CN115404426B - 一种高强度热镀锌钢板及其制备方法 - Google Patents
一种高强度热镀锌钢板及其制备方法 Download PDFInfo
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- CN115404426B CN115404426B CN202210865794.2A CN202210865794A CN115404426B CN 115404426 B CN115404426 B CN 115404426B CN 202210865794 A CN202210865794 A CN 202210865794A CN 115404426 B CN115404426 B CN 115404426B
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- Prior art keywords
- steel sheet
- galvanized steel
- shellac
- steel plate
- dip galvanized
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 81
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims abstract description 130
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 109
- 239000010959 steel Substances 0.000 claims abstract description 109
- 229920001800 Shellac Polymers 0.000 claims abstract description 99
- 239000004208 shellac Substances 0.000 claims abstract description 99
- 229940113147 shellac Drugs 0.000 claims abstract description 99
- 235000013874 shellac Nutrition 0.000 claims abstract description 99
- 238000007747 plating Methods 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 59
- 238000002161 passivation Methods 0.000 claims abstract description 58
- 230000008569 process Effects 0.000 claims abstract description 54
- 238000005406 washing Methods 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 238000005246 galvanizing Methods 0.000 claims abstract description 23
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 22
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 21
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 21
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 19
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 11
- 238000009461 vacuum packaging Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- 238000001816 cooling Methods 0.000 claims description 62
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- 239000012298 atmosphere Substances 0.000 claims description 32
- 238000005098 hot rolling Methods 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 230000001681 protective effect Effects 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 15
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 238000004381 surface treatment Methods 0.000 claims description 12
- 230000000630 rising effect Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000010425 asbestos Substances 0.000 claims description 8
- 238000005097 cold rolling Methods 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 8
- 229910052895 riebeckite Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 7
- 238000004090 dissolution Methods 0.000 claims 2
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010703 silicon Substances 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 28
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 25
- 239000003795 chemical substances by application Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 235000019270 ammonium chloride Nutrition 0.000 description 14
- 239000011592 zinc chloride Substances 0.000 description 14
- 235000005074 zinc chloride Nutrition 0.000 description 14
- 238000002791 soaking Methods 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- -1 iron-aluminum compound Chemical class 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
-
- 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
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
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Abstract
本发明公开了一种高强度热镀锌钢板及其制备方法,包括以下工艺:铬粉、氧化铬混合,与钢板真空封装,热处理,碱洗;助镀,热镀锌,形成镀层;取虫胶树脂、单体,升温反应;加入水合肼反应;加入巯基封端聚乙二醇反应,得到改性虫胶;将改性虫胶、偏钒酸铵、硅酸钠、无水乙醇混合,得到钝化液;将镀锌钢板浸没其中,形成钝化层,得到高强度热镀锌钢板。本发明通过对钢板中的化学成分含量进行控制,提高钢板的基础屈服强度和抗拉强度,并利用预氧化及碱洗工艺,消除硅元素对热镀锌工艺带来的负面影响;在热镀锌的镀液中添加了铝、铅元素,提高了镀层的强硬度;而钝化工艺的设置,使得所制高强度热镀锌钢板具有更为优异的耐腐蚀性能。
Description
技术领域
本发明涉及热镀钢板技术领域,具体为一种高强度热镀锌钢板及其制备方法。
背景技术
钢铁材料作为不可或缺的重要资源,为了延长钢铁材料的使用寿命,目前会在钢铁材料表面镀一层防护膜。因金属锌具有抗腐蚀能力优异、价格低廉的特点,广泛作为涂层材料。常规镀锌工艺有电镀锌、热镀锌,而相较于电镀锌,热镀锌工艺简单、成本低廉并且表面镀锌质量与电镀锌产品相差不多,目前绝大多数企业都采用热镀锌工艺加工生产镀锌钢板。近年来,热镀锌高强钢材得到了广泛的应用,为了提高热镀锌钢板的综合力学性能,在涉及钢基成分时,可以在钢基体中加入一定量的合金元素,然而合金元素在提高热镀锌钢板强度的同时,也会对钢基与锌液之间的浸润性产生一定的影响,从而影响镀锌的质量。因此,我们提出一种高强度热镀锌钢板及其制备方法。
发明内容
本发明的目的在于提供一种高强度热镀锌钢板及其制备方法,以解决上述背景技术中提出的问题。
为了解决上述技术问题,本发明提供如下技术方案:一种高强度热镀锌钢板的制备方法,包括以下工艺:
(1)镀前处理:
取铬粉、氧化铬混合,与钢板共同置于密封装置内,真空封装,750~850℃热处理270~350min,得到预氧化钢板;碱洗,水洗;得到预处理钢板;
(2)镀锌处理:助镀,热镀锌,形成镀层,得到镀锌钢板;
(3)表面处理:取虫胶树脂、单体,升温反应,得到虫胶A;加入水合肼反应,得到虫胶B;加入巯基封端聚乙二醇反应,得到改性虫胶;
将改性虫胶,加入偏钒酸铵、硅酸钠、无水乙醇混合,得到钝化液;
将镀锌钢板浸没于钝化液中,取出,干燥,形成钝化层,得到高强度热镀锌钢板。
进一步的,所述单体为乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸的混合物。
进一步的,所述(1)工艺前包括以下工艺:
取钢板热轧,热轧工艺为:在氮气保护气氛中,初始热轧温度为1190~1210℃,保温时间36~60min,终止热轧温度为920~948℃,保温时间25~30min;水冷至636~680℃,石棉缓冷至室温;
酸洗,酸洗工艺为:15%盐酸酸洗10~20min,去除氧化皮、铁锈、杂质等;冷轧至1.2mm;
退火,退火工艺为:以氮气、氢气为保护气氛,以5℃/s的升温速率升温至700℃,以2℃/s的升温速率升温至800℃,800℃等温70s;以2℃/s的降温速率降温至700℃,以30℃/s的降温速率降温至460℃,460℃等温3s,以20℃/s的降温速率冷却至室温,得到钢板;保护气氛中氮气的体积含量为5%。
进一步的,所述钢板包括以下质量成分:C:0.06~0.10%,Si:0.10~0.18%,Mn:1.22~1.46%,P:0.003~0.005%,S:<0.003%,余量为Fe。
在上述技术方案中,对钢板中的化学成分含量进行控制;其中,硅作为铁素体形成元素,能够扩散铁素体区,抑制渗碳体析出,提高钢板中有效碳浓度,使得钢板能够在退火工艺中形成硬相马氏体,利于所制钢板抗拉强度的提高;而锰元素能够提高钢板的抗拉强度,并能够与退火工艺共同促进晶粒尺寸的细化,确保钢板的屈服强度。对碳、磷元素的含量进行控制,使得钢板具有高磷低碳特征,在退火工艺后,磷元素与碳元素共同对位错造成钉扎作用,降低钢板中可移动位错密度,能够提高钢板的屈服强度。
进一步的,所述(1)中铬粉、氧化铬的质量比为(0.5~1.2):1;平均粒径为68~80μm。
进一步的,所述(1)中的碱洗工艺为:将预氧化钢板置于温度为70~80℃、15%氢氧化钠水溶液中,浸泡15~18min。
在上述技术方案中,在高温下,铬元素的氧势高于硅、锰元素,但低于铁、碳、磷元素,使得铬粉、氧化铬能够对钢板表面的硅、锰元素进行预氧化;利用后续的碱洗去除了预氧化钢板表面的二氧化硅,能够防止钢板中硅的反应性,减少镀锌扩散,利于镀锌钢板附着力及其强度的提高;而表面一氧化锰的存在能够提高镀液在钢板表面的润湿性,利于热镀锌性能的改善。
进一步的,所述(2)中的助镀工艺为:将预处理钢板置于温度为70~80℃的助镀剂中,浸泡3~4min,取出,自然干燥10~15min;
助镀剂为氯化铵、氯化锌混合水溶液,浓度为200~300g/L;助镀剂中氯化铵、氯化锌的质量比为(1.1~1.3):1。
进一步的,所述(2)中的热镀锌工艺为:取助镀后的钢板,以氮气、氢气为保护气氛,置于460~480℃镀液中浸镀3~5s,以10℃/s的降温速率冷却至室温;保护气氛中氮气的体积含量为5%。
进一步的,镀液包括以下重量成分:0.18~0.20%铝、0.08~0.12%铅,余量为锌。
在上述技术方案中,选择在热镀锌的镀液中加入少量金属铝和铅元素;其中,元素铝能够抑制钢板中铁元素与镀液中锌元素间的化学反应,在热镀锌工艺中首先与铁反应形成具有良好严密性的铁铝化合物薄膜,作为中间介质,增强镀层与钢板间的附着力,抑制锌、铁元素的扩散,提高所制镀锌钢板的抗冲击强度;元素铅能增加镀液与钢带基体间合金相的厚度和强度、硬度,有助于提高所制镀锌钢板的屈服强度,实现镀锌钢板的高强度。
进一步的,所述(3)包括以下工艺:
取虫胶树脂、单体混合,加入N,N-二甲基甲酰胺、N,N’-亚甲基双丙烯酰胺、过硫酸铵,搅拌,升温至60~70℃,反应7~10h;加入去离子水,超声洗涤,加入石油醚,超声洗涤,45~50℃真空干燥,得到虫胶A;
取无水乙醇、虫胶A混合,在氮气气氛保护下,加入水合肼,室温反应6~8h,得到虫胶B;
取虫胶B、无水乙醇混合,加入巯基封端聚乙二醇、AIBN,在氮气气氛保护下,60~65℃反应36h,得到改性虫胶;
取改性虫胶、无水乙醇混合,加入偏钒酸铵、硅酸钠,得到钝化液;
将镀锌钢板置于50℃温度的钝化液中,浸没50s;取出,40℃干燥,形成钝化层,得到高强度热镀锌钢板。
进一步的,虫胶树脂、单体的质量比为(1.8~6.0):1。
进一步的,虫胶树脂、N,N-二甲基甲酰胺的比例为2~3g/mL。
进一步的,N,N’-亚甲基双丙烯酰胺为虫胶树脂、单体总质量的0.04~0.06%。
进一步的,过硫酸铵为虫胶树脂、单体总质量的0.8~1.2%。
进一步的,单体为乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸的混合,质量比为1:(3.0~4.0):(2.7~3.0)。
进一步的,虫胶A、无水乙醇的比例为150~200g/L;虫胶A、水合肼的质量比为(15~20):1。
进一步的,虫胶B、巯基封端聚乙二醇、AIBN的质量比为(8~12):2:1;虫胶B在无水乙醇中的质量浓度为25~30%。
进一步的,钝化液中改性虫胶、偏钒酸铵、硅酸钠的浓度依次为1.5~2.0g/L、12~16g/L、20~25g/L。
在上述技术方案中,虫胶首先与乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸共聚,引入硅、氟元素和羧基基团、分子长链;然后利用所制虫胶A中的羰基与水合肼反应,引入氨基;最后所制虫胶B与巯基封端聚乙二醇进行巯基-烯的加成反应,能够提高所制钝化膜与镀锌钢板间的附着力和钝化膜的自润滑、耐腐蚀性能,并对所制钝化膜进行增强增韧。
与现有技术相比,本发明的有益效果如下:
1.本发明的高强度热镀锌钢板及其制备方法,通过对钢板中的化学成分含量进行控制;利用元素硅作为铁素体形成元素,扩散铁素体区,促进硬相马氏体的形成,利于所制钢板抗拉强度的提高;而锰元素在提高钢板的抗拉强度的同时,能够与退火工艺共同促进晶粒尺寸的细化,确保钢板的屈服强度;对碳、磷元素的含量进行控制,退火共同对位错造成钉扎作用,降低钢板中可移动位错密度,能够提高钢板的屈服强度。
2.本发明的高强度热镀锌钢板及其制备方法,通过在高温下,铬元素的氧势高于硅、锰元素,但低于铁、碳、磷元素的特征,使得铬粉、氧化铬对钢板表面的硅、锰元素进行预氧化;利用后续的碱洗去除了预氧化钢板表面的二氧化硅,能够防止钢板中硅的反应性,减少镀锌扩散,利于镀锌钢板附着力及其强度的提高;而表面一氧化锰的存在能够提高镀液在钢板表面的润湿性,利于热镀锌性能的改善。
3.本发明的高强度热镀锌钢板及其制备方法,通过在热镀锌的镀液中加入少量金属铝和铅元素;其中,元素铝能够抑制钢板中铁元素与镀液中锌元素间的化学反应,在热镀锌工艺中首先与铁反应形成具有良好严密性的铁铝化合物薄膜,作为中间介质,增强镀层与钢板间的附着力,抑制锌、铁元素的扩散,提高所制镀锌钢板的抗冲击强度;元素铅能增加镀液与钢带基体间合金相的厚度和强度、硬度,有助于提高所制镀锌钢板的屈服强度,实现镀锌钢板的高强度。
4.本发明的高强度热镀锌钢板及其制备方法,通过虫胶与乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸的共聚,引入硅、氟元素和羧基基团、分子长链;然后利用所制虫胶A中的羰基与水合肼反应,引入氨基,协同后续添加的巯基封端聚乙二醇,络合金属离子,抑制镀锌钢板的腐蚀;最后所制虫胶B与巯基封端聚乙二醇进行巯基-烯的加成反应,能够提高所制钝化膜与镀锌钢板间的附着力和钝化膜的自润滑、耐腐蚀性能,并对所制钝化膜进行增强增韧。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
(1)预处理:
取钢板热轧,热轧工艺为:在氮气保护气氛中,初始热轧温度为1190℃,保温时间36min,终止热轧温度为920℃,保温时间25min;水冷至636℃,石棉缓冷至室温;
酸洗,酸洗工艺为:15%盐酸酸洗10min;冷轧至1.2mm;
退火,退火工艺为:以氮气、氢气为保护气氛,以5℃/s的升温速率升温至700℃,以2℃/s的升温速率升温至800℃,800℃等温70s;以2℃/s的降温速率降温至700℃,以30℃/s的降温速率降温至460℃,460℃等温3s,以20℃/s的降温速率冷却至室温,得到钢板;保护气氛中氮气的体积含量为5%;
(2)镀前处理:
取铬粉、氧化铬混合,与钢板共同置于密封装置内,真空封装,750℃热处理270min,得到预氧化钢板;
碱洗,碱洗工艺为:将预氧化钢板置于温度为70℃、15%氢氧化钠水溶液中,浸泡15min;水洗;得到预处理钢板;铬粉、氧化铬的质量比为0.5:1;平均粒径为68μm;
(3)镀锌处理:
助镀,助镀工艺为:将预处理钢板置于温度为70℃的助镀剂中,浸泡3min,取出,自然干燥10min;助镀剂为200g/L氯化铵、氯化锌混合水溶液,助镀剂中氯化铵、氯化锌的质量比为1.1:1;
热镀锌,热镀锌工艺为:取助镀后的钢板,以氮气、氢气为保护气氛,置于460℃镀液中浸镀3s,以10℃/s的降温速率冷却至室温;保护气氛中氮气的体积含量为5%;镀液包括以下重量成分:0.18%铝、0.08%铅,余量为锌;形成镀层,得到镀锌钢板;
(4)表面处理:
取虫胶树脂、单体混合,加入N,N-二甲基甲酰胺、N,N’-亚甲基双丙烯酰胺、过硫酸铵,搅拌,升温至60℃,反应7h;加入去离子水,超声洗涤,加入石油醚,超声洗涤,45℃真空干燥,得到虫胶A;
虫胶树脂、单体的质量比为1.8:1;单体为乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸的混合物;虫胶树脂、N,N-二甲基甲酰胺的比例为2g/mL;N,N’-亚甲基双丙烯酰胺为虫胶树脂、单体总质量的0.04%;过硫酸铵为虫胶树脂、单体总质量的0.8%;单体为乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸的混合,质量比为1:3.0:2.7;
取无水乙醇、虫胶A混合,在氮气气氛保护下,加入水合肼,室温反应6h,得到虫胶B;虫胶A、无水乙醇的比例为150g/L;虫胶A、水合肼的质量比为15:1;
取虫胶B、无水乙醇混合,加入巯基封端聚乙二醇、AIBN,在氮气气氛保护下,60℃反应36h,得到改性虫胶;虫胶B、巯基封端聚乙二醇、AIBN的质量比为8:2:1;虫胶B在无水乙醇中的质量浓度为25%;
取改性虫胶、无水乙醇混合,加入偏钒酸铵、硅酸钠,得到钝化液;钝化液中改性虫胶、偏钒酸铵、硅酸钠的浓度依次为1.5g/L、12g/L、20g/L;
将镀锌钢板置于50℃温度的钝化液中,浸没50s;取出,40℃干燥,形成钝化层,得到高强度热镀锌钢板。
实施例2
(1)预处理:
取钢板热轧,热轧工艺为:在氮气保护气氛中,初始热轧温度为1200℃,保温时间48min,终止热轧温度为932℃,保温时间27min;水冷至648℃,石棉缓冷至室温;
酸洗,酸洗工艺为:15%盐酸酸洗15min;冷轧至1.2mm;
退火,退火工艺为:以氮气、氢气为保护气氛,以5℃/s的升温速率升温至700℃,以2℃/s的升温速率升温至800℃,800℃等温70s;以2℃/s的降温速率降温至700℃,以30℃/s的降温速率降温至460℃,460℃等温3s,以20℃/s的降温速率冷却至室温,得到钢板;保护气氛中氮气的体积含量为5%;
(2)镀前处理:
取铬粉、氧化铬混合,与钢板共同置于密封装置内,真空封装,80℃热处理300min,得到预氧化钢板;
碱洗,碱洗工艺为:将预氧化钢板置于温度为75℃、15%氢氧化钠水溶液中,浸泡16min;水洗;得到预处理钢板;铬粉、氧化铬的质量比为0.8:1;平均粒径为74μm;
(3)镀锌处理:
助镀,助镀工艺为:将预处理钢板置于温度为75℃的助镀剂中,浸泡3.5min,取出,自然干燥12min;助镀剂为250g/L氯化铵、氯化锌混合水溶液,助镀剂中氯化铵、氯化锌的质量比为1.2:1;
热镀锌,热镀锌工艺为:取助镀后的钢板,以氮气、氢气为保护气氛,置于470℃镀液中浸镀4s,以10℃/s的降温速率冷却至室温;保护气氛中氮气的体积含量为5%;镀液包括以下重量成分:0.19%铝、0.10%铅,余量为锌;形成镀层,得到镀锌钢板;
(4)表面处理:
取虫胶树脂、单体混合,加入N,N-二甲基甲酰胺、N,N’-亚甲基双丙烯酰胺、过硫酸铵,搅拌,升温至65℃,反应8h;加入去离子水,超声洗涤,加入石油醚,超声洗涤,48℃真空干燥,得到虫胶A;
虫胶树脂、单体的质量比为4.0:1;单体为乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸的混合物;虫胶树脂、N,N-二甲基甲酰胺的比例为2.5g/mL;N,N’-亚甲基双丙烯酰胺为虫胶树脂、单体总质量的0.05%;过硫酸铵为虫胶树脂、单体总质量的1.0%;单体为乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸的混合,质量比为1:3.5:2.8;
取无水乙醇、虫胶A混合,在氮气气氛保护下,加入水合肼,室温反应7h,得到虫胶B;虫胶A、无水乙醇的比例为180g/L;虫胶A、水合肼的质量比为18:1;
取虫胶B、无水乙醇混合,加入巯基封端聚乙二醇、AIBN,在氮气气氛保护下,62℃反应36h,得到改性虫胶;虫胶B、巯基封端聚乙二醇、AIBN的质量比为10:2:1;虫胶B在无水乙醇中的质量浓度为27%;
取改性虫胶、无水乙醇混合,加入偏钒酸铵、硅酸钠,得到钝化液;钝化液中改性虫胶、偏钒酸铵、硅酸钠的浓度依次为1.8g/L、14g/L、22g/L;
将镀锌钢板置于50℃温度的钝化液中,浸没50s;取出,40℃干燥,形成钝化层,得到高强度热镀锌钢板。
实施例3
(1)预处理:
取钢板热轧,热轧工艺为:在氮气保护气氛中,初始热轧温度为1210℃,保温时间60min,终止热轧温度为948℃,保温时间30min;水冷至680℃,石棉缓冷至室温;
酸洗,酸洗工艺为:15%盐酸酸洗20min;冷轧至1.2mm;
退火,退火工艺为:以氮气、氢气为保护气氛,以5℃/s的升温速率升温至700℃,以2℃/s的升温速率升温至800℃,800℃等温70s;以2℃/s的降温速率降温至700℃,以30℃/s的降温速率降温至460℃,460℃等温3s,以20℃/s的降温速率冷却至室温,得到钢板;保护气氛中氮气的体积含量为5%;
(2)镀前处理:
取铬粉、氧化铬混合,与钢板共同置于密封装置内,真空封装,850℃热处理350min,得到预氧化钢板;
碱洗,碱洗工艺为:将预氧化钢板置于温度为80℃、15%氢氧化钠水溶液中,浸泡18min;水洗;得到预处理钢板;铬粉、氧化铬的质量比为1.2:1;平均粒径为80μm;
(3)镀锌处理:
助镀,助镀工艺为:将预处理钢板置于温度为80℃的助镀剂中,浸泡4min,取出,自然干燥15min;助镀剂为300g/L氯化铵、氯化锌混合水溶液,助镀剂中氯化铵、氯化锌的质量比为1.3:1;
热镀锌,热镀锌工艺为:取助镀后的钢板,以氮气、氢气为保护气氛,置于480℃镀液中浸镀5s,以10℃/s的降温速率冷却至室温;保护气氛中氮气的体积含量为5%;镀液包括以下重量成分:0.20%铝、0.12%铅,余量为锌;形成镀层,得到镀锌钢板;
(4)表面处理:
取虫胶树脂、单体混合,加入N,N-二甲基甲酰胺、N,N’-亚甲基双丙烯酰胺、过硫酸铵,搅拌,升温至70℃,反应10h;加入去离子水,超声洗涤,加入石油醚,超声洗涤,50℃真空干燥,得到虫胶A;
虫胶树脂、单体的质量比为6.0:1;单体为乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸的混合物;虫胶树脂、N,N-二甲基甲酰胺的比例为3g/mL;N,N’-亚甲基双丙烯酰胺为虫胶树脂、单体总质量的0.06%;过硫酸铵为虫胶树脂、单体总质量的1.2%;单体为乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸的混合,质量比为1:4.0:3.0;
取无水乙醇、虫胶A混合,在氮气气氛保护下,加入水合肼,室温反应8h,得到虫胶B;虫胶A、无水乙醇的比例为200g/L;虫胶A、水合肼的质量比为20:1;
取虫胶B、无水乙醇混合,加入巯基封端聚乙二醇、AIBN,在氮气气氛保护下,65℃反应36h,得到改性虫胶;虫胶B、巯基封端聚乙二醇、AIBN的质量比为12:2:1;虫胶B在无水乙醇中的质量浓度为30%;
取改性虫胶、无水乙醇混合,加入偏钒酸铵、硅酸钠,得到钝化液;钝化液中改性虫胶、偏钒酸铵、硅酸钠的浓度依次为2.0g/L、16g/L、25g/L;
将镀锌钢板置于50℃温度的钝化液中,浸没50s;取出,40℃干燥,形成钝化层,得到高强度热镀锌钢板。
上述虫胶树脂:购买于绿春虫胶有限公司;
N,N-二甲基甲酰胺:购买于上海阿拉丁生化材料科技股份有限公司;
N,N’-亚甲基双丙烯酰胺:购买于济宁三石生物科技有限公司;
过硫酸铵:购买于武汉吉鑫益邦生物科技有限公司;
乙烯基三甲氧基硅烷:购买于上海阿拉丁生化材料科技股份有限公司;
甲基丙烯酸十二氟庚酯:购买于武汉市荣灿生物科技有限公司;
桐油酸:购买于安徽省瑞芬得油脂深加工有限公司;
巯基封端聚乙二醇:购买于上海麦克林生化科技有限公司。
对比例1
(1)预处理:
取钢板热轧,热轧工艺为:在氮气保护气氛中,初始热轧温度为1190℃,保温时间36min,终止热轧温度为920℃,保温时间25min;水冷至636℃,石棉缓冷至室温;
酸洗,酸洗工艺为:15%盐酸酸洗10min;冷轧至1.2mm;
(2)镀前处理:
取铬粉、氧化铬混合,与钢板共同置于密封装置内,真空封装,750℃热处理270min,得到预氧化钢板;
碱洗,碱洗工艺为:将预氧化钢板置于温度为70℃、15%氢氧化钠水溶液中,浸泡15min;水洗;得到预处理钢板;铬粉、氧化铬的质量比为0.5:1;平均粒径为68μm;
(3)镀锌处理:
助镀,助镀工艺为:将预处理钢板置于温度为70℃的助镀剂中,浸泡3min,取出,自然干燥10min;助镀剂为200g/L氯化铵、氯化锌混合水溶液,助镀剂中氯化铵、氯化锌的质量比为1.1:1;
热镀锌,热镀锌工艺为:取助镀后的钢板,以氮气、氢气为保护气氛,置于460℃镀液中浸镀3s,以10℃/s的降温速率冷却至室温;保护气氛中氮气的体积含量为5%;镀液包括以下重量成分:0.18%铝、0.08%铅,余量为锌;形成镀层,得到镀锌钢板。
对比例2
(1)预处理:
取钢板热轧,热轧工艺为:在氮气保护气氛中,初始热轧温度为1190℃,保温时间36min,终止热轧温度为920℃,保温时间25min;水冷至636℃,石棉缓冷至室温;
酸洗,酸洗工艺为:15%盐酸酸洗10min;冷轧至1.2mm;
(2)镀锌处理:
助镀,助镀工艺为:将预处理钢板置于温度为70℃的助镀剂中,浸泡3min,取出,自然干燥10min;助镀剂为200g/L氯化铵、氯化锌混合水溶液,助镀剂中氯化铵、氯化锌的质量比为1.1:1;
热镀锌,热镀锌工艺为:取助镀后的钢板,以氮气、氢气为保护气氛,置于460℃镀液中浸镀3s,以10℃/s的降温速率冷却至室温;保护气氛中氮气的体积含量为5%;镀液包括以下重量成分:0.18%铝、0.08%铅,余量为锌;形成镀层,得到镀锌钢板。
对比例3
(1)预处理:
取钢板热轧,热轧工艺为:在氮气保护气氛中,初始热轧温度为1190℃,保温时间36min,终止热轧温度为920℃,保温时间25min;水冷至636℃,石棉缓冷至室温;
酸洗,酸洗工艺为:15%盐酸酸洗10min;冷轧至1.2mm;
(2)镀锌处理:
助镀,助镀工艺为:将预处理钢板置于温度为70℃的助镀剂中,浸泡3min,取出,自然干燥10min;助镀剂为200g/L氯化铵、氯化锌混合水溶液,助镀剂中氯化铵、氯化锌的质量比为1.1:1;
热镀锌,热镀锌工艺为:取助镀后的钢板,以氮气、氢气为保护气氛,置于460℃镀液中浸镀3s,以10℃/s的降温速率冷却至室温;保护气氛中氮气的体积含量为5%;镀液包括以下重量成分:0.18%铝,余量为锌;形成镀层,得到镀锌钢板。
上述钢板尺寸为220mm×100mm×1.2mm;钢板包括以下质量成分:C:0.081%,Si:0.14%,Mn:1.37%,P:0.0048%,S:0.002%,余量为Fe。
对比例4
钢板包括以下质量成分:C:0.130%,Si:0.02%,Mn:1.37%,P:0.008%,S:0.001%,余量为Fe。
其他工艺与对比例3相同,得到镀锌钢板。
对比例5
(4)表面处理:
取虫胶树脂、单体混合,加入N,N-二甲基甲酰胺、N,N’-亚甲基双丙烯酰胺、过硫酸铵,搅拌,升温至60℃,反应7h;加入去离子水,超声洗涤,加入石油醚,超声洗涤,45℃真空干燥,得到虫胶A;
虫胶树脂、单体的质量比为1.8:1;单体为甲基丙烯酸十二氟庚酯、桐油酸的混合物;虫胶树脂、N,N-二甲基甲酰胺的比例为2g/mL;N,N’-亚甲基双丙烯酰胺为虫胶树脂、单体总质量的0.04%;过硫酸铵为虫胶树脂、单体总质量的0.8%;单体为甲基丙烯酸十二氟庚酯、桐油酸的混合,质量比为3.0:2.7;
取无水乙醇、虫胶A混合,在氮气气氛保护下,加入水合肼,室温反应6h,得到虫胶B;虫胶A、无水乙醇的比例为150g/L;虫胶A、水合肼的质量比为15:1;
取虫胶B、无水乙醇混合,加入巯基封端聚乙二醇、AIBN,在氮气气氛保护下,60℃反应36h,得到改性虫胶;虫胶B、巯基封端聚乙二醇、AIBN的质量比为8:2:1;虫胶B在无水乙醇中的质量浓度为25%;
取改性虫胶、无水乙醇混合,加入偏钒酸铵、硅酸钠,得到钝化液;钝化液中改性虫胶、偏钒酸铵、硅酸钠的浓度依次为1.5g/L、12g/L、20g/L;
将镀锌钢板置于50℃温度的钝化液中,浸没50s;取出,40℃干燥,形成钝化层,得到高强度热镀锌钢板。
对比例6
(4)表面处理:
取虫胶树脂、单体混合,加入N,N-二甲基甲酰胺、N,N’-亚甲基双丙烯酰胺、过硫酸铵,搅拌,升温至60℃,反应7h;加入去离子水,超声洗涤,加入石油醚,超声洗涤,45℃真空干燥,得到虫胶A;
虫胶树脂、单体的质量比为1.8:1;单体为甲基丙烯酸十二氟庚酯;虫胶树脂、N,N-二甲基甲酰胺的比例为2g/mL;N,N’-亚甲基双丙烯酰胺为虫胶树脂、单体总质量的0.04%;过硫酸铵为虫胶树脂、单体总质量的0.8%;
取无水乙醇、虫胶A混合,在氮气气氛保护下,加入水合肼,室温反应6h,得到虫胶B;虫胶A、无水乙醇的比例为150g/L;虫胶A、水合肼的质量比为15:1;
取虫胶B、无水乙醇混合,加入巯基封端聚乙二醇、AIBN,在氮气气氛保护下,60℃反应36h,得到改性虫胶;虫胶B、巯基封端聚乙二醇、AIBN的质量比为8:2:1;虫胶B在无水乙醇中的质量浓度为25%;
取改性虫胶、无水乙醇混合,加入偏钒酸铵、硅酸钠,得到钝化液;钝化液中改性虫胶、偏钒酸铵、硅酸钠的浓度依次为1.5g/L、12g/L、20g/L;
将镀锌钢板置于50℃温度的钝化液中,浸没50s;取出,40℃干燥,形成钝化层,得到高强度热镀锌钢板。
其他工艺与实施例1相同。
对比例7
(4)表面处理:
取虫胶、无水乙醇混合,加入巯基封端聚乙二醇、AIBN,在氮气气氛保护下,60℃反应36h,得到改性虫胶;虫胶B、巯基封端聚乙二醇、AIBN的质量比为8:2:1;虫胶B在无水乙醇中的质量浓度为25%;
取改性虫胶、无水乙醇混合,加入偏钒酸铵、硅酸钠,得到钝化液;钝化液中改性虫胶、偏钒酸铵、硅酸钠的浓度依次为1.5g/L、12g/L、20g/L;
将镀锌钢板置于50℃温度的钝化液中,浸没50s;取出,40℃干燥,形成钝化层,得到高强度热镀锌钢板。
其他工艺与实施例1相同。
对比例8
(4)表面处理:
取虫胶、无水乙醇混合,加入偏钒酸铵、硅酸钠,得到钝化液;钝化液中改性虫胶、偏钒酸铵、硅酸钠的浓度依次为1.5g/L、12g/L、20g/L;
将镀锌钢板置于50℃温度的钝化液中,浸没50s;取出,40℃干燥,形成钝化层,得到高强度热镀锌钢板。
其他工艺与实施例1相同。
实验
取实施例1-3、对比例1-8中得到的高强度热镀锌钢板,制得试样,分别对其性能进行检测并记录检测结果:
镀锌钢板:
力学性能测试:实验万能试验机对试样进行力学性能测试,夹持移动速度为1mm/min,饿到试样的屈服强度、抗拉强度;
钝化层:
抗冲击实验:使用落锤冲击性能测试设备,对试样进行冲击性能测试,实验中钢球至直径为15.875mm,钢球重量为1.8kg,钢球设置高度为50cm;试样后将试样催化剂部位置于5%硫酸铜溶液中浸没30min,洗净,观察有无腐蚀现象;
附着力实验:以GB/T 9286-1998为标准,检测钝化层试样在镀锌钢板上的附着力;
耐腐蚀实验:以GB/T 10125-1997为标准,进行中性盐雾试验,盐雾箱内的温度为35℃,腐蚀溶液为5%的氯化钠水溶液,pH为7.0,对试样连续喷雾96h;试验结束后,室温自然干燥30min,水洗去除试样表面残留的盐雾溶液,利用划格法计算表面未腐蚀的面积。
根据上表中的数据,可以清楚得到以下结论:
实施例1-3中得到的高强度热镀锌钢板与对比例1-8中得到的高强度热镀锌钢板形成对比,检测结果可知,
与对比例1-4相比,实施例1-3中得到的高强度热镀锌钢板,其镀锌钢板的屈服强度、抗拉强度数据明显较高;与对比例5-8相比,实施例1-3中得到的高强度热镀锌钢板,其钝化层冲击后无腐蚀现象,且附着力等级更优、白锈面积更少;这充分说明了本发明实现了对所制高强度热镀锌钢板强度的提高,并实现了对其表面钝化膜强韧性、附着力、耐腐蚀性能的改善。
与实施例1相比,对比例1删除了(1)中的退火工艺;对比例2在对比例1的基础上删除了原工艺(2);对比例3在对比例2的基础上,镀液中不含元素铅;对比例4中的钢板化学成分的含量不同;镀锌钢板的屈服强度、抗拉强度数据劣化;可知本发明对所制高强度热镀锌钢板中镀锌钢板的工艺及其成分设置,能够改善其力学性能;
对比例5删除了表面处理工艺中的组分乙烯基三甲氧基硅烷,并调整了工艺;对比例6在对比例4的基础上删除了表面处理工艺中的组分桐油酸,并调整了工艺;对比例7在对比例5的基础上删除了表面处理工艺中的组分甲基丙烯酸十二氟庚酯、水合肼,并调整了工艺;对比例8中钝化液的组分虫胶未经过改性;其钝化层冲击后腐蚀表现变差,且附着力等级劣化、白锈面积增加;可知,本发明对所制高强度热镀锌钢板中钝化膜的工艺及其成分设置,能够改善其强韧性、附着力和耐腐蚀性能。
需要说明的是,在本文中,诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且,术语“包括”“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程方法物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程方法物品或者设备所固有的要素。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改等同替换改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种高强度热镀锌钢板的制备方法,其特征在于:包括以下工艺:
(1)镀前处理:
取铬粉、氧化铬混合,与钢板共同置于密封装置内,真空封装,750~850℃热处理270~350min,得到预氧化钢板;碱洗,水洗;得到预处理钢板;
(2)镀锌处理:助镀,热镀锌,形成镀层,得到镀锌钢板;
(3)表面处理:取虫胶树脂、单体,升温反应,得到虫胶A;加入水合肼反应,得到虫胶B;加入巯基封端聚乙二醇反应,得到改性虫胶;
将改性虫胶,加入偏钒酸铵、硅酸钠、无水乙醇混合,得到钝化液;
将镀锌钢板浸没于钝化液中,取出,干燥,形成钝化层,得到高强度热镀锌钢板;
所述单体为乙烯基三甲氧基硅烷、甲基丙烯酸十二氟庚酯、桐油酸的混合物;
所述(1)工艺前包括以下工艺:
取钢板热轧,热轧工艺为:在氮气保护气氛中,初始热轧温度为1190~1210℃,保温时间36~60min,终止热轧温度为920~948℃,保温时间25~30min;水冷至636~680℃,石棉缓冷至室温;
酸洗,酸洗工艺为:15%盐酸酸洗10~20min;冷轧至1.2mm;
退火,退火工艺为:以氮气、氢气为保护气氛,以5℃/s的升温速率升温至700℃,以2℃/s的升温速率升温至800℃,800℃等温70s;以2℃/s的降温速率降温至700℃,以30℃/s的降温速率降温至460℃,460℃等温3s,以20℃/s的降温速率冷却至室温,得到钢板;
所述钢板包括以下质量成分:C:0.06~0.10%,Si:0.10~0.18%,Mn:1.22~1.46%,P:0.003~0.005%,S:0.00~0.003%,余量为Fe。
2.根据权利要求1所述的一种高强度热镀锌钢板的制备方法,其特征在于:所述(1)中铬粉、氧化铬的质量比为(0.5~1.2):1;平均粒径为68~80μm。
3.根据权利要求1所述的一种高强度热镀锌钢板的制备方法,其特征在于:所述(1)中的碱洗工艺为:将预氧化钢板置于温度为70~80℃、15%氢氧化钠水溶液中,浸泡15~18min。
4.根据权利要求1所述的一种高强度热镀锌钢板的制备方法,其特征在于:所述(2)中的热镀锌工艺为:取助镀后的钢板,以氮气、氢气为保护气氛,置于460~480℃镀液中浸镀3~5s,以10℃/s的降温速率冷却至室温。
5.根据权利要求4所述的一种高强度热镀锌钢板的制备方法,其特征在于:所述镀液包括以下重量成分:0.18~0.20%铝、0.08~0.12%铅,余量为锌。
6.根据权利要求1所述的一种高强度热镀锌钢板的制备方法,其特征在于:所述(3)包括以下工艺:
取虫胶树脂、单体混合,加入N,N-二甲基甲酰胺、N,N’-亚甲基双丙烯酰胺、过硫酸铵,搅拌,升温至60~70℃,反应7~10h;加入去离子水,超声洗涤,加入石油醚,超声洗涤,45~50℃真空干燥;加入无水乙醇溶解,在氮气气氛保护下,加入水合肼,室温反应6~8h;加入无水乙醇溶解,加入巯基封端聚乙二醇、AIBN,在氮气气氛保护下,60~65℃反应36h,得到改性虫胶;
取改性虫胶、无水乙醇混合,加入偏钒酸铵、硅酸钠,得到钝化液;
将镀锌钢板置于50℃温度的钝化液中,浸没50s;取出,40℃干燥,形成钝化层,得到高强度热镀锌钢板。
7.根据权利要求1所述的一种高强度热镀锌钢板的制备方法,其特征在于:所述钝化液中改性虫胶、偏钒酸铵、硅酸钠的浓度依次为1.5~2.0g/L、12~16g/L、20~25g/L。
8.根据权利要求1-7任一项所述制备方法制得的一种高强度热镀锌钢板。
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