtaining the zinc-aluminum-vanadium alloy liquid. Casting the alloy liquid into a zinc-aluminum-vanadium alloy ingot C with the weight of 10 kg/block 3 Wherein the aluminum content is 5.40wt% and the vanadium content is 0.60wt%;
4. preparing alloy zinc liquid: the conventional zinc bath in example 1 was raised from the normal production temperature to 452 c, incubated for 0.8 hours, then naturally cooled to 432 c, and left to stand for 1.0 hour. Part of iron in the zinc liquid is FeZn 13 The zinc slag is formed by combining forms and is deposited at the bottom of a zinc pot, the zinc slag is fished out by a special tool, the zinc liquid with preliminary iron removal is obtained, and the temperature is raised to 445 ℃ for standby. The Fe content in the zinc liquid is reduced from more than 0.03% to less than 0.023%.
When the zinc-gadolinium-iron alloy ingot is added for the first time, 50 alloy ingots B are added according to the zinc liquid with preliminary iron removal per 100 tons 3 Is added with alloy ingot B in proportion of 3 The method comprises the steps of carrying out a first treatment on the surface of the After normal production, 1 block (10 kg/block) of alloy ingot B is added per 1 ton of galvanized steel 3 Added every 8 hours. Alloy ingot B 3 In the same manner as in example 1, all of the alloy ingots B 3 After the addition, standing and fishing out the scum on the surface of the zinc liquid to obtain low-iron zinc liquid D 3 。
To low iron zinc liquid D 3 Adding zinc-aluminum-vanadium alloy ingot C 3 Zinc-aluminium-vanadium alloy ingot C 3 The primary addition amount of (C) is low-iron zinc liquid D 3 1.0% of the mass, and 1 (10 kg/block) of alloy ingot C is added per 9 tons of galvanized steel according to the weight of the galvanized steel after normal production 3 Added every 8 hours. Alloy ingot C 3 In the same manner as in example 1, all of the alloy ingots C 3 After the addition, standing and fishing out the scum on the surface of the zinc liquid to obtain low-iron zinc liquid E 3 E during hot galvanizing 3 Is 442 DEG C。
5. Hot galvanizing: after the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 65 DEG C 3 Soaking for 40s, lifting to air, and naturally drying for 5min. Then the steel is hung into alloy zinc liquid E with the temperature of 442 DEG C 3 Zinc plating is carried out until no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the zinc liquid surface float, the galvanized steel is lifted out, and the zinc plating time is 160s, thus obtaining the ultrathin galvanized layer steel F 3 。
Example 4
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 75kg of zinc chloride, 20kg of ammonium chloride, 18kg of potassium chloride, 7kg of nickel fluoride, 20kg of stannous chloride, 0.8kg of copper chloride, 0.12kg of Gemini-12-2-12, 2.0kg of hydroxylamine hydrochloride, 1.6kg of glycine, 0.4kg of perfluorobutyl trimethyl quaternary ammonium iodine, the balance of hydrochloric acid and water, and the dosage of the hydrochloric acid is such that the pH value of the plating assistant is adjusted to 1.8. 1m 3 The preparation method of the plating assistant agent comprises the following steps: adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 15 minutes to completely dissolve the components, adding 31% industrial hydrochloric acid with calculated weight into the solution according to the pH value requirement of the final plating assistant, reacting for 40 minutes under the stirring state, and continuously adding water to ensure that the total amount of the solution is 1m 3 The pH value is 1.8, and the plating assistant agent A is obtained 4 . In the actual production process, the dosage of each component is multiplied according to the actual dosage of the plating assistant agent. In this example, plating assistant A 4 Heated to 85 ℃ for use.
2. Preparation of zinc-gadolinium-iron alloy: melting 500kg of No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 550 ℃, adding 7.7kg of gadolinium-iron alloy containing 86.6wt% (the effective gadolinium content is 82.4 wt%) of gadolinium into the zinc liquid, continuously heating to 770 ℃, and preserving heat for 50min to obtain zinc-gadolinium-iron alloy liquid. Casting the alloy liquid into zinc-gadolinium-iron alloy ingot B of 10 kg/block 4 Wherein the effective gadolinium content is 1.25wt%.
3. Preparation of zinc-aluminum-vanadium alloy: melting 475kg No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 480 ℃, and adding into the zinc liquid27kg of aluminum-vanadium alloy containing 10wt% of vanadium, wherein the adding mode is as follows: the aluminum-vanadium alloy is pressed to a position 50cm below the liquid level of zinc by a graphite bell jar, and is fixed. Then the temperature of the zinc liquid is increased to 710 ℃, and the temperature is kept for 50 minutes, so as to obtain zinc-aluminum-vanadium alloy liquid. Casting the alloy liquid into a zinc-aluminum-vanadium alloy ingot C with the weight of 10 kg/block 4 Wherein the aluminum content is 4.84wt% and the vanadium content is 0.54wt%;
4. preparing alloy zinc liquid: the conventional zinc bath in example 1 was raised from the normal production temperature to 455 deg.c, incubated for 0.6 hours, then naturally cooled to 434 deg.c, and left to stand for 1.8 hours. Part of iron in the zinc liquid is FeZn 13 The zinc slag is formed by combining forms and is deposited at the bottom of a zinc pot, the zinc slag is fished out by a special tool, the primary iron-removing zinc liquid is obtained, and the temperature is raised to 440 ℃ for standby. The Fe content in the zinc liquid is reduced from more than 0.03% to less than 0.023%.
When the zinc-gadolinium-iron alloy ingot is added for the first time, 50 alloy ingots B are added according to the zinc liquid with preliminary iron removal per 100 tons 4 Is added with alloy ingot B in proportion of 4 The method comprises the steps of carrying out a first treatment on the surface of the After normal production, 1 block (10 kg/block) of alloy ingot B is added per 1 ton of galvanized steel 4 Added every 8 hours. Alloy ingot B 4 In the same manner as in example 1, all of the alloy ingots B 4 After the addition, standing and fishing out the scum on the surface of the zinc liquid to obtain low-iron zinc liquid D 4 。
To low iron zinc liquid D 4 Adding zinc-aluminum-vanadium alloy ingot C 4 Zinc-aluminium-vanadium alloy ingot C 4 The primary addition amount of (C) is low-iron zinc liquid D 4 1.0% of the mass, and 1 (10 kg/block) of alloy ingot C is added per 11 tons of galvanized steel according to the weight of the galvanized steel after normal production 4 Added every 8 hours. Alloy ingot C 4 In the same manner as in example 1, all of the alloy ingots C 4 After the addition, standing and fishing out the dross on the surface of the zinc liquid to obtain alloy zinc liquid E 4 E during hot galvanizing 4 The temperature of (2) was 445 ℃.
5. Hot galvanizing: after the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 85 DEG C 4 Soaking for 50s, lifting to air, and naturally drying for 5min. Then the steel is hung into alloy zinc liquid E with the temperature of 445 DEG C 4 Is performed in the middle ofZinc plating, namely, after no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the float on the zinc liquid surface, the galvanized steel is lifted out, and the zinc plating time is 154 seconds, so that the ultrathin galvanized steel F is obtained 4 。
Example 5
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 65kg of zinc chloride, 28kg of ammonium chloride, 16kg of potassium chloride, 9kg of nickel fluoride, 12kg of stannous chloride, 1.3kg of copper chloride, 0.06kg of Gemini-12-2-12, 0.9kg of hydroxylamine hydrochloride, 1.2kg of glycine, 0.3kg of perfluorobutyl trimethyl quaternary ammonium iodine, the balance of hydrochloric acid and water, and the dosage of the hydrochloric acid is such that the pH value of the plating assistant is adjusted to 1.4. 1m 3 The preparation method of the plating assistant agent comprises the following steps: adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 15 minutes to completely dissolve the components, adding 31% industrial hydrochloric acid with calculated weight into the solution according to the pH value requirement of the final plating assistant, reacting for 52 minutes in a stirring state, and continuously adding water to ensure that the total amount of the solution is 1m 3 The pH value is 1.4, and the plating assistant agent A is obtained 5 . In the actual production process, the dosage of each component is multiplied according to the actual dosage of the plating assistant agent. In this example, plating assistant A 5 Heated to 78 ℃ for use.
2. Preparation of zinc-gadolinium-iron alloy: melting 500kg of No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 510 ℃, adding 6.75kg of gadolinium-iron alloy containing 86.6wt% (the effective gadolinium content is 82.4 wt%) of gadolinium into the zinc liquid, continuously heating to 800 ℃, and preserving heat for 45min to obtain zinc-gadolinium-iron alloy liquid. Casting the alloy liquid into zinc-gadolinium-iron alloy ingot B of 10 kg/block 5 Wherein the effective gadolinium content is 1.10wt%.
3. Preparation of zinc-aluminum-vanadium alloy: melting 475kg No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 490 ℃, and then adding 29kg of aluminum-vanadium alloy containing 10wt% of vanadium into the zinc liquid in the following manner: the aluminum-vanadium alloy is pressed to a position 50cm below the liquid level of zinc by a graphite bell jar, and is fixed. Then the temperature of the zinc liquid is increased to 740 ℃, and the temperature is kept for 45min, thus obtaining the zinc-aluminum-vanadium alloy liquid. Casting the alloy liquid into a zinc-aluminum-vanadium alloy ingot C with the weight of 10 kg/block 5 Wherein the aluminum content is 5.18wt% and the vanadium content is 0.58wt%;
4. preparing alloy zinc liquid: the conventional zinc bath in example 1 was raised from the normal production temperature to 455 deg.c, kept for 0.7 hours, then naturally cooled to 433 deg.c, and kept at rest for 1.5 hours. Part of iron in the zinc liquid is FeZn 13 The zinc slag is formed by combining forms and is deposited at the bottom of a zinc pot, the zinc slag is fished out by a special tool, the primary iron-removing zinc liquid is obtained, and the temperature is raised to 444 ℃ for standby. The Fe content in the zinc liquid is reduced from more than 0.03% to less than 0.023%.
When the zinc-gadolinium-iron alloy ingot is added for the first time, 50 alloy ingots B are added according to the zinc liquid with preliminary iron removal per 100 tons 5 Is added with alloy ingot B in proportion of 5 The method comprises the steps of carrying out a first treatment on the surface of the After normal production, 1 block (10 kg/block) of alloy ingot B is added per 1 ton of galvanized steel 5 Added every 8 hours. Alloy ingot B 5 In the same manner as in example 1, all of the alloy ingots B 5 After the addition, standing and fishing out the scum on the surface of the zinc liquid to obtain low-iron zinc liquid D 5 。
To low iron zinc liquid D 5 Adding zinc-aluminum-vanadium alloy ingot C 5 Zinc-aluminium-vanadium alloy ingot C 5 The primary addition amount of (C) is low-iron zinc liquid D 5 1.0% of the mass, and 1 (10 kg/block) of alloy ingot C is added per 12 tons of galvanized steel according to the weight of the galvanized steel after normal production 5 Added every 8 hours. Alloy ingot C 5 In the same manner as in example 1, all of the alloy ingots C 5 After the addition, standing and fishing out the dross on the surface of the zinc liquid to obtain alloy zinc liquid E 5 E during hot galvanizing 5 The temperature of (2) was 440 ℃.
5. Hot galvanizing: after the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 78 DEG C 5 Soaking for 35s, lifting to air, and naturally drying for 5min. Then the steel is hung into alloy zinc liquid E with the temperature of 440 DEG C 5 Zinc plating is carried out until no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the zinc liquid surface float, the galvanized steel is lifted out, and the zinc plating time is 136s, thus obtaining the ultrathin galvanized layer steel F 5 。
Example 6
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 63kg of zinc chloride, 25kg of ammonium chloride, 14kg of potassium chloride, 6kg of nickel fluoride, 18kg of stannous chloride, 0.9kg of copper chloride, 0.13kg of Gemini-12-2-12, 1.8kg of hydroxylamine hydrochloride, 1.7kg of glycine, 0.5kg of perfluorobutyl trimethyl quaternary ammonium iodine, the balance of hydrochloric acid and water, and the dosage of the hydrochloric acid is such that the pH value of the plating assistant is adjusted to 1.2. 1m 3 The preparation method of the plating assistant agent comprises the following steps: adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 15 minutes to completely dissolve the components, adding 31% industrial hydrochloric acid with calculated weight into the solution according to the pH value requirement of the final plating assistant, reacting for 38 minutes under the stirring state, and continuously adding water to ensure that the total amount of the solution is 1m 3 The pH value is 1.2, and the plating assistant agent A is obtained 6 . In the actual production process, the dosage of each component is multiplied according to the actual dosage of the plating assistant agent. In this example, plating assistant A 6 Heated to 82 c for use.
2. Preparation of zinc-gadolinium-iron alloy: melting 500kg of No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 520 ℃, adding 7.0kg of gadolinium-iron alloy containing 86.6wt% (the effective gadolinium content is 82.4 wt%) of gadolinium into the zinc liquid, continuously heating to 790 ℃, and preserving heat for 35min to obtain zinc-gadolinium-iron alloy liquid. Casting the alloy liquid into zinc-gadolinium-iron alloy ingot B of 10 kg/block 6 Wherein the effective gadolinium content is 1.14wt%.
3. Preparation of zinc-aluminum-vanadium alloy: melting 475kg No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 500 ℃, and then adding 25kg of aluminum-vanadium alloy containing 10wt% of vanadium into the zinc liquid in the following manner: the aluminum-vanadium alloy is pressed to a position 50cm below the liquid level of zinc by a graphite bell jar, and is fixed. Then the temperature of the zinc liquid is increased to 730 ℃, and the zinc-aluminum-vanadium alloy liquid is obtained after the heat preservation is carried out for 35 min. Casting the alloy liquid into a zinc-aluminum-vanadium alloy ingot C with the weight of 10 kg/block 6 Wherein the aluminum content is 4.5wt% and the vanadium content is 0.50wt%;
4. Preparing alloy zinc liquid: the conventional zinc bath in example 1 was raised from the normal production temperature to 451 deg.c, kept for 1.0 hour, then naturally cooled to 431 deg.c, and kept at rest for 1.5 hours.Part of iron in the zinc liquid is FeZn 13 The zinc slag is formed by combining forms and is deposited at the bottom of a zinc pot, the zinc slag is fished out by a special tool, the primary iron-removing zinc liquid is obtained, and the temperature is raised to 441 ℃ for standby. The Fe content in the zinc liquid is reduced from more than 0.03% to less than 0.023%.
When the zinc-gadolinium-iron alloy ingot is added for the first time, 50 alloy ingots B are added according to the zinc liquid with preliminary iron removal per 100 tons 6 Is added with alloy ingot B in proportion of 6 The method comprises the steps of carrying out a first treatment on the surface of the After normal production, 1 block (10 kg/block) of alloy ingot B is added per 1 ton of galvanized steel 6 Added every 8 hours. Alloy ingot B 6 In the same manner as in example 1, all of the alloy ingots B 6 After the addition, standing and fishing out the scum on the surface of the zinc liquid to obtain low-iron zinc liquid D 6 。
To low iron zinc liquid D 6 Adding zinc-aluminum-vanadium alloy ingot C 6 Zinc-aluminium-vanadium alloy ingot C 6 The primary addition amount of (C) is low-iron zinc liquid D 6 1.0% of the mass, and 1 (10 kg/block) of alloy ingot C is added per 8 tons of galvanized steel according to the weight of the galvanized steel after normal production 6 Added every 8 hours. Alloy ingot C 6 In the same manner as in example 1, all of the alloy ingots C 6 After the addition, standing and fishing out the dross on the surface of the zinc liquid to obtain alloy zinc liquid E 6 E during hot galvanizing 6 The temperature of (2) was 443 ℃.
5. Hot galvanizing: after the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 82 DEG C 6 Soaking for 45s, lifting to air, and naturally drying for 5min. Then the steel is hung into alloy zinc liquid E with the temperature of 443 DEG C 6 Zinc plating is carried out until no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the zinc liquid surface float, the galvanized steel is lifted out, and the zinc plating time is 152 seconds, thus obtaining the ultrathin galvanized layer steel F 6 。
Example 7
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 78kg of zinc chloride, 22kg of ammonium chloride, 12kg of potassium chloride, 10kg of nickel fluoride, 8kg of stannous chloride, 1.2kg of copper chloride, 0.08kg of Gemini-12-2-12, 0.7kg of hydroxylamine hydrochloride, 1.4kg of glycine and 0.3k of perfluorobutyl trimethyl quaternary ammonium iodideg, the rest is hydrochloric acid and water, the use amount of the hydrochloric acid is used for adjusting the pH value of the plating assistant agent to 1.6. 1m 3 The preparation method of the plating assistant agent comprises the following steps: adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 15 minutes to completely dissolve the components, adding 31% industrial hydrochloric acid with calculated weight into the solution according to the pH value requirement of the final plating assistant, reacting for 30 minutes under the stirring state, and continuously adding water to ensure that the total amount of the solution is 1m 3 The pH value is 1.6, and the plating assistant agent A is obtained 7 . In the actual production process, the dosage of each component is multiplied according to the actual dosage of the plating assistant agent. In this example, plating assistant A 7 Heated to 72℃for use.
2. Preparation of zinc-gadolinium-iron alloy: melting 500kg of No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 550 ℃, adding 7.6kg of gadolinium-iron alloy containing 86.6wt% (the effective gadolinium content is 82.4%) of gadolinium into the zinc liquid, continuously heating to 800 ℃, and preserving heat for 55min to obtain zinc-gadolinium-iron alloy liquid. Casting the alloy liquid into zinc-gadolinium-iron alloy ingot B of 10 kg/block 7 Wherein the effective gadolinium content is 1.23wt%.
3. Preparation of zinc-aluminum-vanadium alloy: melting 475kg No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 500 ℃, and then adding 28kg of aluminum-vanadium alloy containing 10wt% of vanadium into the zinc liquid in the following manner: the aluminum-vanadium alloy is pressed to a position 50cm below the liquid level of zinc by a graphite bell jar, and is fixed. Then the temperature of the zinc liquid is increased to 735 ℃, and the heat preservation is carried out for 55min, thus obtaining the zinc-aluminum-vanadium alloy liquid. Casting the alloy liquid into a zinc-aluminum-vanadium alloy ingot C with the weight of 10 kg/block 7 Wherein the aluminum content is 5.01wt% and the vanadium content is 0.56wt%;
4. Preparing alloy zinc liquid: the conventional zinc bath in example 1 was raised from the normal production temperature to 458 deg.c, kept for 0.5 hours, then naturally cooled to 435 deg.c, and kept at rest for 1.8 hours. Part of iron in the zinc liquid is FeZn 13 The zinc slag is formed by combining forms and is deposited at the bottom of a zinc pot, the zinc slag is fished out by a special tool, the primary iron-removing zinc liquid is obtained, and the temperature is raised to 443 ℃ for standby. The Fe content in the zinc liquid is reduced from more than 0.03% to less than 0.023%.
When the zinc-gadolinium-iron alloy ingot is added for the first time, 50 alloy ingots B are added according to the zinc liquid with preliminary iron removal per 100 tons 6 Is added with alloy ingot B in proportion of 7 The method comprises the steps of carrying out a first treatment on the surface of the After normal production, 1 block (10 kg/block) of alloy ingot B is added per 1 ton of galvanized steel 7 Added every 8 hours. Alloy ingot B 7 In the same manner as in example 1, all of the alloy ingots B 7 After the addition, standing and fishing out the scum on the surface of the zinc liquid to obtain low-iron zinc liquid D 7 。
To low iron zinc liquid D 7 Adding zinc-aluminum-vanadium alloy ingot C 7 Zinc-aluminium-vanadium alloy ingot C 7 The primary addition amount of (C) is low-iron zinc liquid D 7 1.0% of the mass, and 1 (10 kg/block) of alloy ingot C is added per 10 tons of galvanized steel to be produced according to the weight of the galvanized steel after normal production 7 Added every 8 hours. Alloy ingot C 7 In the same manner as in example 1, all of the alloy ingots C 7 After the addition, standing and fishing out the dross on the surface of the zinc liquid to obtain alloy zinc liquid E 7 E during hot galvanizing 7 The temperature of (2) was 440 ℃.
5. Hot galvanizing: after the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 72 DEG C 7 Soaking for 55s, lifting to air, and naturally drying for 5min. Then the steel is hung into alloy zinc liquid E with the temperature of 440 DEG C 7 Zinc plating is carried out until no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the zinc liquid surface float, the galvanized steel is lifted out, and the zinc plating time is 141s, thus obtaining the ultrathin galvanized layer steel F 7 。
Example 8
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 72Kg of zinc chloride, 24Kg of ammonium chloride, 17Kg of potassium chloride, 8Kg of nickel fluoride, 13Kg of stannous chloride, 0.7Kg of copper chloride, 0.11Kg of Gemini-12-2-12, 1.3Kg of hydroxylamine hydrochloride, 1.8Kg of glycine, 0.5Kg of perfluorobutyl trimethyl quaternary ammonium iodine, the balance of hydrochloric acid and water, and the dosage of the hydrochloric acid is used for adjusting the pH value of the plating assistant to 1.1. 1m 3 The preparation method of the plating assistant agent comprises the following steps: adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 15 minutes to completely dissolve the components, and then according to the most important conditionAdding 31% industrial hydrochloric acid with calculated weight into the solution according to the pH value requirement of the final plating agent, reacting for 60 minutes under stirring, and continuously adding water to make the total amount of the solution be 1m 3 The pH value is 1.1, and the plating assistant agent A is obtained 8 . In the actual production process, the dosage of each component is multiplied according to the actual dosage of the plating assistant agent. In this example, plating assistant A 8 Heated to 68 ℃ for use.
2. Preparation of zinc-gadolinium-iron alloy: melting 500kg of No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 530 ℃, then adding 6.6kg of gadolinium-iron alloy containing 86.6wt% (wherein the content of effective gadolinium element is 82.4 wt%) of gadolinium into the zinc liquid, continuously heating to 750 ℃, and preserving heat for 40min to obtain zinc-gadolinium-iron alloy liquid. Casting the alloy liquid into zinc-gadolinium-iron alloy ingot B of 10 kg/block 8 Wherein the effective gadolinium content is 1.07wt%.
3. Preparation of zinc-aluminum-vanadium alloy: melting 475kg No. 0 zinc ingot in an intermediate frequency induction furnace, heating to 470 ℃, and then adding 29kg of aluminum-vanadium alloy containing 10wt% of vanadium into the zinc liquid in the following manner: the aluminum-vanadium alloy is pressed to a position 50cm below the liquid level of zinc by a graphite bell jar, and is fixed. Then the temperature of the zinc liquid is increased to 725 ℃, and the temperature is kept for 42min, thus obtaining the zinc-aluminum-vanadium alloy liquid. Casting the alloy liquid into a zinc-aluminum-vanadium alloy ingot C with the weight of 10 kg/block 8 Wherein the aluminum content is 5.18wt% and the vanadium content is 0.58wt%;
4. Preparing alloy zinc liquid: the conventional zinc bath in example 1 was raised from the normal production temperature to 450 ℃, kept for 0.8 hours, then naturally cooled to 430 ℃, and kept at rest for 1.6 hours. Part of iron in the zinc liquid is FeZn 13 The zinc slag is formed by combining forms and is deposited at the bottom of a zinc pot, the zinc slag is fished out by a special tool, the zinc liquid with preliminary iron removal is obtained, and the temperature is raised to 445 ℃ for standby. The Fe content in the zinc liquid is reduced from more than 0.03% to less than 0.023%.
When the zinc-gadolinium-iron alloy ingot is added for the first time, 50 alloy ingots B are added according to the zinc liquid with preliminary iron removal per 100 tons 8 Is added with alloy ingot B in proportion of 8 The method comprises the steps of carrying out a first treatment on the surface of the After normal production, 1 block (10 kg/block) of alloy ingot B is added per 1 ton of galvanized steel 8 Added every 8 hours. AlloyIngot B 8 In the same manner as in example 1, all of the alloy ingots B 8 After the addition, standing and fishing out the scum on the surface of the zinc liquid to obtain low-iron zinc liquid D 8 。
To low iron zinc liquid D 8 Adding zinc-aluminum-vanadium alloy ingot C 8 Zinc-aluminium-vanadium alloy ingot C 8 The primary addition amount of (C) is low-iron zinc liquid D 8 1.0% of the mass, and 1 (10 kg/block) of alloy ingot C is added per 11 tons of galvanized steel according to the weight of the galvanized steel after normal production 8 Added every 8 hours. Alloy ingot C 8 In the same manner as in example 1, all of the alloy ingots C 8 After the addition, standing and fishing out the dross on the surface of the zinc liquid to obtain alloy zinc liquid E 8 E during hot galvanizing 8 The temperature of (2) was 444 ℃.
5. Hot galvanizing: after the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 68 DEG C 8 Soaking for 42s, lifting to air, and naturally drying for 5min. Then the steel is hung into alloy zinc liquid E with the temperature of 444 DEG C 8 Zinc plating is carried out until no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the zinc liquid surface float, the galvanized steel is lifted out, and the zinc plating time is 158s, thus obtaining the ultrathin galvanized layer steel F 8 。
Comparative example 1
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 130kg of zinc chloride, 180kg of ammonium chloride and the balance of water; 1m 3 The preparation method of the plating assistant agent comprises the following steps: adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 15 minutes to completely dissolve the components, adding 31% industrial hydrochloric acid with calculated weight into the solution according to the pH value requirement of the final plating assistant, reacting for 60 minutes under the stirring state, and continuously adding water to ensure that the total amount of the solution is 1m 3 The pH value is 4.0, and the plating assistant agent A is obtained 9 . In this comparative example, plating assistant A 9 Heated to 68 ℃ for use.
2. Preparing a zinc plating solution: adding zinc-nickel alloy N with nickel content of 1wt% into conventional zinc plating zinc liquid 9 The primary addition amount is 3% of the mass of the zinc liquid, and after normal production, the galvanized steel is heavyCalculating the quantity, adding 15 (10 kg/block) alloy ingots N for each 100 tons of galvanized steel to be produced 9 Added every 8 hours. The adding mode is as follows: 2-3 alloy ingots N are filled each time by using a hanging basket 9 Moving back and forth along the length direction of the zinc pot at a position 0.2-0.3 m below the zinc liquid level and at a moving speed of 0.2-0.3 m/s until the solution is complete, and then mixing all alloy ingots N according to the method 9 Adding into zinc liquid.
Continuously adding zinc-aluminum gold ingot D with aluminum content of 5wt% 9 The primary addition amount is 0.2 percent of the mass of the zinc liquid, and 7 (10 kg/block) alloy ingots D are added per 100 tons of galvanized steel after normal production according to the weight of the galvanized steel 9 Added every 8 hours. The adding mode is as follows: 1-2 alloy ingots D are filled each time by using hanging basket 9 Moving back and forth along the length direction of the zinc pot at a position 1.0-1.5 m below the zinc liquid level and at a moving speed of 0.2-0.3 m/s until the solution is complete, and then putting all alloy ingots D according to the method 9 Adding into zinc liquid. Standing, and fishing out dross on the surface of the zinc liquid to obtain conventional zinc liquid E 9 Wherein the mass fraction of Ni is 0.03%, the mass fraction of Al is 0.009%, and E is 9 The temperature is raised to 440 ℃ for standby.
After the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 68 DEG C 9 Soaking for 60s, lifting to air, and naturally drying for 4min. Then, the steel is suspended into a conventional zinc liquid E with the temperature of 440 DEG C 9 Zinc plating is carried out until no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the zinc liquid surface float, the galvanized steel is lifted out, and the galvanization time is 185s, thus obtaining the conventional galvanized steel F 9 。
Comparative example 2
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 150kg of zinc chloride, 190kg of ammonium chloride and the balance of water; 1m 3 The preparation method of the plating assistant agent comprises the following steps: firstly adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 30 minutes to completely dissolve the components, then adding 31% industrial hydrochloric acid with calculated weight into the solution according to the requirement of the pH value of the final plating assistant, reacting for 45 minutes in a stirring state,continuously adding water to make the total amount of the solution be 1m 3 The pH value is 4.0, and the plating assistant agent A is obtained 10 . In this comparative example, plating assistant A 10 Heated to 72℃for use.
2. Preparing a zinc plating solution: adding zinc-nickel alloy N with nickel content of 1wt% into normal zinc plating zinc liquid 10 The primary addition amount is 3 percent of the mass of the zinc liquid, and 15 (10 kg/block) alloy ingots N are added per 100 tons of galvanized steel after normal production according to the weight of the galvanized steel 10 Added every 8 hours. The adding mode is as follows: 2-3 alloy ingots N are filled each time by using a hanging basket 10 Moving back and forth along the length direction of the zinc pot at a position 0.2-0.3 m below the zinc liquid level and at a moving speed of 0.2-0.3 m/s until the solution is complete, and then mixing all alloy ingots N according to the method 10 Adding into zinc liquid.
Continuously adding zinc-aluminum gold ingot D with aluminum content of 5wt% 10 The primary addition amount is 0.3 percent of the mass of the zinc liquid, and after normal production, 11 (10 kg/block) alloy ingots D are added per 100 tons of galvanized steel according to the weight of the galvanized steel 10 Added every 8 hours. The adding mode is as follows: 1-2 alloy ingots D are filled each time by using hanging basket 10 Moving back and forth along the length direction of the zinc pot at a position 1.0-1.5 m below the zinc liquid level and at a moving speed of 0.2-0.3 m/s until the solution is complete, and then putting all alloy ingots D according to the method 10 Adding into zinc liquid. Standing, and fishing out dross on the surface of the zinc liquid to obtain conventional zinc liquid E 10 Wherein the mass fraction of Ni is 0.03%, the mass fraction of Al is 0.014%, E 10 The temperature is raised to 443 ℃ for standby.
After the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 72 DEG C 10 Soaking for 80s, lifting to air, and naturally drying for 4min. Then, the steel is suspended into a conventional zinc bath E with the temperature of 443 DEG C 10 Zinc plating is carried out until no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the zinc liquid surface float, the galvanized steel is lifted out, and the galvanization time is 191s, thus obtaining the conventional galvanized steel F 10 。
Comparative example 3
1. Preparing a plating assistant agent: every 1m 3 The plating assistant comprises the following components: 160kg of zinc chloride, 220kg of ammonium chloride and the balance of water; 1m 3 The preparation method of the plating assistant agent comprises the following steps: adding 650kg of water into a stirring kettle, starting a stirrer, sequentially adding other components, stirring for 25 minutes to completely dissolve the components, adding 31% industrial hydrochloric acid with calculated weight into the solution according to the pH value requirement of the final plating assistant, reacting for 50 minutes under the stirring state, and continuously adding water to ensure that the total amount of the solution is 1m 3 The pH value is 4.2, and the plating assistant agent A is obtained 11 . In this comparative example, plating assistant A 11 Heated to 75 ℃ for use.
2. Preparing hot alloy zinc liquid: adding zinc-nickel alloy N with nickel content of 1wt% into normal zinc plating zinc liquid 11 The primary addition amount is 1 percent of the mass of the zinc liquid, and 1 (10 kg/block) alloy ingot N is added per 10 tons of galvanized steel after normal production according to the weight of the galvanized steel 11 Added every 8 hours. The adding mode is as follows: 2-3 alloy ingots N are filled each time by using a hanging basket 11 Moving back and forth along the length direction of the zinc pot at a position 0.2-0.3 m below the zinc liquid level and at a moving speed of 0.2-0.3 m/s until the solution is complete, and then mixing all alloy ingots N according to the method 11 Adding into zinc liquid.
Continuously adding zinc-aluminum alloy ingot D with aluminum content of 5wt% 11 The primary addition amount is 0.85 percent of the mass of the zinc liquid, and after normal production, 33 (10 kg/block) alloy ingots D are added per 100 tons of galvanized steel according to the weight of the galvanized steel 11 Added every 8 hours. The adding mode is as follows: 2-3 alloy ingots D are filled in each time by using a hanging basket 11 Moving back and forth along the length direction of the zinc pot at a position 1.0-1.5 m below the zinc liquid level and at a moving speed of 0.2-0.3 m/s until the solution is complete, and then putting all alloy ingots D according to the method 11 Adding into zinc liquid. Standing, and taking out dross on the surface of the zinc liquid to obtain zinc liquid E 11 Wherein, the mass fraction of Ni is 0.031, the mass fraction of Al is 0.042%, E 11 The temperature is raised to 443 ℃ for standby.
After the steel is washed by acid and water, suspending the steel into a plating assistant agent A with the temperature of 75 DEG C 11 Soaking for 60s, lifting to the air,naturally drying for 5min. Then, the steel is suspended in a zinc bath E at 443 DEG C 11 Zinc plating is carried out until no obvious bubbles and scum in the zinc liquid are emitted, a gray knife is used for pulling off the zinc liquid surface float, the galvanized steel is lifted out, and the galvanization time is 198s, thus obtaining the conventional galvanized steel F 11 。
The alloy zinc solutions of examples 1 to 8 and the zinc plating solutions of comparative examples 1 to 3 are shown in Table 1, and Table 1 is a comparative table of the alloy element contents and the galvanization effects of the zinc plating solutions of examples 1 to 8 and comparative examples 1 to 3. The galvanization effects of examples 1 to 8 and comparative examples 1 to 3 are shown in Table 2, and Table 2 is a comparative table of galvanization effects of examples 1 to 8 and comparative examples 1 to 3.
TABLE 1 alloy zinc solutions of examples 1 to 8 and alloy element content tables in zinc plating solutions of comparative examples 1 to 3
Table 2 comparison tables of galvanization effects of examples 1 to 8 and comparative examples 1 to 3
| Project | Plating leakage condition | Surface finish | Zinc plating layer thickness/. Mu.m |
| Example 1 | Without any means for | Brightness of | 44 |
| Example 2 | Without any means for | Brightness of | 41 |
| Example 3 | Without any means for | Brightness of | 35 |
| Example 4 | Without any means for | Brightness of | 46 |
| Example 5 | Without any means for | Brightness of | 48 |
| Example 6 | Without any means for | Brightness of | 37 |
| Example 7 | Without any means for | Brightness of | 45 |
| Example 8 | Without any means for | Brightness of | 46 |
| Comparative example 1 | Without any means for | Brightness of | 95 |
| Comparative example 2 | Has more plating leakage points | Slightly worse | 76 |
| Comparative example 3 | Large area drain plating | Very poor | 65 |
As can be seen from tables 1 and 2, the invention shortens the decomposition time of the plating assistant agent and correspondingly reduces the galvanization time by adjusting the components of the plating assistant agent, thereby reducing the reaction time of iron and zinc and the thickness of the galvanization layer; the plating assistant agent can also overcome the problem of plating leakage caused by higher aluminum content in the zinc liquid, so that the thickness of a zinc plating layer can be reduced by increasing the aluminum content in the zinc liquid in batch hot galvanizing production, and the plating leakage phenomenon is avoided; by adding Al to the zinc liquid 3 V-type vanadium is added, so that the 'san-delin effect' of overgrowth of a galvanized layer during galvanization of high-silicon steel can be controlled, and when the aluminum content in zinc liquid at the surface of the steel is excessively consumed during galvanization, the aluminum element is provided, and Fe is increased 2 Al 5 The zinc liquid dissolution resistance of the inhibition layer can better play the role of controlling the iron-zinc reaction by the aluminum element; by adding gadolinium element into the zinc liquid, the iron content in the zinc liquid can be reduced, so that the fluidity of the zinc liquid is improved, and when a galvanized workpiece is lifted out of the zinc liquid, the zinc liquid on the workpiece can flow back into a zinc pot more, thereby having a certain effect of reducing the thickness of a galvanized layer. Through the comprehensive application of the method, the thickness of the galvanized layer is 35-48 mu m, which is far smaller than the minimum thickness of 65 mu m of the comparative example. It can be seen that the present invention adoptsThe reduction effect of the scheme on the thickness of the galvanized layer is obviously better than that of the conventional galvanization production (such as comparative example 1) which adopts the following steps: plating with zinc chloride-ammonium chloride plating assistant agent; the reaction speed of iron and zinc is inhibited by adopting lower aluminum element content (0.005% -0.010%); and the combined use of the 'san dielin effect' which causes the ultra-thick galvanized layer due to the abnormal and rapid iron-zinc reaction when the nickel element is adopted to control the high silicon steel galvanization has the effect of reducing the thickness of the galvanized layer. In addition, the invention does not have the phenomenon of plating leakage caused by too high aluminum content (such as comparative example 2 and comparative example 3) when the conventional zinc chloride-ammonium chloride plating assistant agent is used for zinc plating like the conventional zinc plating production. The galvanized layer obtained by the invention has bright surface, no plating leakage phenomenon and good surface quality.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the batch hot dip galvanized steel ultrathin galvanized layer is characterized by comprising the following steps of:
sequentially carrying out acid washing, water washing, plating assistance and hot galvanizing on the steel to obtain hot galvanized steel;
the plating assistant agent for plating assistant comprises the following components: zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent, a plating assistant thickness control agent, hydrochloric acid and water; the total mass concentration of zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent and a plating-assisting film thickness control agent in the plating assisting agent is less than 170g/L, and the pH value of the plating assisting agent is 1.0-2.0;
the deoxidizer is hydroxylamine hydrochloride, the complexing agent is glycine, and the plating assistant film thickness control agent is perfluorobutyl trimethyl quaternary ammonium iodine; the plating assistant comprises 60-80 g/L of zinc chloride, 20-30 g/L of ammonium chloride, 10-20 g/L of potassium chloride, 5-10 g/L of nickel fluoride, 5-20 g/L of stannous chloride, 0.5-1.5 g/L of copper chloride, 0.05-0.15 g/L of Gemini-12, 0.5-2.0 g/L of hydroxylamine hydrochloride, 1.0-2.0 g/L of glycine and 0.2-1.0 g/L of perfluorobutyl trimethyl quaternary ammonium iodide;
The preparation method of the alloy liquid for hot galvanizing comprises the following steps: carrying out temperature difference method iron removal on the conventional zinc liquid to obtain primary iron-removed zinc liquid; adding gadolinium element into the primarily iron-removed zinc liquid to further remove iron, so as to obtain low-iron zinc liquid; adding zinc-aluminum-vanadium alloy into the low-iron zinc liquid to obtain alloy zinc liquid; the conventional zinc liquid consists of the following components in percentage by mass: zinc is more than or equal to 99.95%, iron is 0.030% -0.035%, aluminum is 0.006% -0.008%, and impurities are less than 0.005%;
the alloy zinc liquid for hot galvanizing comprises the following components in percentage by mass: iron is less than or equal to 0.013%, gadolinium is 0.0010% -0.0015%, vanadium is 0.004% -0.008%, aluminum is 0.038% -0.050%, impurities are less than 0.005%, and the balance is zinc;
the thickness of the hot galvanizing zinc coating is 35-48 mu m.
2. The preparation method according to claim 1, wherein the method for removing iron by the temperature difference method comprises the following steps: and heating the conventional zinc liquid from 440-445 ℃ to 450-455 ℃, preserving heat for 0.5-1 h after the heating, naturally cooling to 430-435 ℃, and preserving heat for 1-2 h after the cooling is finished, so as to obtain the preliminary iron-removing zinc liquid.
3. The preparation method according to claim 1, wherein the gadolinium element is added in a manner of zinc-gadolinium-iron alloy, and the mass of the effective gadolinium element in the zinc-gadolinium-iron alloy is 0.0050% -0.0062% of the total mass of the preliminary iron-zinc removal liquid.
4. A method of producing according to claim 3, wherein the zinc-gadolinium-iron alloy is in the form of a zinc-gadolinium-iron alloy ingot, and the method of producing the zinc-gadolinium-iron alloy ingot comprises the steps of: melting a zinc ingot, adding gadolinium-iron alloy, heating to 750-800 ℃ and preserving heat for 30-60 min to obtain zinc-gadolinium-iron alloy liquid, and casting the zinc-gadolinium-iron alloy liquid to obtain the zinc-gadolinium-iron alloy ingot, wherein the effective gadolinium element content of the zinc-gadolinium-iron alloy ingot is 1.00-1.25wt%; the zinc ingot is a 0# zinc ingot, and the melting temperature of the zinc ingot is 500-550 ℃; the mass ratio of the zinc ingot to the gadolinium-iron alloy is 64.5-81.5:1; the total content of gadolinium element in the gadolinium-iron alloy is 86.6wt%, and the content of effective gadolinium element in the gadolinium-iron alloy is 82.4wt%.
5. The method of claim 1, wherein the zinc-aluminum-vanadium alloy is in the form of a zinc-aluminum-vanadium alloy ingot, and wherein the method of producing the zinc-aluminum-vanadium alloy ingot comprises the steps of: melting a zinc ingot, adding an aluminum-vanadium alloy, heating to 700-750 ℃ and preserving heat for 30-60 min to obtain zinc-aluminum-vanadium alloy liquid, and casting the zinc-aluminum-vanadium alloy liquid to obtain the zinc-aluminum-vanadium alloy ingot, wherein the aluminum content of the zinc-aluminum-vanadium alloy ingot is 4.5-5.4wt% and the vanadium content of the zinc-aluminum-vanadium alloy ingot is 0.50-0.60wt%; the zinc ingot is a 0# zinc ingot, and the melting temperature of the zinc ingot is 450-500 ℃; the mass ratio of the zinc ingot to the aluminum-vanadium alloy is 15.8-19:1; the content of vanadium element in the aluminum-vanadium alloy is 10wt%.
6. The method according to claim 1, wherein the temperature of the hot dip galvanizing is 440-445 ℃, and the time of the hot dip galvanizing is 130-160 s.
7. The method of claim 1, wherein the method of preparing the plating assistant comprises the steps of:
and mixing the zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent, a plating assistant film thickness control agent, hydrochloric acid and water to obtain the plating assistant agent.
8. The method of preparing according to claim 7, wherein the mixing comprises the steps of:
firstly mixing part of water with the zinc chloride, ammonium chloride, potassium chloride, nickel fluoride, stannous chloride, copper chloride, gemini-12-2-12, an deoxidizer, a complexing agent and a plating assistant film thickness control agent to obtain a first mixed solution, wherein the mass of the part of water accounts for 60% -80% of the total mass of the water;
performing second mixing on the first mixed solution and hydrochloric acid to obtain plating assistant agent stock solution;
and thirdly mixing the plating assistant agent stock solution and the rest of water to obtain the plating assistant solution.
9. The method for preparing the metal alloy according to claim 1, wherein the plating assisting temperature is 65-85 ℃ and the plating assisting time is 30-60 s; and the plating assistant is further subjected to natural drying, wherein the natural drying temperature is room temperature, and the natural drying time is 3-5 min.
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