CN110512162A - 由涂覆有基于铝的金属涂层的钢板生产部件的方法 - Google Patents
由涂覆有基于铝的金属涂层的钢板生产部件的方法 Download PDFInfo
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- CN110512162A CN110512162A CN201910863232.2A CN201910863232A CN110512162A CN 110512162 A CN110512162 A CN 110512162A CN 201910863232 A CN201910863232 A CN 201910863232A CN 110512162 A CN110512162 A CN 110512162A
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- 238000000576 coating method Methods 0.000 title claims abstract description 94
- 239000011248 coating agent Substances 0.000 title claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000004411 aluminium Substances 0.000 title claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 96
- 239000010959 steel Substances 0.000 claims abstract description 96
- 239000011701 zinc Substances 0.000 claims abstract description 37
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 229910052745 lead Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims description 12
- 229910000734 martensite Inorganic materials 0.000 claims description 12
- 229910019752 Mg2Si Inorganic materials 0.000 claims description 8
- 229910001563 bainite Inorganic materials 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims description 4
- 229910018137 Al-Zn Inorganic materials 0.000 claims description 3
- 229910018573 Al—Zn Inorganic materials 0.000 claims description 3
- 229910017708 MgZn2 Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910001566 austenite Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 description 23
- 230000007797 corrosion Effects 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000011651 chromium Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 7
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229960002668 sodium chloride Drugs 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229940075397 calomel Drugs 0.000 description 4
- 238000004210 cathodic protection Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000009628 steelmaking Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910021365 Al-Mg-Si alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910018619 Si-Fe Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910008289 Si—Fe Inorganic materials 0.000 description 1
- 229910000635 Spelter Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/012—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C21/04—Modified aluminium-silicon alloys
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Abstract
本发明涉及由涂覆有金属涂层的钢板生产部件的方法。本发明涉及涂覆有金属涂层的钢板，所述金属涂层包含2.0重量％至24.0重量％的锌，7.1重量％至12.0重量％的硅，任选的1.1重量％至8.0重量％的镁和任选的选自Pb、Ni、Zr或Hf的另外的元素，每种另外的元素以重量计的含量小于0.3重量％，余量为铝和任选地不可避免的杂质和残留元素，其中比率Al/Zn大于2.9。
Description
本申请是申请日为2016年7月8日，申请号为“201680044116.2”，发明名称为“涂覆有基于铝的金属涂层的钢板”的中国专利申请的分案申请。
技术领域
本发明涉及由涂覆有金属涂层的钢板生产经涂覆的部件的方法。本发明特别适用于机动车辆的制造。
背景技术
通常使用基于锌的涂层，因为其由于阻挡层保护和阴极保护而允许抗腐蚀保护。屏障作用通过在钢表面上施加金属涂层而获得。因此，金属涂层防止钢与腐蚀性气氛之间的接触。屏障作用与涂层和基材的性质无关。相反，牺牲阴极保护是基于这样的事实，即锌与钢相比是较不贵重的金属。因此，如果发生腐蚀，则锌优先于钢被消耗。阴极保护在钢直接暴露于腐蚀性气氛的区域(例如其中在钢之前将消耗掉周围的锌的切割边缘)中是必需的。
然而，当例如通过热冲压对这种经锌涂覆的钢板进行压制硬化过程时，观察到钢中从涂层扩展出的微裂纹。另外，由于部件的表面存在不牢固的氧化物层，因而在磷酸盐化之前，一些涂覆有锌的硬化部件的上涂料步骤需要进行打磨操作。
通常用于生产机动车辆的其他金属涂层是基于铝和硅的涂层。由于存在金属间化合物层Al-Si-Fe，因而在进行压制硬化过程时，钢中没有微裂纹。此外，其具有良好的上涂料能力。其允许通过屏障作用进行保护，并且可以进行焊接。但是，其不允许阴极保护，或者其具有非常低的阴极保护。
专利申请EP1225246公开了一种Zn-Al-Mg-Si合金镀覆的材料，其中该涂层包含(按重量％计)：Al：至少45％且不大于70％；Mg：至少3％且小于10％；Si：至少3％且小于10％，剩余部分为Zn和不可避免的杂质，其中Al/Zn比为0.89至2.75，并且镀层包含大体积的Mg2Si相。其还公开了一种Zn-Al-Mg-Si合金镀覆的钢材料，其中该涂层包含(按重量％计)：Al：至少45％且不大于70％；Mg：至少1％且小于5％；Si：至少0.5％且小于3％，剩余部分为Zn和不可避免的杂质，其中Al/Zn比为0.89至2.75，并且镀层包含鳞状Mg2Si相。在上涂料之后这些特定涂层在切割边缘部分显示出未上涂料的耐腐蚀性和边缘抗蠕变性。
然而，制造特定的Mg2Si相(鳞状或大体积)是复杂的。事实上，这取决于Mg2Si相的短直径平均尺寸相对于长直径的比率和尺寸，如在5°抛光截面中观察到的。尺寸最主要受热浸镀之后冷却速率的影响。此外，Mg2Si相的制造还取决于Mg和Si的量。
从工业角度来看，由于这些特定标准，Mg2Si相可能难以获得。因此，存在得不到期望Mg2Si相的风险。
发明内容
本发明的目的是提供一种易于成形的经涂覆的钢板，其在成形之前和之后均具有增强的抗腐蚀保护，即除了阻挡层保护之外的牺牲阴极保护。
就牺牲保护性腐蚀而言，电化学电位必须比钢的电位负至少50mV，即，相对于饱和甘汞电极(SCE)的最大电位为-0.78V。优选不使电位降低至-1.4V/SCE的值，甚至-1.25V/SCE的值，这会导致快速消耗，并将最终缩短钢的保护期。
这通过提供根据权利要求1所述的方法来实现。所述方法还可以包括单独或组合的权利要求2至4中的任何特征。
本发明还涉及根据权利要求5所述的方法。
这些方法还可以包括单独或组合的权利要求6至15中的任何特征。
本发明还涵盖根据权利要求16所述的部件。
所述部件还可以包括单独或组合的权利要求17或18的任何特征。
本发明还涵盖根据权利要求19所述的经涂覆的部件用于制造机动车辆的用途。
附图说明
为了说明本发明，将特别参照以下附图来描述非限制性实例的多个实施方案和试验：
图1示出了对应于168小时标准VDA233-102的一个腐蚀循环。
具体实施方式
本发明的其他特征和优点将由以下对本发明的详细描述而变得明显。
任何钢都可以有利地用于本发明的框架中。然而，在需要具有高机械强度的钢的情况下，特别是对于机动车辆结构的部件，可以使用在热处理之前或之后的抗拉性大于500MPa，优选500MPa至2000MPa的钢。钢板的重量组成优选如下：0.03％≤C≤0.50％；0.3％≤Mn≤3.0％；0.05％≤Si≤0.8％；0.015％≤Ti≤0.2％；0.005％≤Al≤0.1％；0％≤Cr≤2.50％；0％≤S≤0.05％；0％≤P≤0.1％；0％≤B≤0.010％；0％≤Ni≤2.5％；0％≤Mo≤0.7％；0％≤Nb≤0.15％；0％≤N≤0.015％；0％≤Cu≤0.15％；0％≤Ca≤0.01％；0％≤W≤0.35％，余量为铁和来自钢制造的不可避免的杂质。
例如，钢板为具有以下组成的22MnB5：0.20％≤C≤0.25％；0.15％≤Si≤0.35％；1.10％≤Mn≤1.40％；0％≤Cr≤0.30％；0％≤Mo≤0.35％；0％≤P≤0.025％；0％≤S≤0.005％；0.020％≤Ti≤0.060％；0.020％≤Al≤0.060％；0.002％≤B≤0.004％，余量为铁和来自钢制造的不可避免的杂质。
钢板可以为具有以下组成的2000：0.24％≤C≤0.38％；0.40％≤Mn≤3％；0.10％≤Si≤0.70％；0.015％≤Al≤0.070％；0％≤Cr≤2％；0.25％≤Ni≤2％；0.020％≤Ti≤0.10％；0％≤Nb≤0.060％；0.0005％≤B≤0.0040％；0.003％≤N≤0.010％；0.0001％≤S≤0.005％；0.0001％≤P≤0.025％；应理解，钛和氮的含量满足Ti/N>3.42；碳、锰、铬和硅的含量满足：
该组成任选地包含以下中的一者或更多者：0.05％≤Mo≤0.65％；0.001％≤W≤0.30％；0.0005％≤Ca≤0.005％，余量为铁和来自钢制造的不可避免的杂质。
例如，钢板为具有以下组成的500：0.040％≤C≤0.100％；0.80％≤Mn≤2.00％；0％≤Si≤0.30％；0％≤S≤0.005％；0％≤P≤0.030％；0.010％≤Al≤0.070％；0.015％≤Nb≤0.100％；0.030％≤Ti≤0.080％；0％≤N≤0.009％；0％≤Cu≤0.100％；0％≤Ni≤0.100％；0％≤Cr≤0.100％；0％≤Mo≤0.100％；0％≤Ca≤0.006％，余量为铁和来自钢制造的不可避免的杂质。
钢板可以根据期望的厚度(其可以为例如0.7mm至3.0mm)通过热轧和任选地冷轧而获得。
钢板涂覆有金属涂层，所述金属涂层包含2.0重量％至24.0重量％的锌，7.1重量％至12.0重量％的硅，任选的1.1重量％至8.0重量％的镁和任选的选自Pb、Ni、Zr或Hf的另外的元素，每种另外的元素以重量计的含量小于0.3重量％，余量为铝和任选地不可避免的杂质和残留元素，其中比率Al/Zn大于2.9。根据本发明的金属涂层具有高的牺牲保护。
优选地，金属涂层不包含选自以下的元素：Cr、Mn、Ti、Ce、La、Nd、Pr、Ca、Bi、In、Sn和Sb或其组合。在另一个优选实施方案中，金属涂层不包含任意以下成分(compound)：Cr、Mn、Ti、Ce、La、Nd、Pr、Ca、Bi、In、Sn和Sb。事实上，不希望受任何理论的束缚，看起来当这些成分存在于涂层中时，存在涂层的特性(例如电化学电位)改变的风险，原因是其与涂层的主要元素的可能相互作用。
优选地，比率Al/Zn小于或等于8.5。优选地，比率Al/Zn为3.0至7.5，有利地为4.0至6.0。不希望受任何理论的束缚，看起来如果不满足这些条件，则存在牺牲保护降低的风险，原因是富锌相在涂层中的量不足。
在一个优选实施方案中，涂层还包含Al-Zn相。
有利地，金属涂层包含10.0重量％至20.0重量％，优选10.0至15.0重量％的锌。
优选地，金属涂层包含8.1重量％至10.0重量％的硅。
有利地，涂层包含3.0重量％至8.0重量％的镁，优选3.0重量％至5.0重量％的镁。不希望受任何理论的束缚，已经发现，以上述范围添加镁进一步改善了抗腐蚀特性。
优选地，所述涂层的显微组织包含Mg2Si相。在另一个优选实施方案中，所述涂层的显微组织还包含MgZn2相。
有利地，铝的量大于71重量％，优选大于76重量％。
涂层可以通过本领域技术人员已知的任何方法沉积，例如热浸镀工艺、电镀工艺、物理气相沉积例如射流气相沉积或磁控溅射。优选地，涂层通过热浸镀工艺沉积。在该工艺中，将通过轧制获得的钢板浸在熔融金属浴中。
浴包含锌、硅、铝和任选的镁。其可以包含选自Pb、Ni、Zr或Hf的另外的元素，每种另外的元素以重量计的含量小于0.3重量％。这些另外的元素可以改善钢板上的涂层附着性、延展性等。
浴还可以包含不可避免的杂质和残留元素，其来自供给锭或来自钢板在熔融浴中的通过。残留元素可以是含量最高至3.0重量％的铁。
涂层的厚度通常为5μm至50μm，优选10μm至35μm，有利地为12μm至18μm或者26μm至31μm。浴温度通常为580℃至660℃。
在沉积涂层之后，通常用喷嘴在经涂覆的钢板的两侧喷射气体来擦拭(wipe)钢板。然后使经涂覆的钢板冷却。优选地，凝固开始和凝固结束之间的冷却速率大于或等于15℃·秒-1。有利地，凝固开始和结束之间的冷却速率大于或等于20℃·秒-1。
然后，可实现光整冷轧(skin-pass)，并允许对经涂覆的钢板进行加工硬化并给予其促进后续成形的粗糙度。可以施加脱脂和表面处理以改善例如附着结合或耐腐蚀性。
然后，可以通过本领域技术人员已知的任何方法(例如冷冲压和/或热成形)使经涂覆的钢板成形。
在一个优选实施方案中，部件通过冷冲压获得。在这种情况下，将经涂覆的钢板切割以获得坯件，然后进行冷冲压以获得部件。
在另一个优选实施方案中，经涂覆的部件通过包括热成形的压制硬化过程获得。在这种情况下，该方法包括以下步骤：
A)提供预涂覆金属涂层的钢板，所述金属涂层包含2.0重量％至24.0重量％的锌，7.1重量％至12.0重量％的硅，任选的1.1重量％至8.0重量％的镁和任选的选自Pb、Ni、Zr或Hf的另外的元素，每种另外的元素以重量计的含量小于0.3重量％，余量为铝和不可避免的杂质和残留元素，其中比率Al/Zn大于2.9，
B)切割经涂覆的钢板以获得坯件，
C)在840℃至950℃的温度下对坯件进行热处理，以在钢中获得完全奥氏体显微组织，
D)将坯件转移至压制工具(press tool)中，
E)使坯件热成形以获得部件，
F)使步骤E)中获得的部件冷却，以在钢中获得这样的显微组织：所述显微组织为马氏体或马氏体-贝氏体，或者由至少75％的等轴铁素体、5％至20％的马氏体和小于或等于10％的量的贝氏体构成。
事实上，在提供根据本发明的预涂覆金属涂层的钢板之后，对钢板进行切割以获得坯件。在炉中在非保护性气氛下在通常为840℃至950℃，优选880℃至930℃的奥氏体化温度Tm下对坯件施加热处理。有利地，在1分钟至12分钟，优选3分钟至9分钟的停留时间tm期间保持所述坯件。在热成形之前的热处理期间，涂层形成具有高耐腐蚀性、抗磨性(resistance to abration)、耐磨性(resistance to wear)和耐疲劳性的合金层。
在热处理之后，然后将坯件转移至热成形工具并在600℃至830℃的温度下进行热成形。热成形包括热冲压和辊轧成形。优选地，对坯件进行热冲压。然后使部件在热成形工具中冷却，或在转移至特定的冷却工具之后冷却。
根据钢组成以如下方式控制冷却速率：使得在热成形之后的最终显微组织主要包含马氏体，优选包含马氏体，或马氏体和贝氏体，或者由至少75％的等轴铁素体、5％至20％的马氏体和小于或等于10％的量的贝氏体构成。
因此，根据本发明的经涂覆的部件可以通过冷成形或热成形获得，而且还可以通过冷冲压和热成形的任何适当组合获得。
对于汽车应用，在磷酸盐化步骤之后，将部件浸在e-涂覆(e-coating)浴中。通常，磷酸盐层的厚度为1μm至2μm，e-涂层的厚度为15μm至25μm，优选地小于或等于20μm。电泳层确保了另外的抗腐蚀保护。
在e-涂覆步骤之后，可以沉积另外的涂料层，例如，涂料的底漆涂层、底涂层(basecoat layer)和顶涂层(top coat layer)。
在将e-涂层施加在部件上之前，预先将部件脱脂和磷酸盐化，以确保电泳的附着性。
现在将在仅用于提供信息而进行的试验中说明本发明。这些试验不是限制性的。
实施例
对于所有样品，所使用的钢板为22MnB5。钢的组成如下：C＝0.2252％；Mn＝1.1735％；P＝0.0126％；S＝0.0009％；N＝0.0037％；Si＝0.2534％；Cu＝0.0187％；Ni＝0.0197％；Cr＝0.180％；Sn＝0.004％；Al＝0.0371％；Nb＝0.008％；Ti＝0.0382％；B＝0.0028％；Mo＝0.0017％；As＝0.0023％；V＝0.0284％。
所有涂层通过热浸镀工艺沉积。所有涂层具有15μm的厚度。
实施例1：切割边缘电位测试：
制备试验件1至4并进行电化学电位测试。
实现了包括测量经涂覆的钢板的切割边缘电位的测试。为此，将各钢板浸入包含2.43重量％硫酸钠和0.1重量％氯化钠的溶液中。将饱和甘汞电极(SCE)也浸入该溶液中。测量切割边缘的耦合电位。结果示于下表1中：
*：根据本发明的实施例。
与包含铝和9重量％硅的涂层相比，根据本发明的试验件(试验件1至3)具有更低的耦合电位。根据需要，试验件1至3的耦合电位小于-0.78V/SCE。
实施例2：切割边缘腐蚀测试
制备试验件5至12并进行腐蚀测试以评估经涂覆的钢板的切割边缘保护。
将所有的试验件浸入包含2.43重量％硫酸钠和0.1重量％氯化钠的溶液中50小时。用肉眼观察经涂覆的钢板切割边缘上腐蚀的存在：0意味着优异，换言之，几乎没有或没有腐蚀；5意味着非常差，换言之，切割边缘上有很多腐蚀。结果示于下表2中：
*：根据本发明的实施例。
试验件5至11在经涂覆的钢板的切割边缘上具有非常好的抗腐蚀保护。相比之下，试验件12在切割边缘上未示出足够的耐腐蚀性。
实施例3：电化学行为测试：
制备试验件13至16并进行电化学电位测试。
实现了包括测量经涂覆的钢表面板的电化学电位的测试。将钢板和涂层分离并浸入包含5重量％氯化钠的溶液(pH为7)中。将饱和甘汞电极(SCE)也浸入该溶液中。随时间测量表面的耦合电位。结果示于下表3中：
*：根据本发明的实施例。
试验件13至15是牺牲层，例如锌涂层。根据需要，耦合电位小于-0.78V/SCE。
实施例4：腐蚀测试：
制备试验件17至20，并进行腐蚀测试以评估经涂覆的钢板的保护。
实现了包括根据标准VDA233-102对经涂覆的钢板进行腐蚀循环的测试。为此，将试验件放入室中，其中使1％重量％的氯化钠水溶液以3mL·小时-1的流量蒸发到试验件上。温度在50℃至-15℃之间变化，并且湿度率在50％至100％之间变化。图1示出了对应于168小时(即一周)的一个周期。
通过肉眼观察经涂覆的钢板上的腐蚀的存在：0意味着优异，换言之，几乎没有或没有腐蚀；5意味着非常差，换言之，有很多腐蚀。结果示于下表4中：
*：根据本发明的实施例，ND：未进行。
试验件17至19显示出优异的抗腐蚀保护，特别是当涂层包含镁(试验件18和19)时。
实施例5：对刮擦试验件的腐蚀测试
制备试验件21至24，并进行腐蚀测试以评估经涂覆的钢板的保护。
首先，以0.5mm、1mm和2mm的宽度对所有试验件进行刮擦。然后根据图1所示的标准VDA 233-102对所有试验件进行腐蚀循环。
通过肉眼观察经涂覆的钢板的划痕周围的腐蚀的存在：0意味着优异，换言之，在划痕周围几乎没有或没有腐蚀；5意味着非常差，换言之，刮痕周围有很多腐蚀。结果示于下表5中：
*：根据本发明的实施例。
根据本发明的试验件(试验件21至23)具有优异的抗腐蚀保护，特别是当涂层包含时(试验件22和23)镁。
实施例6：对经热处理和刮擦的试验件进行的腐蚀测试
制备试验件25至28，并进行腐蚀测试以评估奥氏体化处理之后经涂覆的钢板的保护。
将所有的试验件切割以获得坯件。然后在5分钟至10分钟的停留时间期间在900℃的温度下加热坯件。将坯件转移至压制工具中并进行热冲压以获得部件。然后，使部件冷却以通过马氏体相变获得硬化。根据图1所示的标准VDA 233-102对所有的试验件进行6个腐蚀循环。
通过肉眼观察经涂覆的钢板的划痕周围的腐蚀的存在：0意味着优异，换言之，在划痕周围几乎没有或没有腐蚀；5意味着非常差，换言之，在划痕周围有很多腐蚀。结果示于下表6中：
*：根据本发明的实施例。
与包含铝和硅的涂层(试验件28)相比，试验件25至27显示出良好的抗腐蚀保护。
实施例7：电化学行为测试：
制备试验件29至40，并在奥氏体化处理之后进行电化学电位测试。
将所有的试验件切割以获得坯件。然后在5分钟的停留时间期间将坯件在900℃的温度下加热。将坯件转移至压制工具中并进行热冲压以获得部件。然后，使部件冷却以通过马氏体相变获得硬化。
实现了包括测量经涂覆的钢表面板的电化学电位的测试。将钢板和涂层分离并浸入包含5重量％氯化钠的溶液(pH为7)中。将饱和甘汞电极(SCE)也浸入该溶液中。随时间测量牺牲保护的能力(也称为电耦合(galvanic coupling))。换言之，已经评估了在这些条件下涂层保持牺牲多久的时间。结果示于下表7中：
*：根据本发明的实施例。
根据本发明的试验件32至39为牺牲保护，并且随着时间保持牺牲保护。
本发明还涉及以下实施方案：
实施方案1.一种涂覆有金属涂层的钢板，所述金属涂层包含2.0重量％至24.0重量％的锌，7.1重量％至12.0重量％的硅，任选的1.1重量％至8.0重量％的镁和任选的选自Pb、Ni、Zr或Hf的另外的元素，每种另外的元素以重量计的含量小于0.3重量％，余量为铝和任选地不可避免的杂质和残留元素，其中比率Al/Zn大于2.9。
实施方案2.根据实施方案1所述的钢板，其中比率Al/Zn小于或等于8.5。
实施方案3.根据实施方案2所述的钢板，其中比率Al/Zn为3.0至7.5。
实施方案4.根据实施方案3所述的钢板，其中比率Al/Zn为4.0至6.0。
实施方案5.根据实施方案1至4中任一项所述的钢板，其中所述金属涂层的显微组织包含Al-Zn相。
实施方案6.根据实施方案1至5中任一项所述的钢板，其中所述涂层包含10.0重量％至20.0重量％的锌。
实施方案7.根据实施方案6所述的钢板，其中所述涂层包含10.0重量％至15.0重量％的锌。
实施方案8.根据实施方案1至7中任一项所述的钢板，其中所述涂层包含8.1重量％至10.0重量％的硅。
实施方案9.根据实施方案1至8中任一项所述的钢板，其中所述涂层包含3.0重量％至8.0重量％的镁。
实施方案10.根据实施方案9所述的钢板，其中所述涂层包含3.0重量％至5.0重量％的镁。
实施方案11.根据实施方案1至10中任一项所述的钢板，其中所述涂层的显微组织包含Mg2Si相。
实施方案12.根据实施方案1至11中任一项所述的钢板，其中所述涂层的显微组织包含MgZn2相。
实施方案13.根据实施方案1至12中任一项所述的钢板，其中铝的量大于71重量％。
实施方案14.根据实施方案1至13中任一项所述的钢板，其中铝的量大于76重量％。
实施方案15.根据实施方案1至14中任一项所述的钢板，其中所述涂层的厚度为5μm至50μm。
实施方案16.根据实施方案15所述的钢板，其中所述厚度为10μm至35μm。
实施方案17.根据实施方案16所述的钢板，其中所述厚度为12μm至18μm。
实施方案18.根据实施方案16所述的钢板，其中所述厚度为26μm至31μm。
实施方案19.根据实施方案1至18中任一项所述的钢板，其中所述涂层不包含选自以下的元素：Cr、Mn、Ti、Ce、La、Nd、Pr、Ca、Bi、In、Sn和Sb或其组合。
实施方案20.一种能够通过热成形或冷冲压或这二者由根据实施方案1至19中任一项所述的经涂覆的钢板获得的涂覆有金属涂层的部件。
实施方案21.根据实施方案20所述的部件，所述部件为具有可变厚度的压制硬化的钢部件。
实施方案22.根据实施方案21所述的部件，其中所述可变厚度通过连续柔性轧制过程产生。
实施方案23.根据实施方案20至22中任一项所述的部件，所述部件为不等厚轧制板。
实施方案24.根据实施方案20至23中任一项所述的部件，所述部件为前纵梁、座椅横向构件、门框下边梁构件、前围挡板横向构件、前底板加强件、后底板横向构件、后纵梁、B柱、门框或shotgun。
实施方案25.根据实施方案20至24中任一项所述的部件用于制造机动车辆的用途。
Claims (19)
1.一种通过压制硬化生产经涂覆的部件的方法，包括以下步骤：
A)提供预涂覆有金属涂层的钢板，所述金属涂层包含2.0重量％至24.0重量％的锌，7.1重量％至12.0重量％的硅，任选的1.1重量％至8.0重量％的镁和任选的选自Pb、Ni、Zr或Hf的另外的元素，每种另外的元素以重量计的含量小于0.3％，余量为铝和不可避免的杂质和残留元素，其中比率Al/Zn大于2.9，
B)切割经涂覆的钢板以获得坯件，
C)在840℃至950℃的温度下对所述坯件进行热处理，以在钢中获得完全奥氏体显微组织，
D)将所述坯件转移至压制工具中，
E)使所述坯件热成形以获得部件，
F)使步骤E)中获得的所述部件冷却，以在钢中获得这样的显微组织：所述显微组织为马氏体或马氏体-贝氏体，或者由至少75％的等轴铁素体、5％至20％的马氏体和小于或等于10％的量的贝氏体构成。
2.根据权利要求1所述的方法，其中对所述坯件进行热处理在炉中在非保护性气氛下进行。
3.根据权利要求2所述的方法，其中对所述坯件进行热处理在880℃至930℃的温度下进行。
4.根据权利要求1至3中任一项所述的方法，其中所述热成形在600℃至830℃的温度下进行。
5.一种通过冷冲压生产经涂覆的部件的方法，包括：
-提供预涂覆有金属涂层的钢板，所述金属涂层包含2.0重量％至24.0重量％的锌，7.1重量％至12.0重量％的硅，任选的1.1重量％至8.0重量％的镁和任选的选自Pb、Ni、Zr或Hf的另外的元素，每种另外的元素以重量计的含量小于0.3％，余量为铝和不可避免的杂质和残留元素，其中比率Al/Zn大于2.9，
-切割所述钢板以获得坯件，
-对所述坯进行冷冲压以获得所述经涂覆的部件。
6.根据权利要求1至5中任一项所述的方法，其中比率Al/Zn小于或等于8.5，优选为3.0至7.5，优选为4.0至6.0。
7.根据权利要求1至6中任一项所述的方法，其中所述钢板的所述金属涂层的显微组织包含Al-Zn相。
8.根据权利要求1至7中任一项所述的方法，其中所述钢板的所述金属涂层包含10.0重量％至20.0重量％的锌，优选10.0重量％至15.0重量％的锌。
9.根据权利要求1至8中任一项所述的方法，其中所述钢板的所述金属涂层包含8.1重量％至10.0重量％的硅。
10.根据权利要求1至9中任一项所述的方法，其中所述钢板的所述金属涂层包含3.0重量％至8.0重量％的镁，优选3.0重量％至5.0重量％的镁。
11.根据权利要求1至10中任一项所述的方法，其中所述钢板的所述金属涂层的显微组织包含Mg2Si相。
12.根据权利要求1至11中任一项所述的方法，其中所述钢板的所述金属涂层的显微组织包含MgZn2相。
13.根据权利要求1至12中任一项所述的方法，其中所述钢板的所述金属涂层中铝的量大于71重量％，优选大于76重量％。
14.根据权利要求1至13中任一项所述的方法，其中所述钢板的所述金属涂层的厚度为5μm至50μm，优选为10μm至35μm。
15.根据权利要求1至14中任一项所述的方法，其中所述钢板的所述金属涂层不包含选自以下的元素：Cr、Mn、Ti、Ce、La、Nd、Pr、Ca、Bi、In、Sn和Sb或其组合。
16.一种涂覆有金属涂层的部件，通过对预涂覆有金属涂层的钢板进行压制硬化来生产，所述金属涂层包含2.0重量％至24.0重量％的锌，7.1重量％至12.0重量％的硅，任选的1.1重量％至8.0重量％的镁和任选的选自Pb、Ni、Zr或Hf的另外的元素，每种另外的元素以重量计的含量小于0.3％，余量为铝和不可避免的杂质和残留元素，比率Al/Zn大于2.9，所述部件中钢的显微组织为马氏体或马氏体-贝氏体，或者由至少75％的等轴铁素体、5％至20％的马氏体和小于或等于10％的量的贝氏体构成。
17.根据权利要求16所述的部件，其中所述部件具有可变厚度。
18.根据权利要求16或17中任一项所述的部件，其中所述部件为前纵梁、座椅横向构件、门框下边梁构件、前围挡板横向构件、前底板加强件、后底板横向构件、后纵梁、B柱、门框或shotgun。
19.根据权利要求16至18中任一项所述的部件用于制造机动车辆的用途。
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