CN108431287B - 形成有后处理薄膜的镀锌系钢板及其后处理方法 - Google Patents
形成有后处理薄膜的镀锌系钢板及其后处理方法 Download PDFInfo
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- CN108431287B CN108431287B CN201680075455.7A CN201680075455A CN108431287B CN 108431287 B CN108431287 B CN 108431287B CN 201680075455 A CN201680075455 A CN 201680075455A CN 108431287 B CN108431287 B CN 108431287B
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 43
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 62
- 239000002184 metal Substances 0.000 claims abstract description 62
- 238000000576 coating method Methods 0.000 claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 50
- 239000001301 oxygen Substances 0.000 claims abstract description 50
- 238000007747 plating Methods 0.000 claims abstract description 32
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 28
- 239000010959 steel Substances 0.000 claims abstract description 28
- 239000011701 zinc Substances 0.000 claims abstract description 18
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims description 109
- 239000011248 coating agent Substances 0.000 claims description 45
- 239000010409 thin film Substances 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 8
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- 239000011118 polyvinyl acetate Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 24
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- 230000001070 adhesive effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 238000007611 bar coating method Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000013521 mastic Substances 0.000 description 2
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- 239000003921 oil Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 239000000565 sealant Substances 0.000 description 1
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Classifications
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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
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Abstract
本发明提供形成有后处理薄膜的镀锌系钢板及对镀锌系钢板进行后处理的方法,所述形成有后处理薄膜的镀锌系钢板包括:钢板;锌系镀层,其形成在所述钢板上;以及后处理薄膜,其形成在所述镀层上;所述后处理薄膜包含金属含氧盐和有机化合物,所述后处理薄膜中包含的氧(O)与金属(M)的原子比(O/M)为超过2且小于20,据此,形成有后处理薄膜的镀锌系钢板具有润滑性、焊接性、粘合性、脱膜性及涂装性优异的效果,并且本发明的镀锌系钢板的后处理方法采用简单的涂覆方式而与镀层的种类无关,从而工艺简单且工艺运行成本低廉,因此具有经济性效果。
Description
技术领域
本发明涉及形成有后处理薄膜的镀锌系钢板及其后处理方法。
背景技术
用作汽车板材的镀锌系钢板的价格低廉、耐蚀性优异、表面外观精美,从而作为汽车内外板材的使用量正在逐渐增加。在汽车制造工艺中,所述镀覆钢板依次经过冲压成型工序、如焊接及粘合等组装工序、脱脂工序、磷酸盐处理工序及涂装工序,此时,镀锌钢板需要润滑性、焊接性、粘合性、脱膜性、涂装性等物理性质。
镀锌系钢板根据形成在钢板上的镀层的组成及制造方法所显示出的物理性质不同,针对差的物理性质需要进行增强。例如,就热浸镀锌钢板(GI)和电镀锌钢板(EG)而言,因软质的镀层,在伴随高压及高速摩擦的冲压成型时,存在镀层会脱落而熔合在模具的垫圈(bead)部等的问题。因此,在钢板的表面上会引发划痕或凹痕等缺陷。尤其,热浸镀锌钢板(GI)等由纯锌组成的镀层的熔点低,并且由于包含微量的铝(Al),在焊接工序中镀层成分熔合在电极表面并被氧化而形成非导体污染物,由此存在连续焊点的数量减少的问题。
此外,就合金化热浸镀锌钢板(GA)而言,由于高表面摩擦系数,冲压成型时的润滑特性不充分,从而发生材料自身断裂或硬镀层脱落的粉化现象。进而,就镀层中包含微量的铝(Al)或镁(Mg)的镀锌合金钢板而言,虽然冲压成型性优异,但存在如下问题,即,由于极表层中存在的稳定的金属氧化物而导致粘合性降低,或者由于低熔点的合金相而导致焊接时的连续焊点的数量会减少。
为了解决如上所述的问题,需要对用作汽车板材的镀锌系钢板的表面进行后处理,并需要由此提高差的物理性质。
关于后处理的技术有在锌镀层表面形成磷酸盐层的技术(公开KR2001-0074527)和形成金属氧化物层的技术(公开JP-2014-185381)。但是,形成磷酸盐层的技术需要表面调整、磷酸盐处理、水洗、干燥等过程,在实际操作时需要相当大的设备空间和溶液的管理,并且是依赖于与镀层的反应性的处理方法,因此存在需要根据镀锌系钢板的种类改变溶液组成的麻烦。此外,形成金属氧化物层的技术受到镀层金属成分的限制,因此存在无法应用于所有的镀锌系钢板的问题。
发明内容
要解决的技术问题
本发明的目的在于提供汽车用板材所需要的润滑性、焊接性、粘合性、脱膜性及涂装性等物理性质优异的镀锌系钢板。
此外,本发明的目的在于提供通过简单且低廉的工艺对镀锌系钢板进行后处理的方法。
技术方案
根据本发明的一个实施例,提供形成有后处理薄膜的镀锌系钢板,其包括:钢板;锌系镀层,其形成在所述钢板上;以及后处理薄膜,其形成在所述镀层上;所述后处理薄膜包含金属含氧盐和有机化合物,所述后处理薄膜中包含的氧(O)与金属(M)的原子比(O/M)为超过2且小于20。
所述后处理薄膜可以分为薄膜上部和薄膜下部,所述薄膜上部的氧(O)与金属(M)的原子比(O/M)可以为5以上,所述薄膜下部的氧(O)与金属(M)的原子比(O/M)可以为小于5。
所述薄膜上部的氧(O)与金属(M)的原子比(O/M)可以为3.2以上,所述薄膜下部的氧(O)与金属(M)的原子比(O/M)可以为小于3.2。
所述薄膜下部的厚度可以为后处理薄膜总厚度的1/4~3/4。
所述金属含氧盐还可以包含选自钼(Mo)、硼(B)、硅(Si)、钛(Ti)及锆(Zr)中的一种以上。
根据本发明的另一个实施例,提供镀锌系钢板的后处理方法,其包括在镀锌系钢板上涂布后处理涂覆溶液并进行干燥而形成后处理薄膜的步骤,所述后处理薄膜中包含的氧(O)与金属(M)的原子比(O/M)为超过2且小于20。
所述后处理薄膜可以分为薄膜上部和薄膜下部,所述薄膜上部的氧(O)与金属(M)的原子比(O/M)可以为5以上,所述薄膜下部的氧(O)与金属(M)的原子比(O/M)可以为小于5。
所述薄膜下部的厚度可以为后处理薄膜总厚度的1/4~3/4。
所述后处理涂覆溶液的pH可以为3.0~7.0。
所述后处理薄膜的薄膜附着量可以为100~1000mg/m2。
有益效果
本发明的形成有后处理薄膜的镀锌系钢板具有润滑性、焊接性、粘合性、脱膜性及涂装性优异的效果。
此外,本发明的镀锌系钢板的后处理方法采用简单的涂覆方式而与镀层的种类无关,从而工艺简单且工艺运行成本低廉,因此具有经济性效果。
最佳实施方式
下面,参照各种实施例对本发明的优选的实施方式进行说明。但是,本发明的实施方式可以变形为其他各种方式,本发明的范围并不限定于以下说明的实施方式。
本发明涉及形成有后处理薄膜的镀锌系钢板及其后处理方法,具体地,可以提供如下的形成有后处理薄膜的镀锌系钢板,其包括:钢板;锌系镀层,其形成在所述钢板上;以及后处理薄膜,其形成在所述镀层上;所述后处理薄膜包含金属含氧盐和有机化合物,所述后处理薄膜中包含的氧(O)与金属(M)的原子比(O/M)为超过2且小于20。
本发明的形成有后处理薄膜的镀锌系钢板具有汽车用板材所需要的润滑性、焊接性、粘合性、脱膜性及涂装性等物理性质优异的效果。
在汽车制造工艺中,汽车用板材会依次经过冲压成型工序、如焊接及粘合等组装工序、脱脂工序、磷酸盐处理工序及涂装工序,此时,所述汽车用板材需要润滑性、焊接性、粘合性、脱膜性、涂装性等物理性质。在所述冲压成型工序中,当润滑性不充分时,会发生材料自身断裂或硬镀层脱落的粉化现象。在所述组装工序中,当焊接性不充分时,在进行焊接时焊接电极发生污染,从而电极寿命及连续焊点的数量会减少,当粘合性不充分时,拉伸试验时会发生界面剥离。此外,在所述脱脂工序中,当脱膜性不充分时,无法充分去除后处理薄膜,由此在作为后续工序的磷酸盐处理及涂装工序时引起不良,并且涂装性会降低。
为了提高汽车制造工艺中需要的物理性质,即为了提高润滑性、焊接性、粘合性、脱膜性及涂装性,本发明的镀锌系钢板可以包括形成在镀层上的后处理薄膜,所述后处理薄膜可以包含金属含氧盐和有机化合物。进而,可以控制后处理薄膜中包含的氧(O)与金属(M)的原子比(O/M)超过2且小于20。
所述后处理薄膜中的氧(O)与金属(M)的原子比(O/M)是对所述形成有后处理薄膜的镀锌系钢板进行丙酮脱脂之后利用X射线光电子能谱(X-ray PhotoelectronSpectroscopy,XPS)分析法的纳米级的每单位深度的平均值。
所述后处理薄膜中包含的氧含量是决定镀锌系钢板的物理性质的重要条件,尤其,所述后处理薄膜中包含的氧(O)与金属(M)的原子比(O/M)优选为超过2且小于20,更优选为超过2且小于10。
当所述氧(O)与金属(M)的原子比(O/M)为2以下时,后处理薄膜中的氧含量会过度变少,因此在冲压模具与钢板之间赋予润滑性的金属含氧盐的分率会降低,从而难以确保充分的润滑性,由此在钢板的冲压成型时会发生镀层脱落或钢板材料断裂的问题。此外,高熔点的金属含氧盐的分率会降低,从而在焊接工序中增加电极的污染而导致电极寿命及连续焊点的数量的减少,因此难以确保焊接性。进而,含氧(Oxo)配体和羟基等以氧为媒介的结合位点不足,从而会降低确保镀锌系钢板与粘合剂之间的粘合强度的粘合性。
另外,所述氧(O)与金属(M)的原子比(O/M)为20以上时,后处理薄膜中的氧含量变得过多,尤其,含氧(Oxo)配体或羟基等结合位点的分率会变高,从而导致脱膜性的降低。由此,无法充分去除所述后处理薄膜,从而在磷酸盐处理工序及涂装工序中引起不良,并且涂装性会降低。
优选地,本发明的后处理薄膜可以分为薄膜上部和薄膜下部,所述薄膜上部的氧(O)与金属(M)的原子比(O/M)为5以上,所述薄膜下部的氧(O)与金属(M)的原子比(O/M)为小于5。进而,更优选地,所述薄膜上部的氧(O)与金属(M)的原子比(O/M)为3.2以上,所述薄膜下部的氧(O)与金属(M)的原子比(O/M)小于3.2。
本发明中可以控制所述薄膜上部的氧(O)与金属(M)的原子比(O/M)为5以上,以具有高氧含量。由此,本发明的镀锌系钢板表层的金属含氧盐的分率高,从而润滑性和焊接性优异,并且通过含氧配体和羟基等结合位点密集在表层,提高组装工序中的与粘合剂的亲和性,从而能够确保粘合强度。
此外,本发明中可以控制所述薄膜下部的氧(O)与金属(M)的原子比(O/M)为5以下,以具有低氧含量。由此,所述薄膜下部能够在涂装工序之前进行的脱脂工序中顺利诱导后处理薄膜的脱膜性,因此能够在作为后续工序的磷酸盐处理工序和涂装工序中防止不良以确保涂装性,并且之后基于优异的涂装性能够确保耐蚀性。
另外,所述薄膜下部的厚度可以为后处理薄膜总厚度的1/4~3/4,更优选为1/3~2/3。当所述薄膜下部的厚度小于后处理薄膜总厚度的1/4时,脱膜性优异的薄膜下部的占有率低,从而在磷酸盐处理或电沉积涂装时会引起缺陷,当所述薄膜下部的厚度超过后处理薄膜总厚度的3/4时,粘附性不足,从而难以确保粘合剂的粘合强度。
所述后处理薄膜中包含的金属含氧盐优选还包含选自钼(Mo)、硼(B)、硅(Si)、钛(Ti)及锆(Zr)中的一种以上。此外,所述后处理薄膜可以是单独包含磷(P),或者与所述磷一起包含所述金属含氧盐的后处理薄膜。
另外,所述有机化合物只要是包含羟基(-OH)的有机化合物就不作特别限制。例如,可以是具有羟基、羰基等官能团的有机化合物,进而,例如,可以是包含聚乙酸乙烯酯(PVAc)、聚乙烯醇(PVA)、聚丙烯酸(PAA)、聚乙烯醇缩丁醛(PVB)、聚乙二醇(PEG)等的化合物。
根据本发明的一个实施例,可以提供镀锌系钢板的后处理方法,其包括在镀锌系钢板上涂布后处理涂覆溶液并进行干燥而形成后处理薄膜的步骤,所述后处理薄膜中包含的氧(O)与金属(M)的原子比(O/M)为超过2且小于20。
对镀锌系钢板进行后处理时的涂覆方法可以列举PVD、CVD等干式涂覆法、熔射涂覆等粉末喷射涂覆法、辊涂等溶液涂布法等,但是本发明中通过在镀层上简单涂布后处理涂覆溶液的溶液涂布法进行后处理而与镀层的种类无关,因此工艺简单且工艺运行成本低廉,从而具有经济性效果。
在镀层上涂布后处理涂覆溶液并进行干燥而形成的所述后处理薄膜的氧(O)与金属(M)的原子比(O/M)优选为超过2且小于20,将所述原子比控制在这种范围的理由如上所述。
本发明的后处理薄膜可以分为薄膜上部和薄膜下部,优选地,所述薄膜上部的氧(O)与金属(M)的原子比(O/M)为5以上,所述薄膜下部的氧(O)与金属(M)的原子比(O/M)为小于5。进而,更优选地,所述薄膜上部的氧(O)与金属(M)的原子比(O/M)为3.2以上,所述薄膜下部的氧(O)与金属(M)的原子比(O/M)为小于3.2。另外,所述薄膜下部的厚度可以为后处理薄膜总厚度的1/4~3/4,更优选可以为1/3~2/3。将所述薄膜上部及薄膜下部的所述原子比控制在这种范围的理由以及将所述薄膜下部的厚度控制为这种范围的理由如上所述。
所述后处理薄膜中包含的金属含氧盐优选还包含选自钼(Mo)、硼(B)、硅(Si)、钛(Ti)及锆(Zr)中的一种以上。所述后处理涂覆溶液中包含的金属含氧盐可以使用分散成胶体状的溶液,或者可以以氧化物的形态溶解于溶液中来使用。
另外,所述有机化合物只要是包含羟基(-OH)的有机化合物就不作特别限制。例如,可以是具有羟基、羰基等官能团的有机化合物,进而,例如,可以是包含聚乙酸乙烯酯(PVAc)、聚乙烯醇(PVA)、聚丙烯酸(PAA)、聚乙烯醇缩丁醛(PVB)、聚乙二醇(PEG)等的化合物。
对所述后处理涂覆溶液的pH不作特别限定,但是为了防止镀层的溶解并形成稳定的薄膜,所述后处理涂覆溶液的pH优选为3.0~7.0。
具体实施方式
下面,通过具体的实施例对本发明进行更详细的说明。以下的实施例仅仅是有助于理解本发明的例示,本发明的范围并不限定于此。
实施例
<实施例1>
准备厚度为0.8mm、延伸率为36~37%、镀覆量为40g/m2、镀层由2.5%的Al、3%的Mg、94.5%的Zn组成的镀锌系钢板。通过棒涂法在所述钢板上涂布包含含有1重量%的Mo、0.2重量%的B的金属含氧盐、0.3重量%的PEG及余量的水的涂覆溶液,然后在PMT 100℃的条件下,形成附着量为300mg/m2的后处理薄膜。
<实施例2>
准备厚度为0.8mm、延伸率为36~37%、镀覆量为40g/m2、镀层由2.5%的Al、3%的Mg、94.5%的Zn组成的镀锌系钢板。通过棒涂法在所述钢板上涂布包含含有1重量%的Mo、0.5重量%的B的金属含氧盐、0.5重量%的PEG及余量的水的涂覆溶液,然后在PMT 100℃的条件下,形成附着量为300mg/m2的后处理薄膜。
<实施例3>
准备厚度为0.8mm、延伸率为36~37%、镀覆量为40g/m2、镀层由2.5%的Al、3%的Mg、94.5%的Zn组成的镀锌系钢板。通过棒涂法在所述钢板上涂布包含含有1重量%的Mo、1重量%的B的金属含氧盐、1重量%的PEG及余量的水的涂覆溶液,然后在PMT 100℃的条件下,形成附着量为300mg/m2的后处理薄膜。
<实施例4>
准备厚度为0.8mm、延伸率为36~37%、镀覆量为40g/m2、镀层由2.5%的Al、3%的Mg、94.5%的Zn组成的镀锌系钢板。通过棒涂法在所述钢板上涂布包含含有0.5重量%的Mo、1重量%的B的金属含氧盐、1.5重量%的PEG及余量的水的涂覆溶液,然后在PMT 100℃的条件下,形成附着量为300mg/m2的后处理薄膜。
<比较例1>
准备厚度为0.8mm、延伸率为36~37%、镀覆量为40g/m2、镀层由2.5%的Al、3%的Mg、94.5%的Zn组成的镀锌系钢板,并且没有在上部形成后处理薄膜。
<比较例2>
准备厚度为0.8mm、延伸率为36~37%、镀覆量为40g/m2、镀层由2.5%的Al、3%的Mg、94.5%的Zn组成的镀锌系钢板。通过棒涂法在所述钢板上涂布包含含有1重量%的Mo的金属含氧盐、0.1重量%的PEG及余量的水的涂覆溶液,然后在PMT 100℃的条件下,形成附着量为300mg/m2的后处理薄膜。
<比较例3>
准备厚度为0.8mm、延伸率为36~37%、镀覆量为40g/m2、镀层由2.5%的Al、3%的Mg、94.5%的Zn组成的镀锌系钢板。通过棒涂法在所述钢板上涂布包含含有1重量%的Mo、0.5重量%的B的金属含氧盐、3重量%的PEG及余量的水的涂覆溶液,然后在PMT 100℃的条件下,形成附着量为300mg/m2的后处理薄膜。
对所述实施例1至实施例4和比较例1至比较例3的后处理薄膜中的氧(O)与金属(M)的原子比(O/M)进行测量并示于表1中。所述原子比(O/M)是对所述形成有后处理薄膜的镀锌系钢板进行丙酮脱脂之后利用X射线光电子能谱(X-ray PhotoelectronSpectroscopy,XPS)分析法的纳米级的每单位深度的平均值。将总厚度的1/2位置设为上部与下部的分界线。为了评价基于氧(O)与金属(M)的原子比(O/M)条件的物理性质,对加工性、粘合性及脱膜性进行了评价,并将其结果示于表1中。
<加工性的评价>
为了评价加工性进行了杯突试验(cup drawing),所述杯突试验中使用由凹模和凸模组成的试验机,在增加压边力(Blank Holding Force,BHF)的同时进行试验,并将材料产生断裂之前那一刻的BHF值作为最大BHF值并记载于表1中。最大BHF值越大,则表示加工性优异,本实施例中进行的杯突试验的详细条件为如下。
*杯突试验的详细条件
-凸模直径(Punch diameter):50mm;
-凸模边缘半径(Punch edge radius):6mm;
-凹模直径(Die diameter):52.25mm;
-凸模移动速度:23mm/分钟;
-后处理薄膜与凹模接触,并且在表面上涂布洗油之后进行试验。
<粘合性的评价>
粘合性试验中,以25mm×100mm的尺寸制作两张试片,并在涂布洗油之后垂直放置一天,然后在从试片的末端向内侧10mm的位置以25mm(宽)×25mm(长)×3mm(高)的尺寸涂布乳香密封胶(mastic sealer)粘合剂,然后重叠余下的试片,并在170℃下固化20分钟之后测量上/下试片的粘合剪切强度,将其结果示于表1中。剪切强度是以50mm/分钟的速度进行测量,并将所测量的最大剪切力除以粘合面积6.25cm2来表示。
<脱膜性的评价>
脱膜性试验中,使用汽车制造工艺中使用的脱脂溶液,在50~55℃下搅拌并浸渍材料两分钟后进行水洗,然后测量残留在材料表面的涂膜的量,以百分率计算相对于脱脂之前的薄膜附着量的脱膜率,并示于表1中。对于涂膜的残留量,利用酸溶液溶解一定面积的涂层之后,利用电感耦合等离子体(Inductively Coupled Plasma,ICP)对溶解溶液中的钼含量进行定量分析,并计算每面积的残留量。
[表1]
*O/M是氧(O)与金属(M)的原子比。
如上述表1中所示,形成后处理涂膜的实施例1至实施例4与未进行后处理的比较例1相比,最大BHF值和粘合强度显著高,因此可以确认实施例1至实施例4的加工性和粘合性等可使用为汽车用板材的物理性质显著优异。
此外,氧(O)与金属(M)的原子比(O/M)为超过2且小于20的实施例1至实施例4具有95%以上的脱膜率,因此可以确认脱膜性优异。但是,氧(O)与金属(M)的原子比(O/M)为2以下的比较例2的加工性和粘合性差,氧(O)与金属(M)的原子比(O/M)为20以上的比较例3的加工性和粘合性优异,但是脱膜率为87%以下,因此可以确认脱膜率差。
以上对本发明的实施例进行了详细说明,但是本发明的权利范围并不限定于此,在不脱离权利要求书中记载的本发明的技术思想的范围内可以进行各种修改及变形,这对于本技术领域中具有通常知识者而言是显而易见的。
Claims (6)
1.形成有后处理薄膜的镀锌系钢板,其包括:
钢板;
锌系镀层,其形成在所述钢板上;以及
后处理薄膜,其形成在所述镀层上;
所述后处理薄膜包含金属含氧盐和有机化合物,
所述后处理薄膜中包含的氧(O)与金属(M)的原子比(O/M)为超过2且小于20,
所述后处理薄膜分为薄膜上部和薄膜下部,所述薄膜上部的氧(O)与金属(M)的原子比(O/M)为5以上,所述薄膜下部的氧(O)与金属(M)的原子比(O/M)小于5,
所述金属为选自钼(Mo)、硼(B)、硅(Si)、钛(Ti)及锆(Zr)中的一种以上,
所述有机化合物为选自聚乙酸乙烯酯(PVAc)、聚乙烯醇(PVA)、聚丙烯酸(PAA)、聚乙烯醇缩丁醛(PVB)及聚乙二醇(PEG)中的一种以上。
2.根据权利要求1所述的形成有后处理薄膜的镀锌系钢板,其中,所述薄膜下部的厚度为后处理薄膜总厚度的1/4~3/4。
3.镀锌系钢板的后处理方法,其包括在镀锌系钢板上涂布包含金属含氧盐和有机化合物的后处理涂覆溶液并进行干燥而形成后处理薄膜的步骤,
所述后处理薄膜中包含的氧(O)与金属(M)的原子比(O/M)为超过2且小于20,
所述后处理薄膜分为薄膜上部和薄膜下部,所述薄膜上部的氧(O)与金属(M)的原子比(O/M)为5以上,所述薄膜下部的氧(O)与金属(M)的原子比(O/M)小于5,
所述金属为选自钼(Mo)、硼(B)、硅(Si)、钛(Ti)及锆(Zr)中的一种以上,
所述有机化合物为选自聚乙酸乙烯酯(PVAc)、聚乙烯醇(PVA)、聚丙烯酸(PAA)、聚乙烯醇缩丁醛(PVB)及聚乙二醇(PEG)中的一种以上。
4.根据权利要求3所述的镀锌系钢板的后处理方法,其中,所述薄膜下部的厚度为后处理薄膜总厚度的1/4~3/4。
5.根据权利要求3所述的镀锌系钢板的后处理方法,其中,所述后处理涂覆溶液的pH为3.0~7.0。
6.根据权利要求3所述的镀锌系钢板的后处理方法,其中,所述后处理薄膜的薄膜附着量为100~1000mg/m2。
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JP6684910B2 (ja) | 2020-04-22 |
WO2017111455A1 (ko) | 2017-06-29 |
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