CN114774905B - 一种环保性无铬镀锌铝镁钢板专用钝化剂及钝化工艺 - Google Patents
一种环保性无铬镀锌铝镁钢板专用钝化剂及钝化工艺 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 44
- 239000010959 steel Substances 0.000 title claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 32
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002161 passivation Methods 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 238000005260 corrosion Methods 0.000 claims abstract description 33
- 230000007797 corrosion Effects 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 239000011777 magnesium Substances 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 230000005764 inhibitory process Effects 0.000 claims abstract description 13
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000004756 silanes Chemical class 0.000 claims abstract description 9
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 6
- -1 polydimethylsiloxane Polymers 0.000 claims description 19
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 238000007747 plating Methods 0.000 abstract description 36
- 229910052749 magnesium Inorganic materials 0.000 abstract description 23
- 229910000611 Zinc aluminium Inorganic materials 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000009500 colour coating Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 12
- 239000007921 spray Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
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- 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
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- 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
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- 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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C2/12—Aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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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- 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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
本发明公开了一种环保性无铬镀锌铝镁钢板专用钝化剂及钝化工艺,属于金属材料表面处理领域。钝化剂包括树脂组分、缓蚀组分、耐蚀组分和助剂;其中,所述缓蚀组分包括硅钛盐、磷酸盐、钼酸盐中的一种或两种或三种,所述耐蚀组分为有机改性硅烷PUB。钝化工艺为:于镀锌铝镁钢板表面涂覆权利要求1~5任意一项所述的钝化剂,其中,涂覆辊的辊速V与镀锌铝镁钢板表面的粗糙度A、钝化剂与镀锌铝镁钢板表面的接触角B三者之间存在关系式:V=100+60A‑0.25B。本发明通过分析不同镀层成分的表面状态并对产线工艺进行调整(包括线速度与带料辊速)生产出一种附着性与耐蚀性均良好的适用于低铝锌铝镁镀层的彩涂前处理工艺。
Description
技术领域
本发明属于金属材料表面处理领域,涉及建筑与家电领域绿色、高耐蚀彩涂板的前处理工艺,具体为一种附着性良好的低铝锌铝镁镀层彩涂板的无铬钝化工艺。
背景技术
近年来,随着镀层技术的发展与绿色环保的要求,国内许多钢铁生产企业陆续开展不同镀液成分的锌铝镁镀层技术研究。据了解,锌铝镁分为低铝、中铝和高铝三种体系,不同体系中铝元素和镁元素含量不同从而导致镀层组织结构的差异。目前国内像首钢、宝钢、鞍钢、酒钢等均具备生产锌铝镁镀层板及彩涂板的水平。其中涉及镀层生产技术方面的专利较多,但是彩涂板方面的专利技术较少。
中国专利申请号为202011172906.3的《具有优良镀层塑性的中铝系锌铝镁镀层钢板及生产方法》、中国专利申请号为202011407881.0的《高成形性的热浸镀锌铝镁合金镀层钢板及其制备方法》、中国专利申请号为202011325356.4的《一种热浸镀锌铝镁合金镀层及其制备方法》等专利中分别介绍了不同成分体系的锌铝镁镀层板的制造及生产方法,但并未涉及彩涂板的生产方法,也没有涉及钝化工艺包括钝化液各组分关系以及镀层板线速度等参数的控制。
中国专利申请号为202011179199.0的《一种中铝锌铝镁镀层钢板的表面处理剂及其制作方法》、中国专利申请号为202011416403.6的《锌铝镁镀层表面处理剂及其制备方法和使用方法》中介绍了一种水性表面处理剂,主要作用为抵抗中铝及高铝系镀层板表面发黑现象产生,这与彩涂工艺的前处理工艺不同,也与本专利涉及到的无铬钝化液不同。
关于无铬钝化液的记载,经检索,中国专利申请号为202010796088.8,申请公开日为2021年1月5日的专利申请文件公开了一种用于锌铝镁镀层产品的表面钝化剂及涂覆的生产方法,该生产方法包括钝化剂制备、光整、涂覆、烘干工序。该发明钝化剂由高交联树脂、硅烷、纳米氧化硅、缓蚀剂、抗氧剂、水组成;通过控制光整辊的粗糙度、光整工艺、涂覆工艺、烘干温度等,得到抗黑变性能优异并且集环保性、耐指纹性、耐蚀性、耐热黄变性、耐溶剂性、阻燃性与涂装性等多种优良功能于一体的锌铝镁产品钝化钢板。中国专利申请号为201710588303.3,申请公开日为2018年1月16日的专利申请文件公开了一种用于压铸铝的无铬钝化剂及其制备、应用,该钝化剂主要是以水性聚氨酯树脂为主成膜物质,复配脲丙基硅烷与氨基硅烷提高附着力,并以有机溶剂、有机硅类渗透剂和消泡剂改善成膜均匀性,制备出稳定均匀的无铬钝化剂,用于压铸铝的表面防腐,盐雾可达72h。上述两个专利中钢板耐腐性能有待加强,并且并未改善钝化层与后续工艺的彩涂板之间的附着力。
发明内容
1、要解决的问题
本专利通过研究不同铝镁含量镀层钢板的表面状态及组织形貌;结合马钢彩涂产线钝化工艺及钝化液成分生产一种附着性良好的低铝锌铝镁彩涂板。
2、技术方案
发明人在彩涂板实际调试生产过程中发现,对于同体系的低铝锌铝镁镀层板,不同铝镁含量变化对后期钝化处理中钝化液与镀层表面的附着性有一定的相关性,这必然会对彩涂板的涂层附着性及产品的加工性有一定影响。
本发明通过研究不同铝镁含量镀层钢板的表面状态及组织形貌;结合马钢彩涂产线钝化工艺及钝化液成分生产一种附着性良好的低铝锌铝镁彩涂板。
为解决上述问题,本发明具体采用如下的技术方案。
一种环保性无铬镀锌铝镁钢板专用钝化剂,包括树脂组分、缓蚀组分、耐蚀组分和助剂;其中,所述缓蚀组分包括硅钛盐、磷酸盐、钼酸盐中的一种或两种或三种,所述耐蚀组分为有机改性硅烷PUB,所述有机改性硅烷PUB采用Becker公司的PUB-3C产品。
进一步地,所述缓蚀组分的质量份数为:20-30份的硅钛盐、20-30份的磷酸盐、5-10份钼酸盐;所述有机改性硅烷PUB的质量份数为1.0-1.5份。
进一步地,所述树脂组分为10-15份的水性环氧树脂及10-15份的水性硅丙树脂。
进一步地,所述助剂包括0.5-1.0份的亚磷酸酯抗氧剂、0.2-0.5份的成膜助剂和0.2-0.5份的浸润性助剂。
进一步地,所述浸润性助剂为聚二甲基硅氧烷。
上述涉及的后处理药剂为一种环保性无铬锌铝镁专用钝化剂,该钝化剂中各组分及其质量份数为:
上述钝化剂的具体制备方法为:
(1)准备反应釜:反应釜配套设有搅拌装置,温度计,将设备清洗后烘干备用。
(2)在反应釜中加入去离子水,搅拌均匀后再添加水性环氧树脂与水性硅丙树脂,保证钝化液的致密性及耐蚀性,搅拌均匀后在40℃-50℃温度条件下放置1小时,使其充分融合。
(3)通过加入一定量的硅钛盐、磷酸盐和少量的钼酸盐进行充分搅拌,形成无铬钝化剂的主要缓蚀组分。
(4)进一步地加入有机硅烷偶联剂,用以提高钝化膜的致密性和耐蚀性,并有利于同后期涂层进行交联反应。搅拌30分钟,提高反应活性及程度。本专利中的有机硅烷偶联剂为有机改性硅烷PUB,具有独特的化学和物理性能,不仅可作为基体间的弹性桥联剂,改善材料间的粘结性;还可作为改性剂,提高化学层的耐腐蚀性能。
(5)进一步地加入一定量的抗氧剂,搅拌20分钟。本专利中涉及到的抗氧剂为亚磷酸酯抗氧剂,可提高钝化层在反应中的稳定性。
(6)进一步地加入成膜助剂及浸润性助剂,搅拌30分钟后将上述混合物放置于温度为40-50℃环境下2小时。本专利涉及的浸润性助剂为聚二甲基硅氧烷,其表面张力较小,可提高钝化层与镀层板,钝化层与底漆层间的浸润性。
一种镀锌铝镁钢板专用钝化工艺,钝化工艺为:于镀锌铝镁钢板表面涂覆上述的钝化剂,其中,涂覆辊的辊速V与镀锌铝镁钢板表面的粗糙度A、钝化剂与镀锌铝镁钢板表面的接触角B三者之间存在以下关系式:
V=100+60A-0.25B。
进一步地,涂覆钝化剂的过程中,带料辊的辊速为涂覆辊的辊速V的80%。
进一步地,钝化剂的涂覆膜重以钛含量计为4-12mg/m2之间。
进一步地,镀锌铝镁钢板的锌铝镁镀层中含有1.5%的Al和1.0%的Mg。
包含上述钝化工艺的工艺流程如下:
步骤一、镀锌铝镁基板的制备:钢坯(主要化学成分重量百分比为:C:0.03%~0.20%;Si:≤0.07%;Mn:≤1.50%;P:≤0.03%;S:≤0.02%;Al:≤0.05%,其余为铁和杂质)经过热轧、酸洗、冷轧以及热浸镀工艺后制成表面质量及板形合格的镀层钢带,即锌铝镁基板。注:本专利涉及的镀层重量为ZM120即双面镀层重量为120g/m2。
步骤二、清洗:对低铝锌铝镁基板进行碱洗和漂洗用以去除钢带表面的杂质及油污;
步骤三、钝化:根据基板表面状态对其进行钝化处理,在表面涂敷一层钝化剂并成膜,使镀层板与彩涂涂层可以紧密结合。
由于低铝锌铝镁中添加了一定成分的镁元素,因此会在镀层中形成含镁的二元及三元合金化合物。随着镁元素含量提高,镀层表面硬度提升,表面粗糙度降低;且镀层表面与钝化液的浸润性变差。因此根据经验及试验验证后得出,对于低铝锌铝镁镀层板,要想保证其不同含量基板与钝化液良好的附着性(包括加工性及耐蚀性)需要对产线线速度和带料辊辊速进行调整。
其中,涂覆辊的辊速V与镀锌铝镁钢板表面的粗糙度A以及钝化剂与镀锌铝镁钢板表面的接触角B(基材与钝化液的浸润性)有关。具体关系如下:
V=100+60A-0.25B,
同时,带料辊的辊速为涂覆辊辊速的80%,钝化膜理论膜重在4-12mg/㎡之间(以钛含量计)。
3、有益效果
相比于现有技术,本发明的有益效果为:
本发明通过分析不同镀层成分的表面状态并对产线工艺进行调整(包括线速度与带料辊速)生产出一种附着性与耐蚀性均良好的适用于低铝锌铝镁镀层的彩涂前处理工艺;其中,在钝化液设计方面,为符合国家对彩涂板在环保上的要求,采用无铬钝化成膜药剂代替原有的含铬钝化剂。同时,为了能够满足锌铝镁镀层板与钝化液良好的反应性以及钝化膜的均匀性,采用有机改性硅烷PUB作为偶联剂、以硅钛盐及少量钼酸盐作为主要缓蚀剂。
附图说明
图1为对比例盐雾试验(700h)后的产品状态图;
图2为实施例3盐雾试验(680h)后的产品状态图;
图3为实施例5盐雾试验(960h)后的产品状态图;
图4为实施例8盐雾试验(800h)后的产品状态图;
图5为各实施例加工性能对比图;
图6为各实施例盐雾性能对比图;
具体实施方式
下面结合具体实施例和附图对本发明进一步进行描述。
本专利涉及的创新点主要包括两方面:一是针对不同镀层成分热浸镀后镀层表面状态的差异结合产线实际工艺进行线速度与带料辊的速度调整,保证镀层板与钝化液有较好的结合。二是将钝化液成分进行调整,由有铬转变为无铬满足彩涂前处理工艺绿色环保的需求。其中为了能够更好的将钝化液与镀层紧密结合,且保证产品的耐蚀性对钝化液中主要缓蚀剂、交联剂以及成膜性助剂进行优化设计。具体防范如下:
步骤一、镀锌铝镁基板的制备:钢坯(主要化学成分重量百分比为:C:0.03%~0.20%;Si:≤0.07%;Mn:≤1.50%;P:≤0.03%;S:≤0.02%;Al:≤0.05%,其余为铁和杂质)经过热轧、酸洗、冷轧以及热浸镀工艺后制成表面质量及板形合格的镀层钢带,即锌铝镁基板。注:本专利涉及的镀层重量为ZM120即双面镀层重量为120g/m2。
各实施例的热浸镀工艺如表1所示:
表1各实施例的热浸镀锌铝镁工艺
步骤二、清洗:对低铝锌铝镁基板进行碱洗和漂洗用以去除钢带表面的杂质及油污;
表2清洗工艺
步骤三、钝化:根据基板表面状态对其进行钝化处理,在表面涂敷一层钝化膜,使镀层板与涂层可以紧密结合。其中钢板表面硬度、浸润性及粗糙度如表3所示,具体钝化工艺如表4:
表3表面状态差异
实施例 | HV 0.1/N/m2 | Ra/μm | 接触角/° |
1 | 100 | 1.0~1.2 | 40~45 |
2 | 120 | 0.8~1.0 | 50~55 |
3 | 140 | 0.6~0.8 | 60~65 |
表4钝化工艺
由于低铝锌铝镁中添加了一定成分的镁元素,因此会在镀层中形成含镁的二元及三元合金化合物。随着镁元素含量提高,镀层表面硬度提升,表面粗糙度降低;且镀层表面与钝化液的浸润性变差。因此根据经验及试验验证后得出,对于低铝锌铝镁镀层板,要想保证其不同含量基板与钝化液良好的附着性(包括加工性及耐蚀性)需要对产线线速度和带料辊辊速进行调整。
其中涂覆辊速V与基材表面粗糙度A以及接触角B(基材与钝化液的浸润性)有关。具体关系如下:
V=100+60A-0.25B
带料辊辊速为涂覆辊辊速的80%,钝化膜理论膜重在4-12mg/㎡之间(以钛含量计)。
表5各实施例涂敷辊辊速与表面粗糙度、接触角的关系
实施例 | V,m/min | Ra/μm | 接触角/° |
1 | 150 | 1.0 | 40 |
2 | 135.5 | 0.8 | 50 |
3 | 121 | 0.6 | 60 |
本专利中涉及的后处理药剂为一种环保性无铬锌铝镁专用钝化剂,该钝化剂中各组分及其质量份数为:
该钝化剂的具体制备方法为:
(1)准备反应釜:反应釜配套设有搅拌装置,温度计,将设备清洗后烘干备用。
(2)在反应釜中加入去离子水,搅拌均匀后再添加水性环氧树脂与水性硅丙树脂,保证钝化液的致密性及耐蚀性,搅拌均匀后在40℃-50℃温度条件下放置1小时,使其充分融合。
(3)通过加入一定量的硅钛盐、磷酸盐和少量的钼酸盐进行充分搅拌,形成无铬钝化剂的主要缓蚀组分。
(4)进一步地加入有机硅烷偶联剂,用以提高钝化膜的致密性和耐蚀性,并有利于同后期涂层进行交联反应。搅拌30分钟,提高反应活性及程度。
(5)进一步地加入一定量的抗氧剂,搅拌20分钟。
(6)进一步地加入成膜助剂及浸润性助剂,搅拌30分钟后将上述混合物放置于温度为40-50℃环境下2小时。
具体实施方案为:
表5实施方案
表6原料厂家及型号
性能测试
该类产品的加工性及耐盐雾性能如表7所示,其中对比例为有铬钝化,镀层中1.5%Al+1.0%Mg,双面镀层重量为120g/m2。
表7性能结果
由上述结果可知:加工性实施例5最优;盐雾性能实施例5是对比例的1.3倍,为实施例1的1.5倍。由此可知,实施例5(当镀层成分为1.5%Al+1.0%Mg,钝化液组分在中等含量范围时)加工性及耐蚀性均最好,表明基板与该无铬钝化液的附着性最优。特别的,图1为对比例盐雾试验700h后的产品状态图,图2为实施例3盐雾试验680h后的产品状态图,图3为实施例5盐雾试验960h后的产品状态图,图4为实施例8盐雾试验800h后的产品状态图,图5和图6分别为各实施例加工性能对比、盐雾性能对比图。
本发明所述实例仅仅是对本发明的优选实施方式进行描述,并非对本发明构思和范围进行限定,在不脱离本发明设计思想的前提下,本领域工程技术人员对本发明的技术方案作出的各种变形和改进,均应落入本发明的保护范围。
Claims (5)
1.一种环保性无铬镀锌铝镁钢板专用钝化剂,其特征在于:包括树脂组分、缓蚀组分、耐蚀组分和助剂;其中,所述缓蚀组分包括硅钛盐、磷酸盐、钼酸盐中的一种或两种或三种,所述耐蚀组分为有机改性硅烷PUB;所述树脂组分为10-15份的水性环氧树脂及10-15份的水性硅丙树脂;所述缓蚀组分的质量份数为:20-30份的硅钛盐、20-30份的磷酸盐、5-10份钼酸盐,所述有机改性硅烷PUB的质量份数为1.0-1.5份;所述硅钛盐为上海隆泉化工的PTSC-1产品;所述助剂包括0.5-1.0份的亚磷酸酯抗氧剂、0.2-0.5份的成膜助剂和0.2-0.5份的浸润性助剂,所述浸润性助剂为聚二甲基硅氧烷;所述有机改性硅烷PUB采用Becker公司的PUB-3C产品。
2.一种镀锌铝镁钢板专用钝化工艺,其特征在于:钝化工艺为:于镀锌铝镁钢板表面涂覆权利要求1所述的钝化剂,其中,涂覆辊的辊速V与镀锌铝镁钢板表面的粗糙度A、钝化剂与镀锌铝镁钢板表面的接触角B三者之间存在以下关系式:
V=100+60A-0.25B,
其中,辊速V的单位为m/min,粗糙度A的单位为μm,接触角B的单位为°。
3.根据权利要求2所述的一种镀锌铝镁钢板专用钝化工艺,其特征在于:涂覆钝化剂的过程中,带料辊的辊速为涂覆辊的辊速V的80%。
4.根据权利要求2所述的一种镀锌铝镁钢板专用钝化工艺,其特征在于:钝化剂的涂覆膜重以钛含量计为4-12mg/m2之间。
5.根据权利要求2所述的一种镀锌铝镁钢板专用钝化工艺,其特征在于:镀锌铝镁钢板的锌铝镁镀层中含有1.5%的Al和1.0%的Mg。
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