CN117343557A - 涂料、具有该涂料形成的涂层的取向硅钢板及其制造方法 - Google Patents
涂料、具有该涂料形成的涂层的取向硅钢板及其制造方法 Download PDFInfo
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- CN117343557A CN117343557A CN202210752109.5A CN202210752109A CN117343557A CN 117343557 A CN117343557 A CN 117343557A CN 202210752109 A CN202210752109 A CN 202210752109A CN 117343557 A CN117343557 A CN 117343557A
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- 229910000976 Electrical steel Inorganic materials 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000003973 paint Substances 0.000 title claims abstract description 11
- 239000011247 coating layer Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000576 coating method Methods 0.000 claims abstract description 118
- 239000011248 coating agent Substances 0.000 claims abstract description 112
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 33
- 239000010452 phosphate Substances 0.000 claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008119 colloidal silica Substances 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 4
- 235000019792 magnesium silicate Nutrition 0.000 claims description 4
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 4
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000012002 vanadium phosphate Substances 0.000 claims description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- NAAXGLXYRDSIRS-UHFFFAOYSA-L dihydrogen phosphate;manganese(2+) Chemical compound [Mn+2].OP(O)([O-])=O.OP(O)([O-])=O NAAXGLXYRDSIRS-UHFFFAOYSA-L 0.000 claims description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 2
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 claims description 2
- 235000019785 monomagnesium phosphate Nutrition 0.000 claims description 2
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 22
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 239000011651 chromium Substances 0.000 abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052804 chromium Inorganic materials 0.000 abstract description 9
- 239000011162 core material Substances 0.000 abstract description 4
- 235000021317 phosphate Nutrition 0.000 description 28
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- -1 oxide Chemical compound 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/33—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also phosphates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
Abstract
本发明涉及用于取向硅钢表面涂层的涂料,所述涂料包含:磷酸盐;胶体二氧化硅;选自Ce、Mn、Co、Cu或Fe的钒酸盐中的至少一种;以及所述涂料不含Cr。本发明还涉及具有表面涂层的取向硅钢,所述表面涂层由上述涂料形成。本发明还涉及制备具有由上述涂料形成的表面涂层的取向硅钢的方法。本发明的涂料不含铬,其在保护环境的同时,由该涂料形成的涂层仍可提供足够的耐吸湿性并向取向硅钢板施加足够的张力,进一步降低取向硅钢的铁损和磁滞伸缩,获得优质的变压器铁芯材料。
Description
技术领域
本发明涉及钢板涂层领域,尤其涉及用于取向硅钢表面涂层的涂料、具有该表面涂层的取向硅钢板及其制造方法。
背景技术
取向硅钢板是指硅含量在2.8wt.%-3.5wt.%范围之间,并采用冷轧和热处理工艺获得的具有{110}<001>织构的钢板,其沿轧向的磁性能明显优于横向的磁性能。取向硅钢板主要应用于变压器铁芯材料,为了降低变压器的能量损耗和噪音水平,优选取向硅钢板具有低铁损和低噪声。目前已知通过对取向硅钢板施加适当的拉应力可以降低取向硅钢板的铁损值和磁滞伸缩值。
现有技术中,通常在取向硅钢板表面施加含铬涂层来解决上述问题,含铬涂层不但具有良好的绝缘性,而且在热处理过程中由于涂层与钢板热膨胀系数不同,涂层会对钢板产生拉应力,从而可以降低钢板的铁损和磁滞伸缩值。然而,由于该涂层所使用的涂液中含有六价铬,其生产中产生的废液含有大量对环境有害的六价铬,这将严重污染环境。
随着近年来对环境保护关注度的提高,对不含铬、铅等有害物质的产品的需求提高,对于取向硅钢也希望开发无铬(不含铬)的涂层。然而,使用无铬涂层的取向硅钢通常存在耐吸湿性的显著下降、张力施加不足的问题,因此无铬涂层的使用场景较少,甚至无法采用。
公开号为“CN101790599A”,公开日为2010年7月28日,名称为“方向性电磁钢板用绝缘覆膜处理液以及具有绝缘覆膜的方向性电磁钢板的制造方法”的中国专利文献公开了一种方向性电磁钢板用无铬绝缘覆膜处理液,其包含Mg、Ca、Ba、Sr、Zn、Al及Mn的磷酸盐中至少一种,以及胶体二氧化硅和钛的螯合物。其可提供改善的粘着性和涂层张力,然而螯合物在热处理过程中容易分解产生碳,会对涂层的张力产生不利的影响。
公开号为“CN101223300A”,公开日为2008年7月16日,名称为“具有不含铬的绝缘皮膜的取向电磁钢板及其绝缘皮膜剂”的中国专利文献公开了一种不含铬的取向电磁钢板用绝缘皮膜剂,其主要成分为磷酸盐、胶体二氧化硅和粒径为15nm以下的Fe、Ni、Co、Cu、Sr、Mo的无机化合物,例如氢氧化物、氧化物、碳酸盐、硅酸盐或钼酸盐。然而氢氧化物胶体在磷酸盐溶液体系中并不稳定,固定游离磷酸根的能力也不够充分,容易降低取向硅钢板的耐吸湿性和抗粘片性。
公开号为“CN102119239A”,公开日为2011年7月6日,名称为“用于取向电工钢板的无铬涂布剂、其制备方法、使用该涂布剂的电工钢板及该钢板的制备方法”的中国专利文献公开了一种用于取向硅钢板的无铬涂布剂,该涂布剂包含磷酸盐、胶体二氧化硅和赤铁矿硅溶胶。然而赤铁矿硅溶胶在磷酸盐体系中难以稳定存在,且制备较为困难,难以实现工业化生产。
基于上述问题,希望获得一种满足工业化生产要求的用于取向硅钢板的涂料,该涂料不含铬并且在热处理过程中可保持稳定,还具有良好的可涂覆性。通过此种涂料获得的取向钢板表面涂层具有良好的耐吸湿性、耐腐蚀性、耐热性和抗粘片性,同时还可提供足够的张力效果以进一步降低取向硅钢的铁损和磁滞伸缩。
发明内容
本发明的目的在于提供一种用于取向硅钢表面涂层的涂料,该涂料不含铬,其在保护环境的同时,可为取向硅钢提供具有良好的耐吸湿性、张力、耐腐蚀性、耐热性和抗粘片性的涂层,由此进一步降低取向硅钢的铁损和磁滞伸缩。
为实现以上目的,本发明人潜心研究后意外地发现,通过在涂料中将选自Ce、Mn、Co、Cu、Fe的钒酸盐中的至少一种与磷酸盐组合使用,可以在涂料的热处理过程中使该钒酸盐与磷酸盐中的磷酸根形成不溶物,从而起到固定磷酸根的作用并向取向硅钢施加张力,由此在取向硅钢表面上形成具有良好耐吸湿性、张力、耐腐蚀性、耐热性和抗粘片性的涂层,由此获得具有良好铁损和磁滞伸缩的取向硅钢。
本发明提供一种用于取向硅钢表面涂层的涂料,其中所述涂料包含:
磷酸盐;
胶体二氧化硅;
选自Ce、Mn、Co、Cu或Fe的钒酸盐中的至少一种;
所述涂料不含Cr。
上述涂料在涂覆取向硅钢板后,涂料需经热处理形成涂层,其中磷酸盐在经热处理之后可以在钢板表面形成具有网状或链状结构的磷酸盐涂层。胶体二氧化硅在本发明中作为填充物,在热处理之后形成具有较低热膨胀系数的陶瓷层,从而为涂层提供张力,并有利于改善涂料的涂布性能。本发明中,“胶体二氧化硅”通常是指纳米级二氧化硅的水分散体系,具有硅烷醇基团。热处理过程中,钒酸盐中的Ce、Mn、Co、Cu、Fe及V均能与磷酸盐中的磷酸根形成不溶的磷酸盐化合物,从而在取向硅钢上固定磷酸根,防止游离磷酸根残留在涂层中,由此提高涂层的耐吸湿性、张力、耐蚀性和抗粘片性等。
本发明对钒酸盐没有特别限制,只需其能与磷酸根形成不溶的磷酸钒即可,钒酸盐的实例可为正钒酸盐、焦钒酸盐或偏钒酸盐。优选地,所述钒酸盐为Ce、Mn、Co、Cu或Fe的正钒酸盐(VO4 3-)、焦钒酸盐(V2O7 4-)和/或偏钒酸盐(VO3 -)。
优选地,所述涂料以质量百分比计包含:25~50%的磷酸盐,25-50%的胶体二氧化硅以及10~50%的钒酸盐。
优选地,所述磷酸盐为选自Mg、Al、Ca、Zn、及Mn的磷酸盐中的至少一种。
优选地,所述磷酸盐为磷酸二氢镁、磷酸二氢铝、磷酸二氢钙、磷酸二氢锌和磷酸二氢锰。
优选地,所述胶体二氧化硅与所述磷酸盐的质量比为0.5-1.5,优选1.0~1.5,在此范围内可获得良好的涂覆性,有利于改善本发明所述的涂料的涂布性能。
优选地,所述钒酸盐与所述磷酸盐的质量比为0.2-2.0,优选0.2~1.5,进一步优选0.2-1.0,更优选0.2-0.5。
在本发明所述的技术方案中,钒酸盐(例如正钒酸盐、焦钒酸盐和偏钒酸盐)中的至少一种与磷酸盐的质量比在0.2以上时,可以显著改善涂层的耐吸湿性,但当钒酸盐与磷酸盐的质量比大于2.0时,会导致涂层的张力和耐蚀性降低,因此,本发明所述的用于取向硅钢板的涂料中,钒酸盐与磷酸盐的质量比限定在0.2-2.0。
优选地,所述用于取向硅钢表面涂层的涂料还包含硼酸,通过在涂料中添加硼酸,可进一步改善涂层的烧结致密性、张力和耐热性。
优选地,相对于100质量份所述胶体二氧化硅,所述硼酸的含量为0.02-0.2质量份。
添加适量的硼酸可以进一步改善涂层的烧结致密性、张力和耐热性。然而,当硼酸与胶体二氧化硅的质量比超过0.2时,会导致张力效果、耐热性、耐蚀性下降,因此,本发明所述的涂料中,硼酸与胶体二氧化硅的质量比限定在0.02-0.2范围内。
优选地,所述胶体二氧化硅的粒径为5-50nm。通过调整胶体二氧化硅的粒径,有利于在热处理后形成致密的陶瓷层,获得更好的张力效果和涂层表面形貌。
本发明还提供了一种取向硅钢板,所述取向硅钢板包括基板和在所述基板表面形成的涂层,所述涂层由前述涂料形成。本发明的取向硅钢板通过在其表面形成上述涂料的涂层,利用该涂层在取向硅钢板上施加的拉应力,降低了取向硅钢板的铁损值和磁滞伸缩值,使其适用于变压器铁芯材料,并且有效降低变压器的能量损耗和噪音水平。
优选地,所述涂层包含磷酸钒。
优选地,在本发明所述的取向硅钢板中,所述涂层的单面干膜量为2-10g/m2。如果涂层的单面干膜量低于2g/m2,涂层将无法提供足够的张力;如果涂层的单面干膜量高于10g/m2,则涂料的量过多,使得热处理后的涂层厚度不均,容易导致钢板的叠片系数降低。
本发明的取向硅钢的基板没有特别限定,可以使用本领域中常用的取向硅钢基板,例如可使用Si元素含量为2-4wt%的取向硅钢基板。
优选地,所述基板的厚度为0.18-0.35mm。
优选地,所述取向硅钢板还具有硅酸镁底层,其由隔离剂(通常为MgO)与钢板表面的氧化硅(SiO2)在高温退火条件下(例如1200℃)反应形成,所述硅酸镁底层位于所述取向硅钢板的基板和所述涂层之间,从而增加涂层在钢板上的附着力。
本发明还提供了一种取向硅钢板的制造方法,所述取向硅钢板的表面具有由上述涂料形成的涂层,所述方法包括以下步骤:
1)在取向硅钢板的基板上涂覆上述涂料,在基板表面形成涂层;以及
2)进行烧结。
优选地,在步骤2)中,在基板表面温度为800-900℃的条件下进行烧结,烧结时间为20秒以上。如果该温度低于800℃,则钢板不够平整,且涂层对钢板赋予的张力效果不显著;如果该温度高于900℃,涂层中的二氧化硅则容易晶化,会导致涂层致密性和张力效果下降。
优选地,所述涂料以在水中的溶液形式涂敷在取向硅钢板的基板上。
本发明所述的涂料以及具有由该涂料形成的涂层的取向硅钢板与现有技术相比,具有如下有益效果:
(1)本发明所述涂料不含有害金属元素铬,对周边环境所产生的污染小,环保效益好:
(2)本发明所述的涂料具有良好的稳定性和涂敷性,可以实现工业化生产和使用;以及
(3)本发明所述的取向硅钢板表面涂层具有良好的耐吸湿性、张力、耐腐蚀性、耐热性和抗粘片性,可进一步降低取向硅钢的铁损和磁滞伸缩。
具体实施方式
以下通过实施例对本发明的内容进行更具体的说明,以使本发明的内容更加清楚和便于理解。但需要说明的是,以下公开的实施例只是本发明的具体实施方式的例举,本发明并不局限于这些实施例。
1.用于取向硅钢表面涂层的涂料的制备
本发明的实施例1-28和比较例1-6的用于取向硅钢表面涂层的涂料通过以下方法制备:根据表1列出的配方,将磷酸盐溶液和胶体二氧化硅直接混合,之后可选地将硼酸以固体试剂形式加入(实施例28未加入硼酸),充分搅拌使硼酸完全溶解,然后将钒酸盐粉末以高速分散或者超声分散的形式加入溶液,形成涂料。
表1列出了实施例1-28和比较例1-6的涂料中各组分质量百分比(wt%)及胶体二氧化硅的粒径。其中,比较例1-6中的钒酸盐的量均不符合本发明的钒酸盐与磷酸盐的质量比为0.2-2.0的要求。
表1
2.具有表面涂层的取向硅钢板的制造
将实施例1-28和比较例1-6的涂料涂覆在取向硅钢板的基板上,并通过以下步骤获得具有由所述涂料形成的涂层的各取向硅钢板(关键的技术参数列于表2),其中,取向硅钢板的基板以质量百分比计包含如下化学元素:C:0.046%,Si:3.32%,S:0.006%,可溶性Al:0.027%,N:0.006%,Mn:0.012%,余量为Fe和其他不可避免的杂质:
(1)按照上述各化学元素的质量百分比进行冶炼铸造,得到钢坯。
(2)将钢坯在1150℃下加热后,热轧成2.8mm厚的热轧板。
(3)热轧板经酸洗并冷轧成0.18-0.35mm厚的冷轧板。
(4)冷轧板经过脱碳退火处理后,在湿润的通氨气的氮气和氢气保护气氛中进行连续渗氮处理。
(5)在渗氮处理后的钢板上涂布以氧化镁为主的隔离剂。
(6)卷取钢板,之后在干燥的保护性气氛(如氮气和氢气的混合气)中进行二次再结晶退火,退火温度为1200℃,保温20小时,得到表面覆盖硅酸镁底层的具有高斯织构的基板。
(7)在基板的表面涂敷本发明的如上所述的涂料。
(8)在800-900℃条件下烧结20s以上,得到具有表面涂层的取向硅钢板,表面涂层的单面干膜涂敷量为2-10g/m2。
实施例1-28和比较例1-6的取向硅钢板的制造方法的关键工艺参数如表2所示。
表2
3.具有表面涂层的取向硅钢板的性能评价
对本发明的实施例1-28和比较例1-6的取向硅钢板进行性能测试,包括测试其涂层张力、耐吸湿性、耐热性、耐蚀性和抗粘片性,测试方法具体如下:
(1)涂层张力σ:以轧制方向为长度方向,将取向硅钢板剪为长300mm×宽30mm的样板,然后去除涂层,弯曲样板以测试其翘曲量,并通过以下公式计算得出涂层的张力σ。
上式中,σ表示涂层张力,其单位可以为MPa;E表示钢板杨氏模量,其单位可以为GPa;t表示钢板的厚度,其单位可以为mm;H表示翘曲量,其单位可以为mm;L表示钢板的长度,其单位可以为mm。
(2)耐吸湿性:将取向硅钢板在100℃纯水中煮沸,然后定量分析单位面积涂层中溶出的磷含量,单位为μg/150cm2。
(3)耐热性:测试取向硅钢板经消除应力退火处理后表面涂层的张力劣化程度和绝缘性劣化程度,其中,消除应力退火处理的工艺条件是在850℃下,在100%N2气体中保温4h。评价耐热性的4个等级为:优(张力和绝缘性降低<20%)、良(20%≤张力和绝缘性降低<30%)、中(30%≤张力和绝缘性降低<40%))和差(张力和绝缘性降低≥40%)。
(4)耐蚀性:通过盐雾试验评估涂层的耐蚀性,盐雾试验溶液为5%NaCl溶液,测试温度为35℃,测试时间为10h。评价耐蚀性的4个等级为:优(锈蚀面积<5%)、良(5%≤锈蚀面积<10%)、中(10%≤锈蚀面积<30%)和差(锈蚀面积≥30%)。
(5)抗粘片性:将相同尺寸的取向硅钢钢板叠放在一起,对叠放的取向硅钢板垂直板面施加80kg/cm2的压力。然后在露点为10℃的N2气体中在850℃下热处理4h,通过测试每片取向硅钢板之间的剥离力F的均值来评价涂层的抗粘片性,剥离力越小,抗粘片性能越好。评价抗粘片性的4个等级为:优(F<100g/m2)、良(100≤F<250g/m2)、中(250≤F<500g/m2)和差(F≥500g/m2)。
根据上述方法获得的实施例1-28及比较例1-6的取向硅钢板的测试结果如表3所示。
表3
由表3可以看出,本发明实施例1-28的取向硅钢板的涂层具有优异的张力效果(张力范围7.1~10.5MPa)、耐吸湿性(磷溶出含量<75μg/150cm2),以及优良的耐热性、耐蚀性和抗粘片性能。
而比较例1-6的取向硅钢板的涂层则无法同时满足实施例1-28的各项性能,具体地,当钒酸盐含量过少时,虽然张力涂层具有满足要求的张力,但其磷溶出量较高,说明其耐吸湿性较差。当钒酸盐含量过多时,虽然磷酸根通过过量的钒酸盐固定于涂料中,但其涂层张力无法满足本发明的要求,也无法确保本发明要求的优异耐热性、耐蚀性和抗粘片性。
以上详细描述了本发明的较佳具体实施例。应当理解,本领域的普通技术人员无需创造性劳动就可以根据本发明的构思作出各种修改和变化。因此,凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案,皆应在由权利要求书所确定的保护范围内。
此外,本案中各技术特征的组合方式并不限本案权利要求中所记载的组合方式或是具体实施例所记载的组合方式,本案记载的所有技术特征可以以任何方式进行自由组合或结合,除非相互之间产生矛盾。
Claims (11)
1.用于取向硅钢表面涂层的涂料,其中所述涂料包含:
磷酸盐,优选地,所述磷酸盐为选自Mg、Al、Ca、Zn、及Mn的磷酸盐中的至少一种,更优选地,所述磷酸盐为磷酸二氢镁、磷酸二氢铝、磷酸二氢钙、磷酸二氢锌和/或磷酸二氢锰;
胶体二氧化硅;
选自Ce、Mn、Co、Cu或Fe的钒酸盐中的至少一种,优选地,所述钒酸盐为Ce、Mn、Co、Cu或Fe的正钒酸盐、焦钒酸盐和/或偏钒酸盐;
其中所述涂料不含Cr。
2.根据权利要求1所述的涂料,其中,所述涂料以质量百分比计包含25~50%的磷酸盐,25-50%的胶体二氧化硅以及10~50%的钒酸盐。
3.根据权利要求1所述的涂料,其中,所述胶体二氧化硅与所述磷酸盐的质量比为0.5-1.5,优选1.0~1.5。
4.根据权利要求1所述的涂料,其中,所述钒酸盐与所述磷酸盐的质量比为0.2-2.0,优选0.2~1.0。
5.根据权利要求1所述的涂料,其中,所述涂料还包含:
硼酸,其中相对于100质量份的所述胶体二氧化硅,所述硼酸的含量为0.02-0.2质量份。
6.根据权利要求1所述的涂料,其中,所述胶体二氧化硅的粒径为5-50nm。
7.取向硅钢板,所述取向硅钢板具有基板和在所述基板表面形成的涂层,所述涂层使用权利要求1-6中任一项所述的涂料形成。
8.根据权利要求7所述的取向硅钢板,其中,所述涂层包含磷酸钒。
9.根据权利要求7所述的取向硅钢板,其中,所述涂层的单面干膜量为2-10g/m2。
10.根据权利要求7所述的取向硅钢板,其中,所述取向硅钢板还具有硅酸镁层,所述硅酸镁层位于所述取向硅钢板的基板和所述涂层之间。
11.取向硅钢板的制造方法,所述方法包括以下步骤:
1)在取向硅钢板的基板上涂覆权利要求1至6中任一项中所述的涂料;以及
2)进行烧结,在所述取向硅钢板的基板表面上形成涂层,在烧结过程中,基板表面温度为800-900℃,烧结时间为20秒以上。
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