CN104302802A - 设置有提供牺牲阴极保护的涂层的钢板、利用这样的板制造部件的方法以及所得部件 - Google Patents
设置有提供牺牲阴极保护的涂层的钢板、利用这样的板制造部件的方法以及所得部件 Download PDFInfo
- Publication number
- CN104302802A CN104302802A CN201280073231.4A CN201280073231A CN104302802A CN 104302802 A CN104302802 A CN 104302802A CN 201280073231 A CN201280073231 A CN 201280073231A CN 104302802 A CN104302802 A CN 104302802A
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- China
- Prior art keywords
- coating
- steel plate
- steel
- supercoat
- sacrificing cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 82
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 74
- 239000010959 steel Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000004210 cathodic protection Methods 0.000 title abstract 2
- 239000011701 zinc Substances 0.000 claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 229910052738 indium Inorganic materials 0.000 claims abstract description 11
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004411 aluminium Substances 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 230000001186 cumulative effect Effects 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 31
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910001563 bainite Inorganic materials 0.000 claims description 3
- 229910000734 martensite Inorganic materials 0.000 claims description 3
- 238000003825 pressing Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- 208000034189 Sclerosis Diseases 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 229910000765 intermetallic Inorganic materials 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001374 Invar Inorganic materials 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 229910020900 Sn-Fe Inorganic materials 0.000 description 2
- 229910019314 Sn—Fe Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229910018619 Si-Fe Inorganic materials 0.000 description 1
- 229910008289 Si—Fe Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 230000005495 cold plasma Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/12—Electrodes characterised by the material
- C23F13/14—Material for sacrificial anodes
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- 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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- 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
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/001—Heat treatment of ferrous alloys containing Ni
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C—CHEMISTRY; METALLURGY
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- 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
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- C21D6/008—Heat treatment of ferrous alloys containing Si
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- 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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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
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- C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C—ALLOYS
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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Abstract
本发明涉及设置有提供牺牲阴极保护的涂层的钢板,该涂层包含:5wt%至50wt%之间的锌、0.1wt%至15wt%之间的硅、以及任选的最高达10wt%的镁和根据累积含量最高达0.3wt%的附加元素,该涂层还包含:选自0.1wt%至5wt%之间的锡、0.01wt%至0.5wt%之间的铟、及其组合的保护元素;余量为铝和残余元素或不可避免的杂质。本发明还涉及用于通过热压或冷压来制造部件的方法以及所得部件。
Description
本发明涉及设置有牺牲阴极保护涂层的钢板,特别是旨在制造汽车部件的钢板,但是该钢板并不限于该应用。
目前,仅有锌或锌合金涂层由于双重阻挡层和阴极保护而提供了提高的防腐蚀保护程度。通过将涂层应用到钢的表面获得了阻挡层效应,因此防止了钢与腐蚀性介质之间的任何接触,并且不依赖于涂层和基板的性质。另一方面,牺牲阴极保护基于如下事实:锌是比钢廉价的金属,并且在腐蚀条件下,锌比钢先被消耗。在钢直接暴露于腐蚀性环境的区域中(例如其中钢是裸露的切割边缘或损坏区)和其中周围锌会在对未涂覆区的任何侵蚀之前被消耗的区域中,这种阴极保护尤其至关重要,。
然而,由于锌的熔点低,所以锌在部件必须被焊接时由于存在锌会蒸发的危险而产生问题。解决该问题的一种可能的方法是减小涂层的厚度,但是这限制了表面被防腐蚀保护的时间长度。此外,当板特别地通过热冲压被压制硬化时,观察到在钢中从涂层扩展的微裂纹的形成。同样地,由于在预先涂覆有锌然后被压制硬化的某些部件表面上存在脆性氧化物层,因此这样的部件的喷涂在涂覆磷酸锌之前需要喷砂操作。
通常用于生产汽车部件的其他类型的金属涂层是基于铝和硅的涂层类型。当这些涂层变形时由于存在金属间化合物Al-Si-Fe的层,这些涂层在钢中不产生微裂纹并且对喷涂有很好的适用性。尽管它们有可能通过阻挡层效应获得保护并且可焊接,但是它们不提供阴极保护。
因此,本发明的目的是通过制造可用的涂覆钢板来弥补现有技术的涂层的缺点,所述涂覆钢板在特别通过冲压处理前后具有高度的防腐蚀保护。当板被用于压制硬化(特别地通过热冲压)时,还期望对抗钢中微裂纹扩展并且在先于压制硬化的热处理期间在时间和温度方面优选具有尽可能最大的利用窗口。
在表面阴极保护方面,目的是实现比钢的电化学电位更负至少50mV的电化学电位,即相对于饱和甘汞电极(SCE)的最小值-0.75V。然而,不期望低于-1.4V或甚至低于-1.25V的值,这将导致涂层的过快消耗,最终会减少钢受保护的时间长度。
为此,本发明的目的是设置有牺牲阴极保护涂层的钢板,该涂层包含:5wt%至50wt%的锌、0.1wt%至15wt%的硅、以及任选的最高达10wt%的镁和累积含量最高达0.3wt%的附加元素,并且该涂层还包含:选自按重量百分比计在0.1%至5%之间的锡、按重量百分比计在0.01%至0.5%之间的铟、以及它们的组合的一种保护元素;余量为铝和残余元素或不可避免的杂质。
本发明所要求保护的板也可以并入以下单独或组合考虑的特征:
-涂层的保护元素为按重量百分比计在1%至3%之间的锡,
-涂层的保护元素为按重量百分比计在0.02%至0.1%之间的铟,
-涂层包含20wt%至40wt%的锌和任选的含量为1wt%至10wt%的镁,
-涂层包含20wt%至30wt%的锌和任选的含量为3wt%至6wt%的镁,
-涂层包含8wt%至12wt%的硅,
-涂层包含含量为2wt%至5wt%的铁作为残余元素,
-钢板的钢包含:按重量百分比计0.15%<C<0.5%、0.5%<Mn<3%、0.1%<硅<0.5%、Cr<1%、Ni<0.1%、Cu<0.1%、Ti<0.2%、Al<0.1%、P<0.1%、S<0.05%、0.0005%<B<0.08%、以及余量为铁和因钢的加工而产生的不可避免的杂质,
-涂层的厚度在10μm至50μm之间,
-涂层通过热浸镀获得。
本发明的另一目的包括用于制造设置有牺牲阴极保护涂层的钢部件的方法,该方法包括依次进行的以下步骤,所述步骤包括:
-获得本发明所要求保护的预先涂覆的钢板,然后
-对该板进行切割以获得坯料,然后
-将坯料在非保护性气氛中加热至840℃至950℃之间的奥氏体化温度Tm,
-将坯料在此温度Tm下保持1分钟至8分钟之间的时间段tm,然后
-对该坯料进行热冲压以获得经涂覆钢部件,所述经涂覆钢部件以一定速率冷却,使得钢的显微组织包括选自马氏体和贝氏体中的至少一种组分,
-其中温度Tm、时间段tm、预先涂覆层的厚度以及该预先涂覆层中的保护元素、锌和任选的镁的含量被选择成使得在所述部件的涂层上部中的铁的最终平均含量小于75wt%。
在一个优选的实施方案中,预先涂覆层的厚度大于或等于27μm,预先涂覆层中的锡含量大于或等于1wt%,预先涂覆层中的锌含量大于或等于20wt%。
本发明的另一目的包括设置有牺牲阴极保护涂层的部件,该部件能够通过本发明所要求保护的方法来获得或者通过对本发明所要求保护的板进行冷冲压来获得,并且该部件旨在特别用于汽车行业。
以下将参照通过非限制性实施例的方式示出的具体实施方案对本发明进行更详细地描述。
正如所要证实的,本发明涉及设置有涂层的钢板,该涂层首先包含选自锡、铟以及其组合的保护元素。
鉴于其在市场上各自的可用性,优选使用百分比在0.1wt%至5wt%之间、优选为在0.5wt%至4wt%之间、更优选为在1wt%至3wt%之间、或者甚至为在1wt%至2wt%之间的锡。然而,可以考虑使用铟,其与锡相比具有更大的保护能力。其可以单独使用或者附加锡使用,铟的含量为0.01wt%至0.5wt%,优选为0.02wt%至0.1wt%,并且最优选为0.05wt%至0.1wt%。
本发明所要求保护的板的涂层还包含5wt%至50wt%的锌和任选的最高达10%的镁。发明人已经发现,在包含或不包含氯离子的环境中,与上述保护元素相关联的这些元素使得可以降低涂层相对于钢的电化学电位。因此,本发明所要求保护的涂层提供了牺牲阴极保护。
优选使用锌,其保护效果大于镁的保护效果,并且锌因为不易氧化而较容易使用。另外,优选使用10wt%至40wt%、20wt%至40wt%、或者甚至20wt%至30wt%的锌,其与1wt%至10wt%或甚至3wt%至6wt%的镁结合或不结合使用。
本发明所要求保护的板的涂层还包含0.1wt%至15wt%、优选为0.5wt%至15wt%、最优选为1wt%至15wt%、或甚至8wt%至12wt%的硅,硅是特别使得可以赋予板高水平抗高温氧化的一种元素。硅的存在还使得在最高达650℃下使用板而不存在涂层剥落的危险。另外,硅使得可以防止在热浸镀涂覆期间形成金属间铁-锌厚层,所述金属间化合物层会降低涂层的粘附性和可成形性。存在大于8wt%的硅含量也使得板最特别地适合于压制硬化,尤其适用于通过热冲压成形。优选使用量在8%至12%之间的硅。含量大于15wt%是不期望的,因为随后它形成可能劣化涂层的性质、尤其是耐腐蚀性的初晶硅。
本发明所要求保护的板的涂层还可以包含累积含量最高达0.3wt%,优选最高达0.1wt%,或甚至小于0.05wt%的附加元素,例如Sb、Pb、Ti、Ca、Mn、La、Ce、Cr、Ni、Zr或Bi。例如,这些不同元素尤其可以改善涂层的耐腐蚀性或者甚至它的脆性或粘附性。熟悉这些元素对涂层特性的作用的本领域技术人员会知道如何作为所寻求的附加目的的功能而使用它们,达到该效果的合适比例通常会在20ppm至50ppm之间。也已经证实这些元素不阻碍本发明的内容所寻求的主要特性。
本发明所要求保护的板的涂层还可以包含残余元素以及特别地源于由钢带的传送所引起的热浸镀锌槽污染的不可避免的杂质、或者由于用于供给这些槽的铸锭或用于供应真空沉积工艺的铸锭产生的杂质。可特别提及的是作为残余元素的铁,其可以在热浸镀涂层中以最高达5wt%的量、一般为2wt%至4wt%存在。
最后,本发明所要求保护的板的涂层包含铝,铝的含量可以为约20wt%至近90wt%。该元素可以通过阻挡层效应提供板的防腐蚀保护。其提高了涂层的熔化温度和蒸发温度,从而使得可以更容易地使用板特别地用于热冲压并且在延长范围的时间和温度下使用。当钢板的组成和/或工件的最终显微组织需要其在高温和/或长时间下经受奥氏体化时,这可特别引起关注。
因此,会理解的是,根据本发明所要求保护的部件所需要的性质,涂层中的主要元素可以是锌或铝。
涂层的厚度将优选为10μm至50μm。低于10μm时,对带的防腐蚀保护可能不足。高于50μm时,防腐蚀保护超过所需水平,特别是在汽车领域。另外,如果厚度在此范围内的涂层经受显著的温度升高和/或长时间段,则存在涂层的上部可能会熔化并流到炉辊上或流到冲压模具中的风险,这会对它们造成损坏。
关于用于本发明所要求保护的板的钢,钢的类型不是关键的,只要涂层可以充分地粘附到钢即可。
但是,对于需要高水平机械强度的某些应用如用于汽车的结构部件,根据部件将被使用的条件,优选组成能使得部件具有500MPa至1600MPa的拉伸强度的钢。
在此强度范围内,特别优选使用以下钢组成,该钢组成包含:按重量百分比计:0.15%<C<0.5%、0.5%<Mn<3%、0.1%<Si<0.5%、Cr<1%、Ni<0.1%、Cu<0.1%,Ti<0.2%、Al<0.1%、P<0.1%、S<0.05%、0.0005%<B<0.08%、余量为铁和因钢的加工而产生的不可避免的杂质。市售钢的一个实例是22MnB5。
当期望的强度水平为约500MPa时,优选使用以下钢组成,该钢组成包含:0.040%≤C≤0.100%、0.80%≤Mn≤2.00%、Si≤0.30%、S≤0.005%、P≤0.030%、0.010%≤Al≤0.070%、0.015%≤Nb≤0.100%、0.030%≤Ti≤0.080%、N≤0.009%、Cu≤0.100%、Ni≤0.100%、Cr≤0.100%、Mo≤0.100%、Ca≤0.006%、余量为铁和因钢的加工而产生的不可避免的杂质。
根据可在例如0.7mm至3mm之间变化的所需最终厚度,钢板可以通过热轧并且可以任选地被再冷轧来制造。
钢板可以通过任何合适的方法进行涂覆,例如电沉积法、或者真空沉积法或在接近大气压的压力下沉积(如通过溅射磁控管、冷等离子体或真空蒸发法),不过优选通过在熔融金属槽中的热浸镀法获得钢板。值得注意的是,表面阴极保护对于通过热浸镀获得的涂层比通过其他涂覆方法获得的涂层更显著。
然后,本发明所要求保护的板可以使用任何适合于待制造部件的结构和形式的方法如冷冲压形成。
然而,本发明所要求保护的板最特别地适合于制造压制硬化的部件,特别是通过热冲压来制造。
此方法包括:获得本发明所要求保护的已预先涂覆的钢板,然后对该板进行切割以获得坯料。然后将该坯料在炉中在非保护性气氛下加热至840℃至950℃之间、优选在880℃至930℃之间的奥氏体化温度Tm;然后将该坯料在此温度Tm下保持1分钟至8分钟之间、优选为4分钟至6分钟之间的时间段tm。
温度Tm和保持时间段tm不仅取决于钢的性质,而且取决于待被冲压的板的厚度,在其成型之前必须是完全处于奥氏体范围内。温度Tm越高,保持时间段tm会越短,反之亦然。另外,温度上升的速率也会影响这些参数,从而高的上升速率(例如,大于30℃/秒)也使得可以减少保持时间段tm。
然后将坯料转移到热冲压模具并且进行冲压。然后将所获得的部件在冲压模具本身中进行冷却或转移到特定的冷却模具之后进行冷却。
在所有情况下控制冷却速率作为钢的组分的函数,使得在热冲压完成时钢的最终显微组织包括选自马氏体和贝氏体中的至少一种成分,以实现期望水平的机械强度。
保证经涂覆和热冲压的部件将确实具有牺牲阴极保护的要点是调节温度Tm、时间段tm、预先涂覆层的厚度以及该预先涂覆层中的保护元素、锌和任选的镁的含量,使得在部件的涂层上部中的铁的最终平均含量小于75wt%,优选小于50wt%,或者甚至小于30wt%。所述上部的厚度为至少5μm。
在加热至奥氏体化温度Tm的作用下,源自基板的铁扩散到预先涂覆层并提高了预先涂覆层的电化学电位。为了维持满意的阴极保护,因此有必要限制在部件的最终涂层上部中的平均铁含量。
为此,可以限制温度Tm和/或保持时间段tm。也可以提高预先涂覆层的厚度以防止铁的扩散前缘到达涂层的表面。在这方面,优选使用预先涂覆层厚度大于或等于27μm、优选大于或等于30μm或甚至大于或等于35μm的板。
为了限制最终涂层的阴极保护能力的降低,也可以增加在预先涂覆层中的保护元素、锌和任选的镁的含量。
在任何情况下本领域的技术人员将能够在考虑钢性质的同时调节这些不同的参数,以获得表现出本发明所要求品质的压制硬化的经涂覆的钢部件,特别是热冲压的部件。
进行试验以说明本发明的某些实施方案。
试验
实施例1-Al-Si-Zn-In-Fe涂层
利用1.5mm厚的设置有热浸镀涂层的22MnB5冷轧板进行试验,该热浸镀涂层包含:按重量百分比计20%的锌、10%的硅、3%的铁,0.1%的铟、余量为铝和不可避免的杂质,该热浸镀涂层的厚度为约15μm。
将这些板在5%NaCl的环境中进行常规电化学测量,以饱和甘汞电极为参比电极。
值得注意的是,经涂覆板的电化学电位为-0.95V/SCE。因此本发明所要求保护的板确实具有牺牲阴极保护作用。在相同的测量条件下,验证了其他相同但设置有既不含有锌也不含有铟的涂层的板的电化学电位为-0.70V/SCE,该涂层对该板不提供阴极保护。
为了评估热冲压之后的残余保护,附加测试包括将本发明所要求保护的板(该板与之前使用的那些板相同)加热至900℃的温度持续可变的时间长度。观察到经处理3分钟的板的电化学电位仍然为-0.95V/SCE,从而表明保持有牺牲阴极保护。高于该处理温度,超过5μm厚度的涂层的上部中的平均铁含量大于75wt%,并且电化学电位下降到-0.70V/SCE。
关于微裂纹从涂层到板的扩展,在钢涂层界面处观察到形成厚的金属间化合物层,该金属间化合物层在奥氏体化完成时仍存在。
实施例2-Al-Si-Zn-Mg-Sn-Fe涂层
利用1.5mm厚的设置有热浸镀涂层的22MnB5冷轧板进行试验,该热浸镀涂层包含:按重量百分比计10%的硅、10%的锌、6%的镁、3%的铁和0.1%的锡,余量为铝和不可避免的杂质,该热浸镀涂层的平均厚度为17μm。
将这些板在5%NaCl的环境中进行常规电化学测量,以饱和甘汞电极为参比电极。
值得注意的是,经涂覆板的电化学电位为-0.95V/SCE。同时设置有包含10%的硅和余量由铝和不可避免的杂质组成的涂层的相同板的电化学电位为-0.70V/SCE。因此本发明所要求保护的板确实具有牺牲阴极保护。
为了评估热冲压之后的残余保护,附加测试包括将本发明所要求保护的板(该板与之前使用的那些板相同)加热至900℃的温度持续可变的时间长度。观察到经处理2分钟的板的电化学电位仍然为-0.95V/SCE,从而表明保持有牺牲阴极保护。高于该处理温度,超过5μm厚度的涂层的上部中的平均铁含量大于75wt%,并且电化学电位下降到-0.70V/SCE。
然后验证了使用平均厚度为27μm的涂层使得可以在保持该阴极保护的情况下在900℃下增加奥氏体化Tm的持续时间至5分钟。
关于微裂纹从涂层到板的扩展,在钢涂层界面处观察到形成厚的金属间化合物层,该金属间化合物层在奥氏体化完成时仍存在。
实施例3-具有In或不具有In的Al-Zn-Si-Sn-Fe涂层
利用1.5mm厚的设置有热浸镀涂层的22MnB5冷轧板进行类似附加试验,下表中给出了该热浸镀涂层的特征,该热浸镀涂层的厚度为约32μm。
参考 | %Al | %Zn | %Si | %Sn | %Fe | %In |
A | 76 | 10 | 10 | 1 | 3 | - |
B | 66 | 20 | 10 | 1 | 3 | - |
C | 56 | 30 | 10 | 1 | 3 | - |
D | 46 | 40 | 10 | 1 | 3 | - |
E | 45.9 | 40 | 10 | 1 | 3 | 0.1 |
这些试验的结果将证实确实已经实现本发明寻求的性质。
Claims (14)
1.一种设置有牺牲阴极保护涂层的钢板,所述涂层包含:5wt%至50wt%的锌、0.1wt%至15wt%的硅、以及任选的最高达10wt%的镁和累积含量最高达0.3wt%的附加元素,并且所述涂层还包含:选自按重量百分比计0.1%至5%的锡、按重量百分比计0.01%至0.5%的铟及其组合的保护元素;余量为铝和残余元素或不可避免的杂质。
2.根据权利要求1所述的设置有牺牲阴极保护涂层的钢板,其中所述保护元素为按重量百分比计1%至3%的锡。
3.根据权利要求1所述的设置有牺牲阴极保护涂层的钢板,其中所述保护元素为按重量百分比计在0.02%至0.1%之间的铟。
4.根据权利要求1至3中任一项所述的设置有牺牲阴极保护涂层的钢板,所述钢板的所述涂层包含20wt%至40wt%的锌和任选的含量为1wt%至10wt%的镁。
5.根据权利要求4所述的设置有牺牲阴极保护涂层的钢板,所述钢板的所述涂层包含20wt%至30wt%的锌和任选的含量为3wt%至6wt%的镁。
6.根据权利要求1至5中任一项所述的设置有牺牲阴极保护涂层的钢板,所述钢板的所述涂层包含8wt%至12wt%的硅。
7.根据权利要求1至6中任一项所述的设置有牺牲阴极保护涂层的钢板,所述钢板的所述涂层包含2wt%至5wt%的含量的铁作为残余元素。
8.根据权利要求1至7中任一项所述的设置有牺牲阴极保护涂层的钢板,其中所述钢包含:按重量百分比计0.15%<C<0.5%、0.5%<Mn<3%、0.1%<硅<0.5%、Cr<1%、Ni<0.1%、Cu<0.1%、Ti<0.2%、Al<0.1%、P<0.1%、S<0.05%、0.0005%<B<0.08%、以及余量为铁和因所述钢的加工而产生的不可避免的杂质。
9.根据权利要求1至8中任一项所述的设置有牺牲阴极保护涂层的钢板,其中所述涂层的厚度为10μm至50μm。
10.根据权利要求1至9中任一项所述的设置有牺牲阴极保护涂层的钢板,所述钢板的所述涂层通过热浸镀获得。
11.一种用于制造设置有牺牲阴极保护涂层的钢部件的方法,所述方法包括依次进行的以下步骤,所述步骤包括:
-获得根据权利要求1至10中任一项所述的预先涂覆的钢板,然后
-对所述板进行切割以获得坯料,然后
-将所述坯料在非保护性气氛中加热至840℃至950℃之间的奥氏体化温度Tm,然后
-将所述坯料在所述温度Tm下保持1分钟至8分钟之间的时间段tm,然后
-对所述坯料进行热冲压以获得经涂覆钢部件,以一定速率冷却所述经涂覆钢部件,使得所述钢的显微组织包括选自马氏体和贝氏体中的至少一种成分,
-所述温度Tm、所述时间段tm、预先涂覆层的厚度以及所述预先涂覆层中的保护元素、锌和任选的镁的含量被选择成使得在所述部件的所述涂层上部中的铁的最终平均含量小于75wt%。
12.根据权利要求11所述的方法,其中所述预先涂覆层的厚度大于或等于27μm,所述预先涂覆层中的锡含量大于或等于1wt%,所述预先涂覆层中的锌含量大于或等于20wt%。
13.一种设置有牺牲阴极保护涂层的钢部件,所述钢部件能够通过根据权利要求11或12所述的方法来获得。
14.一种设置有牺牲阴极保护涂层的钢部件,所述钢部件能够通过对根据权利要求1至10中任一项所述的板进行冷冲压来获得。
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AU2012377741B2 (en) | 2016-03-17 |
RS56715B1 (sr) | 2018-03-30 |
HRP20171855T1 (hr) | 2018-01-12 |
CA2870532C (fr) | 2016-12-13 |
NO2839049T3 (zh) | 2018-03-17 |
KR101886611B1 (ko) | 2018-08-09 |
ZA201407327B (en) | 2017-08-30 |
EP2839049A1 (fr) | 2015-02-25 |
EA030016B1 (ru) | 2018-06-29 |
UA112688C2 (uk) | 2016-10-10 |
JP6348105B2 (ja) | 2018-06-27 |
KR20150008114A (ko) | 2015-01-21 |
EP2839049B1 (fr) | 2017-10-18 |
CA2870532A1 (fr) | 2013-10-24 |
EA201401136A1 (ru) | 2015-03-31 |
AU2012377741A1 (en) | 2014-12-04 |
PT2839049T (pt) | 2018-01-08 |
ES2652028T3 (es) | 2018-01-31 |
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