CN114107736A - 含v、b的锌铝镁合金镀层钢材及其制备方法 - Google Patents
含v、b的锌铝镁合金镀层钢材及其制备方法 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 108
- 239000010959 steel Substances 0.000 title claims abstract description 108
- -1 zinc-aluminum-magnesium Chemical compound 0.000 title claims abstract description 40
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 34
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 25
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000007747 plating Methods 0.000 claims description 64
- 238000000576 coating method Methods 0.000 claims description 51
- 239000011248 coating agent Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 32
- 238000000137 annealing Methods 0.000 claims description 15
- 238000005238 degreasing Methods 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000794 TRIP steel Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004886 process control Methods 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 28
- 238000005260 corrosion Methods 0.000 abstract description 28
- 238000009851 ferrous metallurgy Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 23
- 150000003839 salts Chemical class 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000007921 spray Substances 0.000 description 17
- 229910045601 alloy Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 15
- 229910018134 Al-Mg Inorganic materials 0.000 description 13
- 229910018467 Al—Mg Inorganic materials 0.000 description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 13
- 238000005452 bending Methods 0.000 description 9
- 238000005507 spraying Methods 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- 229910017708 MgZn2 Inorganic materials 0.000 description 1
- 229910007981 Si-Mg Inorganic materials 0.000 description 1
- 229910008316 Si—Mg Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- 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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
-
- 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
-
- 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
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
- C23C2/18—Removing excess of molten coatings from elongated material
- C23C2/20—Strips; Plates
-
- 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
- C23C2/34—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
Abstract
本发明涉及含V、B的锌铝镁合金镀层钢材及其制备方法,属于钢铁冶金生产技术领域。本发明提供了含V、B的锌铝镁合金镀层钢材,镀层的化学成分按质量百分比计为:铝0.4%~2.8%,镁0.5%~3.0%,钒0.005%~0.8%,硼0.001%~0.20%,其余为锌及不可避免的杂质;其中Al/Mg为0.8~1.5,钒+硼总量为0.01%~0.50%。本发明提供的锌铝镁合金镀层钢材能够满足用户对于钢材耐蚀性和成形性双高的要求,尤其适用于家电和汽车领域,具有良好的推广应用前景。
Description
技术领域
本发明涉及含V、B的锌铝镁合金镀层钢材及其制备方法,属于钢铁冶金生产技术领域。
背景技术
Zn-Al-Mg合金镀层于20世纪80年代在国外引起广泛关注,成为热浸镀锌及锌合金镀层专业领域的研究重点。从国内外同行的研究结果来看,在镀层Zn、Al含量同等水平条件下,添加Mg的热浸镀Zn-Al-Mg合金镀层钢板具有更优的耐蚀性,且材料的加工应用性能(成形性、焊接性及涂装性)优良,可替代现行相应的热浸镀锌或锌合金镀层钢板,市场需求前景十分广阔。
热浸镀Zn-Al-Mg合金镀层钢板于21世纪初期先后在新日铁、日新制钢、蒂森克虏伯等钢铁公司实现了工业化生产及应用,目前主要应用领域在建筑行业,正逐步在向家电、汽车制造等行业推广应用。我国对Zn-Al-Mg合金镀层的研究较晚,目前仅宝钢、首钢、酒钢、攀钢等企业推出了热浸镀Zn-Al-Mg合金镀层钢板。
现有热浸镀Zn-Al-Mg合金镀层钢板可分为“低铝”(WAl<5%)、“中铝”(5%≤WAl<13%)和“高铝”(47%≤WAl≤57%)三种类型。对于不同品种的Zn-Al-Mg合金镀层钢板,其镀层中的Al、Mg含量不同,镀层组织结构和质量性能存在差异,因而应用领域也有所不同。CN105063532A公开了一种高耐蚀性单镀型锌铝镁稀土防护镀层及制备工艺,该单镀型锌铝镁稀土防护镀层工艺利用单次热浸镀方法在金属表面获得锌铝镁合金镀层。镀层与金属基体各自保持原有的性能,但是拥有99.9%以上冶金结合界面,同时镀层结构致密、成分稳定、无漏镀,耐蚀性能优异,盐雾腐蚀达2060h。合金镀层耐蚀性能较普通热浸镀纯锌层好,提高了使用寿命。该单镀型工艺,可重复使用和工业化生产,克服了金属与锌铝镁合金液助镀困难、两者之间难形成优异结合界面、易产生漏镀等不足,能广泛适用于金属表面制备5%-12%Al、1%-6%Mg含量的锌铝镁合金镀液,所制备的共渗层形成Zn/Al/MgZn2三元共晶以及多种类型的二元共晶体,是共渗层具有高耐蚀性能的主要原因。上述高耐蚀性单镀型锌铝镁稀土防护镀层采用的是中铝成分体系。
CN109402547A提供了一种抗腐蚀性能优良的热浸镀层钢板及其制造方法,所述热浸镀层钢板包括基板和镀覆于基板上的Al-Zn-Si-Mg镀层,所述镀层的化学成分质量百分比为:Al:45%~65%,Si:0.1%~3%,Mg:0.2%~5%,Zr:0.001%~0.15%,Cr:0.001%~0.5%,余量为Zn和不可避免的杂质。其制造方法包括步骤:(1)钢板预处理;(2)将钢板浸入镀液池热浸镀,所述镀液池的温度为560~595℃;(3)将钢板从镀液取出,进行分段冷却。该热浸镀层钢板抗腐蚀性能优良,对白锈发生及红锈的发展、对抗源自切口的处理膜失效蔓延的抑制效果显著。上述抗腐蚀性能优良的热浸镀层钢板采用的是高铝成分体系镀层。
可以看出,高耐蚀性的锌铝镁钢板主要为中高铝成分体系的锌铝镁钢板,随着Al和Mg含量的增多,镀层的耐蚀性升高,但同时会导致成形性能和焊接性能下降。在家电、汽车应用领域,为保证Zn-Al-Mg合金镀层钢板满足用户的冲压成型要求,要具有良好的成形性,目前中高铝成分体系的Zn-Al-Mg合金镀层钢板尚不能满足用户要求。
发明内容
本发明所要解决的技术问题是:提供一种成形性和耐蚀性双高的含V、B的锌铝镁合金镀层钢材及其制备方法。
本发明为解决上述技术问题采用的技术方案是:首先提供了一种含V、B的锌铝镁合金镀层钢材,镀层的化学成分按质量百分比计为:铝0.4%~2.8%,镁0.5%~3.0%,钒0.005%~0.50%,硼0.001%~0.20%,其余为锌及不可避免的杂质;其中Al/Mg为0.8~1.5,钒+硼总量为0.01%~0.50%。
进一步的是:镀层的化学成分满足以下至少一项:镀层中含有铝1.0%~2.5%,镁
1.0%~2.0%,钒0.02%~0.30%,硼0.03%~0.20%;
Al/Mg为0.75~1.25;
钒+硼总量为0.05%~0.20%。
进一步的是:所述不可避免的杂质总和≤0.010%,其中铅≤0.003%,锑≤0.002%,锡≤0.002%,砷≤0.001%,碲≤0.001%,镉≤0.002%。
进一步的是:所述镀层的重量为20~600g/m2,以双面计;优选地,所述镀层的重量为40~400g/m2,以双面计。
进一步的是:所述钢材的钢基选自IF钢、烘烤硬化钢、SPCC、SEDDQ、QP钢、DP钢、TRIP钢中至少一种;优选地,所述的IF钢为含P高强IF钢。
进一步的是:包括以下步骤:钢基脱脂清洗,连续退火,热浸镀,气刀吹扫。
进一步的是:连续退火过程控制炉内氢气≥4.0%,以体积百分含量计;优选地,连续退火过程控制炉内氢气4.0%~6.0%,以体积百分含量计。
进一步的是:钢基入锌锅温度控制在400℃~520℃,热浸镀过程镀液温度为390℃~500℃,入锌锅温度与镀液温度的温差控制在±20℃。
进一步的是:镀后快冷,控制带钢到达顶部转向辊的温度≤280℃;优选地,镀后快冷,控制带钢到达顶部转向辊的温度为240℃~260℃。
本发明的有益效果是:本发明提供的锌铝镁合金镀层钢材采用低铝成分体系,通过对镀层成分的控制生产出耐蚀性和成形性双高的Zn-Al-Mg合金镀层钢板。经检测,本发明锌铝镁合金镀层钢材在中性盐雾试验条件下出现红锈的时间长达400h甚至4500h以上,0T折弯后肉眼未见有明显裂纹且弯曲部位在中性盐雾试验条件下出现红锈的时间在300h甚至4000h以上,喷涂后喷涂涂层的附着性优良。该锌铝镁合金镀层钢材尤其适用于家电和汽车领域,具有良好的推广应用前景。
具体实施方式
本发明提供了含V、B的锌铝镁合金镀层钢材,镀层的化学成分按质量百分比计为:铝0.4%~2.8%,镁0.5%~3.0%,钒0.005%~0.50%,硼0.001%~0.20%,其余为锌及不可避免的杂质;其中Al/Mg为0.8~1.5,钒+硼总量为0.01%~0.50%。
为了保证Zn-Al-Mg合金镀层钢材的耐蚀性能,目前本领域主要采用中高铝成分体系,但随着Al和Mg含量的增多,钢材的成形性能和焊接性能下降明显,难以满足家电、汽车等领域对冲压成型性能的要求。针对上述问题,本发明通过优化镀层中Mg、Al含量和其他合金元素的添加,V在镀层形成过程中提供了异质形核点,细化并降低了镀层的晶粒尺寸,在改善了镀层的延展性的情况下提高了镀层的耐蚀性,而B填充在镀层晶体的间隙中,减少镀层内部缺陷,固溶强化增强了镀层强度,提高了镀层硬度,增强了镀层的耐磨性能,可满足用户对高耐蚀性和高成形性的使用要求。
在镀层制备过程中,为保证镀层具有良好的表面质量和性能,需进行工艺的限制,由于气刀能力和镀液流动性,其镀层厚度控制有一定的范围,太大时则气刀压力小,则表面质量和厚度不易控制,而气刀流量有限且镀层流动性一定,则无法控制的过于薄了;镀液在不同钢板表面的润湿性不同,其仅能在润湿性好的钢板上形成附着力优良的镀层;而退火的气氛则是为了提升钢基表面良好的还原性,一般H2含量越高越好,但H2含量越高爆炸危险增高;镀液温度需保证镀液处于熔融状态且流动性好,V的加入使镀液温度范围有所提升,但温度太高,则易氧化锌渣增多;为保证镀层凝固完全,则需在第一个转向辊前将钢板温度降至凝固点以下,且锌铝镁易氧化,快冷可使其表面质量更佳。
下面将结合实施例对本发明的方案进行解释。本领域技术人员将会理解,下面的实施例仅用于说明本发明,而不应视为限定本发明的范围。实施例中未注明具体技术或条件的,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。
实施例1本发明锌铝镁合金镀层钢材的制备
镀层重量60g/m2(双面),镀层的主要成分为:铝2.8%,镁2.0%,钒0.10%,硼0.02%,铅0.002%,锑0.001%,铬0.001%,镉0.001%,锡0.001%,其余为锌;钢基为TRIP钢。
制备方法为:脱脂清洗、连续退火、热浸镀、气刀吹扫、冷却,其中脱脂清洗是脱脂处理后漂洗干净,连续退火过程以体积百分含量计控制炉内氢气6.0%,钢板入锌锅温度为500℃,热浸镀过程镀液温度为480℃,镀后快冷,带钢到达顶部转向辊的温度260℃。
测试方法:
耐蚀性能:采用中性盐雾加速腐蚀试验,试验条件及方法按GB/T10125-2012《人造气氛腐蚀试验盐雾试验》执行,试验仪器为盐雾腐蚀试验箱,以浓度50g/L、pH值6.5的NaCl去离子水溶液为腐蚀介质,试验温度为35±2℃;试样规格为75mm*150mm×0.8mm,且用透明胶带进行尺寸为5mm的封边,以防止端部锈蚀影响结果;试样采取与竖直方向呈15°~25°角放置。观测试样表面产生红色锈蚀的时间。
成形性:将试样进行0T折弯(180°折弯,弯心半径为0),肉眼观测是否出现裂纹,并对弯曲部位在中性盐雾试验条件下测试出现红锈的时间,中性盐雾试验条件及方法按GB/T10125-2012《人造气氛腐蚀试验盐雾试验》执行。
硬度:采用INNOVATESTEuropeBV通用硬度计选取三个位置测量镀层表面硬度(HV0.01),取平均值。
涂装性:对涂油后的镀层钢板经脱脂清洗、陶化或磷化后进行喷涂烘干,然后采用划格法测试喷涂涂层与钢板的结合程度,若未有涂层脱落,则为附着性良好。
经检测,本实施例制备的锌铝镁合金镀层钢材表面质量良好,具有优良的耐蚀性、成形性和涂装性。在中性盐雾试验条件下出现红锈的时间在600h以上,0T折弯后肉眼未见有明显裂纹且弯曲部位在中性盐雾试验条件下出现红锈的时间在500h以上,镀层硬度为110,喷涂后喷涂涂层的附着性优良,满足用户要求。
实施例2本发明锌铝镁合金镀层钢材的制备
镀层重量200g/m2(双面),镀层的主要成分为:铝1.5%,镁2.0%,钒0.05%,硼0.10%,铅0.001%,锑0.002%,铬0.001%,镉0.001%,锡0.001%,其余为锌;钢基为SEDDQ钢。
制备方法为:脱脂清洗、连续退火、热浸镀、气刀吹扫、冷却,其中脱脂清洗是脱脂处理后漂洗干净,连续退火过程以体积百分含量计控制炉内氢气5.0%,钢板入锌锅温度为450℃,热浸镀过程镀液温度为450℃,镀后快冷,带钢到达顶部转向辊的温度240℃。
测试方法同实施例1。经检测,本实施例制备的锌铝镁合金镀层钢材表面质量良好,具有优良的耐蚀性、成形性和涂装性。在中性盐雾试验条件下出现红锈的时间在2000h以上,镀层硬度为120,0T折弯后肉眼未见有明显裂纹且弯曲部位在中性盐雾试验条件下出现红锈的时间在1800h以上,喷涂后喷涂涂层的附着性优良,满足用户要求。
实施例3本发明锌铝镁合金镀层钢材的制备
镀层重量500g/m2(双面),镀层的主要成分为:铝1.0%,镁1.0%,钒0.20%,硼0.15%,钙0.05%,铅0.002%,锑0.001%,铬0.001%,镉0.002%,锡0.002%,其余为锌;钢基为QP钢。
制备方法为:脱脂清洗、连续退火、热浸镀、气刀吹扫、冷却,其中脱脂清洗是脱脂处理后漂洗干净,连续退火过程以体积百分含量计控制炉内氢气4.0%,钢板入锌锅温度为440℃,热浸镀过程镀液温度为430℃,镀后快冷,带钢到达顶部转向辊的温度260℃。
测试方法同实施例1。经检测,本实施例制备的锌铝镁合金镀层钢材表面质量良好,具有优良的耐蚀性、成形性和涂装性。在中性盐雾试验条件下出现红锈的时间在4500h以上,镀层硬度为110,0T折弯后肉眼未见有明显裂纹且弯曲部位在中性盐雾试验条件下出现红锈的时间在4000h以上,喷涂后喷涂涂层的附着性优良,满足用户要求。
对比例
镀层重量180g/m2(双面),镀层的主要成分为:铝1.6%,镁1.8%,铅0.001%,锑0.001%,铬0.001%,镉0.001%,锡0.001%,其余为锌;钢基为烘烤硬化钢。
制备方法为:脱脂清洗、连续退火、热浸镀、气刀吹扫、冷却,其中脱脂清洗是脱脂处理后漂洗干净,连续退火过程以体积百分含量计控制炉内氢气4.0%,钢板入锌锅温度为460℃,热浸镀过程镀液温度为450℃,镀后快冷,带钢到达顶部转向辊的温度320℃。
测试方法同实施例1。经检测,本对比例制备的锌铝镁合金镀层钢材表面质量较差,存在横线缺陷,耐蚀性、成形性和涂装性略差。在中性盐雾试验条件下出现红锈的时间在1200h以上,镀层硬度为90,0T折弯后肉眼有轻微裂纹且弯曲部位在中性盐雾试验条件下出现红锈的时间在1100h以上,喷涂后喷涂涂层的附着性良好。
需要说明的是,本说明书中描述的具体特征、结构、材料或者特点可以在任一个或多个实施例中以合适的方式结合。此外,在不相互矛盾的情况下,本领域的技术人员可以将本说明书中描述的不同实施例以及不同实施例的特征进行结合和组合。
Claims (10)
1.含V、B的锌铝镁合金镀层钢材,其特征是:镀层的化学成分按质量百分比计为:铝0.4%~2.8%,镁0.5%~3.0%,钒0.005%~0.50%,硼0.001%~0.20%,其余为锌及不可避免的杂质;其中Al/Mg为0.8~1.5,钒+硼总量为0.01%~0.50%。
2.如权利要求1所述的锌铝镁合金镀层钢材,其特征是:镀层的化学成分满足以下至少一项:镀层中含有铝1.0%~2.5%,镁1.0%~2.0%,钒0.02%~0.30%,硼0.03%~0.20%;
Al/Mg为0.75~1.25;
钒+硼总量为0.05%~0.20%。
3.如权利要求1所述的锌铝镁合金镀层钢材,其特征是:所述不可避免的杂质总和≤0.010%,其中铅≤0.003%,锑≤0.002%,锡≤0.002%,砷≤0.001%,碲≤0.001%,镉≤0.002%。
4.如权利要求1所述的锌铝镁合金镀层钢材,其特征是:所述镀层的重量为20~600g/m2,以双面计;优选地,所述镀层的重量为40~400g/m2,以双面计。
5.如权利要求1所述的锌铝镁合金镀层钢材,其特征是:所述钢材的钢基选自IF钢、烘烤硬化钢、SPCC、SEDDQ、QP钢、DP钢、TRIP钢中至少一种;优选地,所述的IF钢为含P高强IF钢。
6.权利要求1~5任意一项所述锌铝镁合金镀层钢材的制备方法,其特征是:包括以下步骤:钢基脱脂清洗,连续退火,热浸镀,气刀吹扫。
7.如权利要求6所述的锌铝镁合金镀层钢材的制备方法,其特征是:连续退火过程控制炉内氢气≥4.0%,以体积百分含量计;优选地,连续退火过程控制炉内氢气4.0%~6.0%,以体积百分含量计。
8.如权利要求6所述的锌铝镁合金镀层钢材的制备方法,其特征是:钢基入锌锅温度控制在400℃~520℃,热浸镀过程镀液温度为390℃~500℃,入锌锅温度与镀液温度的温差控制在±20℃。
9.如权利要求6所述的锌铝镁合金镀层钢材的制备方法,其特征是:镀后快冷,控制带钢到达顶部转向辊的温度≤280℃;优选地,镀后快冷,控制带钢到达顶部转向辊的温度为240℃~260℃。
10.锌铝镁合金镀层钢材,其特征是:按照权利要求6~9任意一项所述的锌铝镁合金镀层钢材的制备方法得到。
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