CN114787420A - 镀铝系合金钢板及制造其的方法 - Google Patents
镀铝系合金钢板及制造其的方法 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 79
- 239000010959 steel Substances 0.000 title claims abstract description 79
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000007747 plating Methods 0.000 claims abstract description 116
- 229910007570 Zn-Al Inorganic materials 0.000 claims abstract description 34
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 29
- 239000000956 alloy Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 229910000838 Al alloy Inorganic materials 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 238000005240 physical vapour deposition Methods 0.000 claims description 8
- 238000001771 vacuum deposition Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000005328 electron beam physical vapour deposition Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 68
- 239000011701 zinc Substances 0.000 description 38
- 229910019142 PO4 Inorganic materials 0.000 description 29
- 239000010452 phosphate Substances 0.000 description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 28
- 238000011282 treatment Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 229910001338 liquidmetal Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- 229910000797 Ultra-high-strength steel Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
本发明涉及一种镀铝系合金钢板及制造其的方法,更详细地,涉及一种可以优选应用于汽车钢板等的镀铝系合金钢板及制造其的方法。本发明的一个实施方案提供一种镀铝系合金钢板及制造其的方法,所述镀铝系合金钢板包括:基础钢板;Al系合金镀层,其形成在所述基础钢板的至少一面上;以及Zn‑Al系镀层,其形成在所述Al系合金镀层上,以重量%计,所述Zn‑Al系镀层包含Al:0.5‑1.0%、余量的Zn和不可避免的杂质,并且所述Zn‑Al系镀层的镀覆附着量为3‑12g/m2。
Description
技术领域
本发明涉及一种镀铝系合金钢板及制造其的方法,更详细地,涉及一种可以优选应用于汽车钢板等的镀铝系合金钢板及制造其的方法。
背景技术
镀铝钢板和镀铝合金钢板由于具有镀锌钢板和镀锌合金钢板所不具有的各种优点,已经用于各种工业领域。特别是在近年来开发的各种高强度钢上进行这种铝合金镀覆时,不发生点焊时发生的液态金属致脆现象,可以确保牺牲防蚀性特性和涂膜粘附性,因此对铝合金的镀覆的关注度正在逐渐增加。
如上所述,镀铝系钢板通过与各种元素的合金化来持续改善和完善其缺点,但由于镀层的大部分由铝组成,因此具有本质上不可能进行现有汽车公司中最常用的锌系后处理的局限性。最具有代表性的磷酸盐处理的情况下,磷酸盐被锌取代并形成薄膜的形式,但铝合金镀覆的情况下,没有可以与磷酸盐溶液反应的锌或锌的量不足,从而无法形成正常的磷酸盐薄膜。因此,为了将镀铝合金钢板应用于汽车,需要在汽车生产线以外的额外的产线进行镀铝用磷酸盐处理后使用,或者将现有的锌系磷酸盐处理溶液全部变更为铝用溶液,因此需要额外的处理,不可能进行连续生产,并且发生变更溶液导致的生产成本和生产时间大幅增加的问题。
因此,即使镀铝合金钢板可以解决现有镀锌系钢板的由来已久的问题并具有各种优点,但由于汽车公司的生产成本增加的问题,目前其应用受到很大限制,例如,仅用于无需后处理的部分结构用内饰材料。
为了克服这种问题,专利文献1中提出了一种通过PVD方法将Zn镀覆在镀Al钢板表面来进行改善的方法。但是,在专利文献1中提出的技术的情况下,由于镀覆的Zn的高延展性,耐刮擦性降低,在冲压等成型工艺中在镀覆钢板表面产生大量的划痕,或者由于摩擦系数和拉毛性低,模具的污染严重,发生生产性降低的新问题,因此在实际应用中受到限制。
[现有技术文献]
(专利文献1)韩国专利公开公报第1995-0027278号
发明内容
本发明要解决的技术问题
为了解决上述现有技术的问题,本发明的一个方面提供一种可以进行汽车公司通常进行的锌系后处理,焊接部不发生液态金属致脆(LME)现象,并且还具有优异的拉毛性的汽车用镀铝系合金钢板及制造其的方法。
本发明的技术问题并不限定于上述内容。本发明所属技术领域中的技术人员从本发明的说明书的全文理解本发明的进一步的技术问题是没有任何困难的。
解决技术问题的技术手段
本发明的一个实施方案提供一种镀铝系合金钢板,其包括:基础钢板;Al系合金镀层,其形成在所述基础钢板的至少一面上;以及Zn-Al系镀层,其形成在所述Al系合金镀层上,以重量%计,所述Zn-Al系镀层包含Al:0.5-1.0%、余量的Zn和不可避免的杂质,并且所述Zn-Al系镀层的镀覆附着量为3-12g/m2。
本发明的另一个实施方案提供一种制造镀铝系合金钢板的方法,其包括以下步骤:准备基础钢板;利用热浸镀铝方法在所述基础钢板上形成Al系合金镀层以获得镀铝合金钢板;利用真空蒸镀方法在所述镀铝合金钢板的表面形成Zn-Al系镀层,以重量%计,所述Zn-Al系镀层包含Al:0.5-1.2%、余量的Zn和不可避免的杂质,并且所述Zn-Al系镀层的镀覆附着量为3-12g/m2。
发明效果
根据本发明的一个方面,可以提供一种镀铝系合金钢板,其可以使从普通钢种到超高强度钢种不发生焊接部的液态金属致脆现象,可以进行与现有的镀Zn钢板相同的磷酸盐处理和后处理,特别是以维氏硬度为基准的镀层的硬度为65Hv以上,并且具有优异的拉毛性的汽车用镀铝系合金钢板。
本发明的多种有益的优点和效果并不限定于上述的内容,在对本发明的具体的实施方案进行说明的过程中可以更容易理解。
附图说明
图1是示意性地示出本发明的优选的一个具体实施方案的镀铝系合金钢板的镀层结构的示意图。
图2是用扫描电子显微镜(SEM)观察通过真空蒸镀方法制造的Zn镀覆和Zn-1重量%的Al合金镀覆的表面的照片和测量维氏硬度的结果。
图3是对本发明的一个实施方案的比较例1、比较例5和发明例1、发明例2、发明例4进行磷酸盐处理后用扫描电子显微镜(SEM)观察其表面的照片。
图4是示出对本发明的一个实施方案的发明例1至发明例4、比较例8至比较例10测量的根据测量重复次数的摩擦系数的结果。
最佳实施方式
在此使用的专业术语仅用于描述特定实施方案,并不旨在限定本发明。除非语句明确表示相反的含义,否则在此使用的单数形式还包括复数形式。
说明书中使用的“包含”或“包括”的含义是具体化特定特性、区域、整数、步骤、操作、要素和/或成分,并不排除其它特定特性、区域、整数、步骤、操作、要素、成分和/或组的存在或附加。
尽管没有另有定义,但在此使用的包括技术术语和科学术语的所有术语具有与本发明所属技术领域的技术人员通常理解的含义相同的含义。通常使用的词典中定义的术语进一步解释为具有符合相关技术文献和目前公开的内容的含义,除非定义,否则不解释为理想或非常正式的含义。
本发明人为了确保镀铝钢板的磷酸盐处理性的同时确保优异的加工性的方法进行了深入研究。其结果,新发现了在现有的Al系镀层上形成Zn镀层,且限制为适当的镀覆量,并在所述Zn镀层中添加适量的Al而将Zn镀层的硬度提高至65Hv以上时,可以进行与现有的镀Zn钢板相同的磷酸盐处理和后处理的同时可以确保优异的耐蚀性和拉毛性,基于此完成了本发明。
以下,对本发明的一个方面的镀铝系合金钢板进行详细说明。需要注意的是,本发明中表示各元素的含量时,除非另有特别定义,否则表示重量%。此外,除非另有特别说明,否则晶体或组织的比例以面积为基准。
图1是示意性地示出本发明的优选的一个具体实施方案的镀铝系合金钢板的镀层结构的示意图。参照图1,本发明的镀铝系合金钢板可以包括:基础钢板1;Al系合金镀层2,其形成在所述基础钢板1的至少一面上;以及Zn-Al系镀层3,其形成在所述Al系合金镀层2上。
在本发明中,对基础钢板的种类可以不进行特别限定。所述基础钢板可以是用作常规的镀锌钢板的基础钢板的Fe系基础钢板,即可以是热轧钢板或冷轧钢板,但并不受限于此。此外,所述基础钢板可以是用作例如汽车用材料的碳钢、超低碳钢或高锰钢,但并不受限于此。特别地,优选可以使用点焊时容易发生液态金属致脆的拉伸强度为800MPa以上的用于汽车结构体的DP、TRIP、TWIP、MART等的超高强度和极超高强度钢,但并不受限于此。
基础钢板的至少一面上可以形成Al系合金镀层。详细地,Al系合金镀层可以仅形成在基础钢板的一面上,也可以形成在基础钢板的两面上。
所述Al系合金镀层可以由铝系合金组成。本发明中铝系合金可以定义为将铝作为主要成分并包含少量的合金元素和不可避免的杂质的合金。如果是本技术领域中通常用作汽车用钢板的铝系合金层,则可以优选用作本发明的Al系合金镀层,因此对形成Al系合金镀层的铝系合金可以不进行特别限定。但是,作为一个实例,以重量%计,可以包含Si:5-12%、Zn:5-30%、Mg:0.5-5%、Mn:0.01-2%、Fe:0.1-2%、余量的Al和不可避免的杂质,但并不受限于此。
所述Al系合金镀层上可以形成Zn-Al系镀层。以重量%计,所述Zn-Al系镀层可以包含Al:0.5-1.0%、余量的Zn和不可避免的杂质,且并不排除包含其它合金元素。
当形成一定厚度以上的Zn-Al系镀层时,可以进行与现有的镀Zn钢板相同的各种磷酸盐处理和后处理。但是,如现有技术的问题所指出,当形成Zn-Al系镀层时,由于Zn的延展性(维氏硬度值为52-55Hv水平),拉毛特性迅速变差导致发生镀层的剥离,或者由于模具清洁周期的增加引起的生产性的降低和生产成本的增加,因此作为汽车用镀覆钢板的使用可能受限。在本发明中,为了解决这种现有技术的问题,通过在Zn-Al系镀层中含有0.5-1.0%的Al,可以确保适当的水平以上的硬度。这种硬度的上升是由于微量的合金化导致的固溶强化和晶粒微细化。图2是用扫描电子显微镜(SEM)观察通过真空蒸镀方法制造的Zn镀覆和Zn-1重量%的Al合金镀覆的表面的照片和测量维氏硬度的结果。通过图2可知,当在Zn-Al系镀层中添加1.0%的Al时,与纯Zn镀覆相比,平均颗粒的尺寸减少至一半以下,根据上述强化原理,硬度值大幅增加至85Hv。
当所述Zn-Al系镀层中包含的Al的含量小于0.5%时,以维氏硬度为基准,可能难以确保65Hv以上的硬度。另一方面,当Al含量超过1.0%时,可以确保65Hv以上的硬度,从而可以获得优异的拉毛性,但在后续工艺中进行磷酸盐处理时可能会发生形成异常的磷酸盐薄膜的问题。因此,所述Zn-Al系镀层中包含的Al含量优选具有0.5-1.2%的范围。所述Al含量的下限更优选为0.6%,进一步优选为0.7%,最优选为0.8%。所述Al含量的上限更优选为1.1%,进一步优选为1.0%,最优选为0.9%。
所述Zn-Al系镀层的镀覆附着量可以为3-12g/m2。为了在后工艺的磷酸盐处理过程中形成致密且稳定的磷酸盐层,并为了确保与结构用密封剂的优异的粘附力,Zn-Al系镀层需要具有3g/m2以上的镀覆附着量。当小于所述镀覆附着量时,后工艺中进行的磷酸盐处理时可能难以形成正常的磷酸盐薄膜。另一方面,当所述镀覆附着量超过12g/m2时,磷酸盐处理性可能会变良好,但随着在点焊过程中以液相存在的Zn的量增加,可能发生Zn引起的焊接部液态金属致脆(LME)现象,由于不必要的镀覆附着量的增加,生产成本会增加。因此,所述Zn-Al系镀层的镀覆附着量优选具有3-12g/m2的范围。所述Zn-Al系镀层的镀覆附着量的下限更优选为4g/m2,进一步优选为5g/m2,最优选为6g/m2。所述Zn-Al系镀层的镀覆附着量的上限更优选为11g/m2,进一步优选为10g/m2,最优选为9g/m2。
以维氏硬度(Vicker's Hardness)基准,所述Zn-Al系镀层的硬度可以为65Hv以上。与现有的表现出高延展性的Zn镀层不同,通过添加Al来确保一定水平以上的硬度,从而可以获得优异的加工性。
接着,对本发明的另一个方面的制造镀铝系合金钢板的方法进行详细说明。但是,以下说明的制造方法仅仅是所有可能的实施方案中的一种实施方案,并不表示本发明的镀铝系合金钢板只能通过下述制造方法制造。
首选,准备基础钢板,通过热浸镀铝方法在所述基础钢板上形成Al系合金镀层,从而制造镀铝合金钢板。
对热浸镀铝方法可以不进行特别限制,可以应用通常利用的热浸镀铝方法。作为一个实例,以重量%计,基础钢板包含5-30%的Zn、0.5-5%的Mg、0.01-3%的Mn、余量的Al和不可避免的杂质,使浸入保持520-560℃的镀浴温度的镀浴中,从而可以形成Al系合金镀层。
之后,在形成有Al系合金镀层的镀覆钢板的表面上形成Zn-Al系镀层,以重量%计,所述Zn-Al系镀层包含Al:0.5-1.0%、余量的Zn和不可避免的杂质,并且所述Zn-Al系镀层的附着量为3-12g/m2。此时,对形成Zn-Al系镀层的方法可以不进行特别限制。但是,在形成Al系合金镀层时已经应用了热浸镀覆方法,因此形成Zn-Al系镀层时难以再次应用热浸镀覆方法,考虑到除Zn之外还需要包含少量的Al成分,而且需要以3-12g/m2的水平的附着量薄薄地形成时,优选利用真空蒸镀方法。特别地,可以应用可以确保高生产性的EML-PVD、喷射(Jet)-PVD、EB PVD和其它热(Thermal)法,但并不受限于此。
具体实施方式
以下,通过实施例对本发明进行更具体的说明。但是,需要注意的是,下述实施例仅用于例示本发明而进行更具体的说明,并不用于限制本发明的权利范围。这是因为本发明的权利范围由权利要求中记载的内容和由此合理推导的内容所决定。
(实施例)
首先,准备超高强度基础钢板,以重量%计,所述超高强度基础钢板具有包含C:0.16%、Mn:2.5%、Si:1.5%、余量的Fe和不可避免的杂质的合金组成,并且所述超高强度基础钢板的拉伸强度为1.2Gpa级,利用热浸镀覆方法在所述基础钢板上形成Al系合金镀层。此时,通过湿式分析(ICP)方法测量所述Al系合金镀层的成分的结果,确认了含有Zn:20%、Mg:3%、Mn:2%、Si:7%、Fe:0.9%、余量的Al。之后,利用EML-PVD方法,在所述Al系合金镀层上形成Zn-Al系镀层。此时,如下表1所示改变所述Zn-Al系镀层的镀覆附着量和Al含量。
根据以下方法,对通过上述方法获得的镀覆钢板进行物理性能的评价,并将其结果示于下表1中。
利用显微硬度计(Micro Hardness Tester)测量Zn-Al系镀层的硬度。测量条件为将荷重设为5mN,荷重到达时间设为10秒,最大分析深度设为镀层厚度的10%的厚度,并测量各实施例后取平均值。
拉毛性通过连续摩擦系数测量方法测量,以5MPa的荷重,200mm/秒的速度,涂覆洗涤油后各测量40次,测量40次期间,摩擦系数小于0.3时判定为良好,摩擦系数为0.3以上时判定为不良。
磷酸盐溶液和处理条件是用汽车公司在GI镀覆钢板的磷酸盐处理中使用的相同的防锈和底涂用锌系磷酸盐处理液在87-95℃下浸渍10-45分钟来进行处理,对于磷酸盐处理性,将与现有的GI镀覆钢板的磷酸盐处理后的表面状态相似的情况评价为良好,将磷酸盐处理不足的情况评价为不良。
对于焊接部是否发生液化脆性,以SEP1220焊接条件,在-0.2kA和-0.4kA的最大焊接电流分别焊接4对试片,以15放大倍率观察各焊接截面时,根据是否观察到裂纹,判定为发生/未发生焊接部液化脆性。
[表1]
从所述表1可以确认,Zn-Al系镀层含有0.5-1.0%的Al且镀覆附着量满足3-12g/m2的发明例1至发明例8的情况下,Zn-Al系镀层的硬度确保为最小65Hv以上,拉毛性和磷酸盐处理性良好,也不发生焊接部液化脆性。
比较例1和比较例2是Zn-Al系镀层的镀覆量为1g/m2且过少的情况,并且可以确认磷酸盐处理性不良。
比较例3至比较例6是Zn-Al系镀层的Al含量为1.5%且过高的情况,可以确认由于镀层的硬度高而显示良好的拉毛性,但磷酸盐处理性不良。
比较例7至比较例10是Zn-Al系镀层的Al含量为0.1%且过低的情况,可以确认镀层硬度为低至55Hv以下的水平,磷酸盐处理性也不良。
比较例11和比较例12是Zn-Al系镀层的镀覆量为15g/m2且过高的情况,可以确认拉毛性和磷酸盐处理性良好,但在焊接部中观察到液化脆化现象。
图3是对比较例1、比较例5和发明例1、发明例2、发明例4进行磷酸盐处理后用扫描电子显微镜(SEM)观察其表面的照片。通过图3可知,符合本发明的条件的发明例1、发明例2、发明例4的情况下,可以确认磷酸盐涂覆性(覆盖率(coverage))和晶粒尺寸等与现有的GI材料(参考例)的磷酸盐处理后的外观是相似的水平,另一方面,比较例1和比较例5的情况下,可以确认磷酸盐晶体几乎不生长,因此没有形成正常的磷酸盐薄膜。
图4是示出对发明例1至发明例4、比较例8至比较例10测量的根据测量重复次数的摩擦系数的结果。通过图4可知,发明例1至发明例4的情况下,即使测量重复次数为40次,摩擦系数为低的水平,但比较例8至比较例10的情况下,可知在约20次左右的重复次数下,摩擦系数迅速增加至0.3以上,由此可以预测不适合作为汽车用材料。
以上,通过参考实施例进行说明,但本技术领域的技术人员可以理解,在不脱离权利要求中记载的本发明的思想和领域的范围内,可以对本发明进行各种修改和改变。
[附图标记说明]
1:基础钢板
2:Al系合金镀层
3:Zn-Al系镀层
Claims (5)
1.一种镀铝系合金钢板,其包括:
基础钢板;
Al系合金镀层,其形成在所述基础钢板的至少一面上;以及
Zn-Al系镀层,其形成在所述Al系合金镀层上,以重量%计,所述Zn-Al系镀层包含Al:0.5-1.0%、余量的Zn和不可避免的杂质,并且所述Zn-Al系镀层的镀覆附着量为3-12g/m2。
2.根据权利要求1所述的镀铝系合金钢板,其中,所述Zn-Al系镀层的硬度为65Hv以上。
3.根据权利要求1所述的镀铝系合金钢板,其中,以重量%计,所述Al系合金镀层包含Si:5-12%、Zn:5-30%、Mg:0.5-5%、Mn:0.01-2%、Fe:0.1-2%、余量的Al和不可避免的杂质。
4.一种制造镀铝系合金钢板的方法,其包括以下步骤:
准备基础钢板;
利用热浸镀铝方法在所述基础钢板上形成Al系合金镀层以获得镀铝合金钢板;
利用真空蒸镀方法在所述镀铝合金钢板的表面形成Zn-Al系镀层,以重量%计,所述Zn-Al系镀层包含Al:0.5-1.2%、余量的Zn和不可避免的杂质,并且所述Zn-Al系镀层的镀覆附着量为3-12g/m2。
5.根据权利要求4所述的制造镀铝系合金钢板的方法,其中,所述真空蒸镀方法利用电磁悬浮-物理气相沉积(EML-PVD)、喷射-物理气相沉积(Jet-PVD)、电子束物理气相沉积(EBPVD)和热法中的一种。
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US20230019519A1 (en) | 2023-01-19 |
JP7301233B2 (ja) | 2023-06-30 |
KR20210070681A (ko) | 2021-06-15 |
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