CN111094614B - 金属板处理方法和用该方法处理的金属板 - Google Patents
金属板处理方法和用该方法处理的金属板 Download PDFInfo
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- CN111094614B CN111094614B CN201880058460.6A CN201880058460A CN111094614B CN 111094614 B CN111094614 B CN 111094614B CN 201880058460 A CN201880058460 A CN 201880058460A CN 111094614 B CN111094614 B CN 111094614B
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- sulphate
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- 229910052751 metal Inorganic materials 0.000 title claims description 46
- 239000002184 metal Substances 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 22
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 235000009529 zinc sulphate Nutrition 0.000 claims abstract description 37
- 239000011686 zinc sulphate Substances 0.000 claims abstract description 37
- 239000011701 zinc Substances 0.000 claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 12
- 239000010959 steel Substances 0.000 claims abstract description 12
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005864 Sulphur Substances 0.000 claims abstract description 8
- 238000007605 air drying Methods 0.000 claims description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 3
- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 abstract description 25
- 239000000758 substrate Substances 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 14
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 abstract description 10
- KSLUMEQTEAUMJZ-UHFFFAOYSA-L zinc;sulfate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O KSLUMEQTEAUMJZ-UHFFFAOYSA-L 0.000 abstract description 7
- 238000003672 processing method Methods 0.000 abstract description 2
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- 238000002129 infrared reflectance spectroscopy Methods 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 12
- 229960001763 zinc sulfate Drugs 0.000 description 11
- 229910000368 zinc sulfate Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000004566 IR spectroscopy Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
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- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
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- 239000012535 impurity Substances 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 2
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Abstract
本发明涉及钢基材,所述钢基材在其至少一个面上涂覆有基于锌或其合金的金属涂层,其中所述金属涂层本身涂覆有包含选自一水合硫酸锌、四水合硫酸锌和七水合硫酸锌的至少一种化合物的基于硫酸锌的层,其中所述基于硫酸锌的层既不包含羟基硫酸锌,也不包含游离水分子,也不包含游离羟基,所述基于硫酸锌的层中的硫的表面密度大于或等于0.5mg/m2。本发明还涉及相应的处理方法。
Description
本发明涉及包括钢基材的金属板,所述钢基材在其至少一个面上涂覆有基于锌或其合金的金属涂层。
本发明特别涉及该经涂覆的钢基材的预润滑及其在包含硫酸盐的水溶液中的处理。
这种类型的金属板特别旨在用于制造汽车的部件,尽管其不限于那些应用。
由WO00/15878已经知晓用包含硫酸锌的水溶液处理锌涂覆的金属板以在基于锌的涂层上形成羟基硫酸锌的层。该羟基硫酸锌的转化层提供了具有比通过磷化获得的性能更高的性能的预润滑的锌涂覆的金属板。
然而,已经观察到,该基于羟基硫酸锌的转化层可能向汽车工业中使用的粘合剂,尤其是基于环氧的粘合剂提供不足的粘合性。
因此,本发明的目的是通过提供向汽车工业中使用的粘合剂,尤其是基于环氧的粘合剂提供足够的粘合性的表面处理来改进现有技术的(设施和工艺的)缺陷。
为此目的,本发明的第一主题由在其至少一个面上涂覆有基于锌或其合金的金属涂层的钢基材构成,其中所述金属涂层本身涂覆有包含选自一水合硫酸锌、四水合硫酸锌和七水合硫酸锌的至少一种化合物的基于硫酸锌的层,其中所述基于硫酸锌的层既不包含羟基硫酸锌,也不包含游离水分子,也不包含游离羟基,基于硫酸锌的层中的硫的表面密度大于或等于0.5mg/m2。
根据本发明的钢基材还可以具有单独或组合考虑的以下列出的任选特征:
-基于锌或其合金的金属涂层包含0.2重量%至0.4重量%的铝,其余为锌和由制造过程产生的不可避免的杂质,
-基于锌或其合金的金属涂层包含至少0.1重量%的镁,
-基于锌或其合金的金属涂层包含以下中的至少一种元素:至多10重量%含量的镁、至多20重量%含量的铝、至多0.3重量%含量的硅,
-基于硫酸锌的层中的硫的表面密度为3.7mg/m2至27mg/m2。
本发明的第二主题由根据本发明的钢基材制成的汽车部件构成。
本发明的第三主题由用于移动金属带的处理方法构成,所述方法包括根据以下的步骤:
-(i)提供在其至少一个面上涂覆有基于锌或其合金的金属涂层的钢带,
-(ii)通过简单接触将包含至少0.01mol/L硫酸锌的水性处理溶液施加至金属涂层以形成湿膜,
-(iii)随后将水性处理溶液在干燥器中在高于170℃的空气干燥温度下干燥,将水性处理溶液施加在金属涂层上与离开干燥器之间的时间小于4秒,其中带速度、湿膜厚度、初始带温度和空气流量适合于在金属涂层上形成既不包含游离水分子也不包含游离羟基的基于硫酸锌的层,基于硫酸锌的层中的硫的表面密度大于或等于0.5mg/m2。
根据本发明的处理方法还可以具有单独或组合考虑的以下列出的任选特征:
-在熔融锌浴中通过热浸镀工艺获得金属涂层,所述熔融锌浴最终包含以下中的至少一种元素:至多10重量%含量的镁、至多20重量%含量的铝、至多0.3重量%含量的硅,
-在施加水性处理溶液之前对金属涂层进行脱脂,
-水性处理溶液包含20g/L至160g/L的七水合硫酸锌,
-带速度为60m/分钟至200m/分钟,
-湿膜厚度为0.5μm至4μm,
-初始带温度为20℃至50℃,
-空气流量为5000Nm3/小时至50000Nm3/h。
-以小于2g/m2的涂覆重量将油膜施加在基于硫酸锌的层上。
发明人已经出乎意料地观察到,在转化层中羟基硫酸锌本身的存在导致经处理的金属板对一些粘合剂,尤其是基于环氧的粘合剂的弱粘合性。
不受任何科学理论的束缚,发明人的理解是羟基硫酸锌结构的羟基与粘合剂的环氧体系反应并导致粘合问题。特别地,它们的存在使界面结合锌/环氧化物劣化并且还引起粘合剂的塑化。
从层组成中排除羟基硫酸锌先验地是不可能的,因为一旦将水溶液施加在金属涂层上,pH一由于金属涂层氧化而达到7,羟基硫酸锌就在金属涂层上沉淀。
此外,发明人已经观察到,即使当转化层明显干燥时,在转化层中也可以存在游离水分子和/或游离羟基。这些游离水分子和/或游离羟基也与粘合剂的特定化合物(例如,如基于环氧的化合物)极具反应性,这导致粘合问题。
发明人已经进行了深入的研究以获得不包含羟基硫酸锌且完全干燥的层,从而获得在保留最初的基于羟基硫酸锌的层的其他特性的同时对环氧粘合剂具有良好粘合性的层。
从产品的角度来看,这些研究显示,只要转化层既不包含羟基硫酸锌,也不包含游离水分子,也不包含游离羟基,以及只要转化层包含选自一水合硫酸锌、四水合硫酸锌和七水合硫酸锌的至少一种化合物,良好的对环氧粘合剂的粘合性就是可能的。
从工艺的角度来看,这些研究显示,只要小心地控制干燥器中的空气干燥温度以有利于形成一水合硫酸锌、四水合硫酸锌或七水合硫酸锌而不是硫酸锌的其他水合物,就可以获得这样的转化层。此外,已经确定,带速度、湿膜厚度、初始带温度和空气流量必须适合于空气干燥温度以完全干燥转化层并因此形成既不包含游离水分子也不包含游离羟基的基于硫酸锌的层。此外,已经确定,在溶液的施加与干燥器的末端之间的水溶液在金属涂层上的接触时间必须小于4秒,以避免形成羟基硫酸锌。
本发明的其他特征和优点将在以下描述中更详细地描述。
通过参照以下阅读以下描述将更好地理解本发明,以下描述仅出于说明目的而提供,而绝非旨在进行限制。
-图1是示出本发明要求保护的钢的结构的示意性截面图,
-图2是根据本发明的基于硫酸锌的层和现有技术的羟基硫酸锌层的IRRAS光谱,
-图3是示出根据带速度、湿膜厚度、初始带温度、空气流量和空气干燥温度的金属带在干燥器出口处完全干燥的条件的图,
在图1中,呈金属带形式的金属板1包括钢基材3,优选热轧然后冷轧的钢基材,并且金属板可以是卷绕的,例如,随后用作例如汽车车体的部件。
在该实例中,然后将金属板1从卷上解开,然后切割并成形以形成部件。
基材3在一个面5上涂覆有涂层7。在某些变型中,这种类型的涂层7可以存在于基材3的两个面上。
涂层7包括至少一个基于锌的层9。“基于锌的”意指涂层7可以是锌或其合金,即包含一种或更多种合金元素例如但不限于铁、铝、硅、镁和镍的锌。
该层9通常具有小于或等于20μm的厚度,并且旨在用于以常规方式保护基材3免受穿孔腐蚀影响的目的。应注意,在图1中未按比例绘制基材3和涂覆其的不同层的相对厚度,以使图示更易于解释。
在本发明的一种变型中,基于锌的层9包含0.2重量%至0.4重量%的铝,其余为锌和由制造过程产生的不可避免的杂质。
在本发明的一种变型中,基于锌的层9包含至少0.1重量%的镁以改善耐腐蚀性。优选地,层9包含至少0.5重量%,并且更优选至少2重量%的镁。在该变型中,在层9中镁含量被限于20重量%,因为已经观察到更高的比例将导致涂层7的过快消耗,并且因此矛盾地导致抗腐蚀作用的劣化。
当层9包含锌、镁和铝时,特别优选的是如果层9包含0.1重量%至10重量%的镁和0.1重量%至20重量%的铝。还优选地,层9包含1重量%至4重量%的镁和1重量%至6重量%的铝。
在某些变型中,涂层7可以包括在层9与基材3的面5之间的附加层11。该层可以例如由涂层7的热处理产生,所述涂层7包含在真空下沉积在例如通过电沉积预先沉积在基材3上的锌上的镁。热处理使镁和锌合金化,从而在包含锌的层11的顶部上形成包含锌和镁的层9。
层9可以在熔融锌浴中通过热浸镀工艺获得,所述熔融锌浴最终包含以下中的至少一种元素:至多10重量%含量的镁、至多20重量%含量的铝、至多0.3重量%含量的硅。该浴还可以包含至多0.3重量%的任选另外的元素,例如Sb、Pb、Ti、Ca、Mn、Sn、La、Ce、Cr、Ni、Zr或Bi。
此外,这些不同的元素可以改善延展性或层9对基材3的粘附性。熟悉其对层9的特性的影响的本领域技术人员将知晓如何根据所寻求的额外目的来使用它们。
最后,浴可以包含源自熔化的铸锭或由基材3穿过浴而产生的残余元素,例如至多0.5重量%并且通常为0.1重量%至0.4重量%的含量的铁。这些残余元素部分地掺入层9中,在这种情况下,它们用术语“由制造过程产生的不可避免的杂质”来表示。
也可以使用真空沉积工艺,例如,经由焦耳效应的真空蒸镀或磁控溅射,通过感应或通过电子束或喷射气相沉积来沉积层9。
涂层7被基于硫酸锌的层13覆盖。
层13包含选自一水合硫酸锌、四水合硫酸锌和七水合硫酸锌的至少一种化合物,并且既不包含羟基硫酸锌,也不包含游离水分子,也不包含游离羟基。
羟基硫酸锌包含羟基,基于发明人的理解,羟基与粘合剂的环氧体系反应并导致粘合问题。羟基的不存在显著改善了基于环氧的粘合剂在金属板上的粘合性。羟基硫酸锌意指以下通式的化合物:
[Znx(SO4)y(OH)z,tH2O]
其中2x=2y+z,其中y和z不同于零。
z优选高于或等于6,并且更优选z=6且3≤t≤5。特别地,在来自现有技术的金属板上已经观察到x=4、y=1、z=6且t=3的化合物。
游离水分子和游离羟基也与粘合剂的特定化合物(例如,如基于环氧的化合物)极具反应性,这导致粘合问题。它们的不存在显著改善了基于环氧的粘合剂在金属板上的粘合性。
一水合硫酸锌、四水合硫酸锌和七水合硫酸锌是稳定的化合物。由于它们的存在,避免了由于不稳定的硫酸锌水合物的分解而导致的羟基硫酸锌的随后产生。
基于硫酸锌的层13中的硫的表面密度大于或等于0.5mg/m2。低于该值,在形成金属板时金属涂层7劣化,这导致在金属板的表面处形成锌或其合金的粉末或颗粒。这些颗粒或这种粉末在成形工具中的积累和/或团聚可能由于形成倒钩和/或颈缩而损坏成形部件。
基于硫酸锌的层13可以通过如下来获得:可能在脱脂之后,将包含浓度大于或等于0.01mol/L的硫酸锌ZnSO4的水性处理溶液施加至涂层7。
当硫酸锌的浓度小于0.01mol/L时,不可以形成这样的层13,但是还发现太高的浓度不会显著提高沉积速率,并且甚至可能略微降低沉积速率。
可以通过将硫酸锌溶解在纯水中来制备水性处理溶液。例如,可以使用七水合硫酸锌(ZnSO4,7H2O)。因此Zn2+离子的浓度等于SO4 2-阴离子的浓度。
所使用的水性处理溶液优选包含20g/L至160g/L的七水合硫酸锌,这相当于0.07mol/L至0.55mol/L的Zn2+离子的浓度和SO4 2-离子的浓度。已经发现,在该浓度范围内,沉积速率不受浓度值的显著影响。
水性处理溶液的pH优选对应于溶液的自然pH,而不添加碱或酸。该pH值通常为4至7。
水性处理溶液的温度为20℃至60℃。
水性处理溶液以常规方式,例如通过浸渍、辊涂、喷洒最后随后是挤压来施加。
水性处理溶液与涂层7的接触时间小于4秒。“接触时间”意指将水性处理溶液施加在金属板上(例如,金属板进入处理浴中或施加在辊涂设备的辊的金属板上)与离开干燥器之间的时间。高于该4秒的限制,pH有时间升高至高于羟基硫酸锌的沉淀极限,这导致在基于硫酸锌的层的生产期间该化合物在金属板上的有害沉积。
从实际的角度来看,可以通过IRRAS模式的红外光谱法(入射角为80°的红外反射-吸收光谱法)来控制羟基硫酸锌的不存在。如图2的下部所示,如果基于硫酸锌的层包含羟基硫酸锌,则IRRAS光谱呈现多个吸收峰,所述吸收峰归属于υ3硫酸盐振动1077-1136-1177cm-1和OH拉伸区域3000-3400cm-1中的活性水带。这些结果与文献中指出的羟基硫酸锌结构相匹配(υ1硫酸盐振动:1000cm-1,υ2硫酸盐振动:450cm-1,υ3硫酸盐振动:1068–1085–1130cm-1,υ4硫酸盐振动:611-645cm-1,羟基振动:3421cm-1)。
干燥器中的空气干燥温度适合于有利于形成一水合硫酸锌、四水合硫酸锌或七水合硫酸锌而不是硫酸锌的其他水合物。出乎意料地观察到,高于170℃的空气干燥温度有利于这些化合物的产生。
由于这些稳定的化合物的存在,避免了由于不稳定的硫酸锌水合物的分解导致的羟基硫酸锌的随后产生。
从实际的角度来看,这些稳定的硫酸锌水合物的存在可以通过IRRAS模式的红外光谱法(入射角为80°的红外反射-吸收光谱法)来控制。如图2的上部所示,如果基于硫酸锌的层包含稳定的硫酸锌水合物而不含羟基硫酸锌,则IRRAS光谱呈现位于1172cm-1附近的一个单一的硫酸盐峰而不是3个峰。更具体地,这些稳定的硫酸锌水合物中的每一者的存在可以通过与差示扫描量热法(DSC)耦合的IRRAS模式的红外光谱法通过追踪硫酸盐带和游离水带来控制。
带速度、湿膜厚度、初始带温度和空气流量适合于在金属涂层上形成既不包含游离水分子也不包含游离羟基的基于硫酸锌的层,所述基于硫酸锌的层中的硫的表面密度大于或等于0.5mg/m2。优选地,基于硫酸锌的层中的硫的表面密度为3.7mg/m2至27mg/m2。
湿膜厚度可以用定位在干燥器之前的红外测量仪测量。所述红外测量仪由光源、红外检测器和特定的过滤器构成。测量原理基于红外光吸收。
空气流量被定义为在整个干燥器中每秒吹送并冲击金属带的空气的量。因此,干燥器中的喷嘴的配置可以尤其在数量、尺寸、设计、位置等方面变化。
优选地,干燥器包括6至12个喷嘴,以更好地将空气喷射冲击分配在金属带上。优选地,干燥器包括定位在距离金属带4cm至12cm的喷嘴,以在不从金属带上移除湿膜的情况下避免喷射中的压力损失。优选地,喷嘴具有宽度为2mm至8mm的开口,以优化喷嘴出口处的空气速度。
在干燥器的出口,基于硫酸锌的层中水的不存在可以尤其用高光谱相机来控制。该后者由与光谱仪(其将光分散成波长)耦合的红外矩阵检测器构成。测量设备可以由线形IR灯(800mm长)和双向反射配置的MWIR(中波IR)高光谱相机组成。相机的检测范围为3μm至5μm,其对应于液态水的主要吸收带。测量原理在于测量从金属带反射的光的强度。如果水残留在基于硫酸锌的层中,则其吸收一部分光,并且反射较小的强度。
在一种变型中,通过监测干燥器中的钢带的温度来控制干燥器出口处的基于硫酸锌的层中不存在水。只要膜中存在水,就消耗热空气的热能来使水蒸发,并且由于水蒸发而使金属带的温度保持恒定或甚至降低。一旦膜是干燥的,就消耗热空气的热能来加热金属带。通过监测干燥器中的钢带的温度,因此易于控制金属带的温度在离开干燥器之前开始升高。
在一种变型中,通过IRRAS模式的红外光谱法(入射角为80°的红外反射-吸收光谱法)来控制干燥器出口处的基于硫酸锌的层中不存在水。如图2的下部所示,如果基于硫酸锌的层包含游离水,则IRRAS光谱呈现位于1638cm-1和1650cm-1附近的峰。
通过IRRAS模式的红外光谱法(入射角为80°的红外反射-吸收光谱法)来控制干燥器出口处的基于硫酸锌的层中不存在游离羟基。如图2的下部所示,如果基于硫酸锌的层包含游离羟基,则IRRAS光谱呈现位于3600cm-1处的峰。
干燥过程基本上是同时传热和传质的操作,其中以干燥空气提供从溶液中蒸发液体的能量。因此,热空气既用于供应用于蒸发的热量,又用于从产品中带走蒸发的水分。外部条件(带速度、初始湿膜厚度、初始带温度、空气流量)是控制该现象的关键参数。
参数是相互依赖的。这主要是由现象的复杂性质引起的,因为单个参数的变化(例如不同的空气干燥温度)引起其他参数例如空气流量的变化。因此,难以确定基于硫酸锌的层既不包含游离水分子也不包含游离羟基的所有范围。然而,本领域技术人员将知晓如何基于以下描述的实施例调节参数。
实施例1:
如图3a)所示,基于硫酸锌的层在干燥器的末端是干燥的范围根据带速度(A,以m/分钟计)和空气流量(B,以Nm3/小时计)给出。等高线对应于干燥器出口处的水膜的厚度。因此,对于高于等高线0.1μm的条件(白色区域),基于硫酸锌的层是干燥的。
这些结果是在以下条件下获得的:
-空气干燥温度:175℃
-初始带温度:30℃
-初始膜厚度:2μm
-接触时间:<4秒
实施例2:
如图3b)所示,基于硫酸锌的层在干燥器的末端是干燥的范围根据带速度(A,以m/分钟计)和初始带温度(B,以℃计)给出。
这些结果是在以下条件下获得的:
-空气干燥温度:175℃
-空气流量:8280Nm3/小时
-初始膜厚度:2μm
-接触时间:<4秒
实施例3:
如图3c)所示,基于硫酸锌的层在干燥器的末端是干燥的范围根据空气流量(A,以Nm3/小时计)和带温度(B,以℃计)给出。
这些结果是在以下条件下获得的:
-空气干燥温度:175℃
-带速度:120m/分钟
-初始膜厚度:2μm
-接触时间:<4秒
实施例4:
如图3d)所示,基于硫酸锌的层在干燥器的末端是干燥的范围根据空气流量(A,以Nm3/小时计)和初始膜厚度(B,以μm计)给出。
这些结果是在以下条件下获得的:
-空气干燥温度:175℃
-带速度:120m/分钟
-初始带温度:30℃
-接触时间:<4秒
实施例5:
如图3e)所示,基于硫酸锌的层在干燥器的末端是干燥的范围根据空气流量(A,以Nm3/小时计)和空气干燥温度(B,以℃计)给出。
这些结果是在以下条件下获得的:
-初始带温度:30℃
-带速度:120m/分钟
-初始膜厚度:2μm
-接触时间:<4秒
优选地,带速度为60m/分钟至200m/分钟。优选地,湿膜厚度为0.5μm至4μm。优选地,初始带温度为20℃至50℃。优选地,空气流量为5000Nm3/小时至50000Nm3/小时。
在表面上形成层13之后,层13可以任选地被润滑。
该润滑可以通过以小于2g/m2的涂覆重量在层13上施加油膜(未示出)来进行。
如将在以下仅通过说明的方式提供的非限制性实施例中看出的,发明人已经表明,层13的存在使得可以改善与汽车工业中使用的粘合剂,尤其是基于环氧的粘合剂的粘合性,而不降低其他性能例如耐腐蚀性和可拉性。
通过在镀锌钢上施加包含50g/L至130g/L的七水合硫酸锌的水性处理溶液并通过使用以下条件在4秒内干燥湿膜来评估不同参数对羟基硫酸锌的不存在的影响:
-样品A:
o空气干燥温度:110℃
o带速度:100m/分钟
o初始带温度:30℃
o初始膜厚度:3μm
o空气流量:45000Nm3/小时
-样品B:
o空气干燥温度:140℃,
o带速度:110m/分钟
o初始带温度:30℃
o初始膜厚度:2μm
o空气流量:12000Nm3/小时
-样品C:
o空气干燥温度:150℃,
o带速度:120m/分钟
o初始带温度:22℃
o初始膜厚度:3μm
o空气流量:8300Nm3/小时
样品D:
o空气干燥温度:175℃,
o带速度:120m/分钟
o初始带温度:40℃
o初始膜厚度:2μm
o空气流量:33000Nm3/小时
通过IRRAS红外光谱法评估基于硫酸锌的层的组成。如图4所示,仅样品D呈现归属于稳定的硫酸锌水合物的在1172cm-1附近的单个硫酸盐峰。样品A、B和C呈现归属于羟基硫酸锌结构的υ3硫酸盐振动的多个吸收峰。
通过单搭接剪切测试(single lap shear test)评估基于环氧的粘合剂在形成在样品A至D上的基于硫酸锌的层上的粘合性。首先,在没有脱脂的情况下使用AnticoritFuchs 3802-39S(1g/m2)对100mm长和25mm宽的测试件进行重新涂油(re-oiled)。然后两个测试件(一个经水性处理溶液处理,一个未经处理)如下组装:用来自的基于环氧的粘合剂通过使用特氟龙垫片将它们叠置在12.5mm长上,以保持两个件之间的0.2mm的均匀厚度。使整个组合件在190℃下在烘箱中固化20分钟。然后在粘合测试和老化测试之前调整样品24小时。对于每个测试条件,测试了5个组合件。
已经根据DIN EN 1465标准对粘合性进行了评估。在该测试中,使用50KN的单元力(cell force)将每个接合的组合件固定在拉力机的夹爪中(在每个夹具中抓住每个测试件的50mm,每个测试件的50mm留空)。在室温下以10mm/分钟的速率拉动样品。最大剪切应力值以MPa记录,破坏模式在视觉上分类为:
-如果在大部分粘合剂中出现撕裂,则内聚破坏,
-表面内聚破坏是在靠近带/粘合剂界面的大部分粘合剂中出现撕裂,
-如果撕裂出现在带/粘合剂界面处,则粘合失效。
如果观察到粘合失效,则测试不通过。
已经通过泥敷剂测试(cataplasm test)评估了粘合性的老化。在该测试中,将每个接合的组合件(每次5个试样)包裹在具有去离子水(棉重量的10倍)的棉(重量为45g+/-5)中,放入聚乙烯袋中,然后密封。将密封的袋在70℃、100%HR下在烘箱中保持7天。一旦已经进行了泥敷剂测试,就根据DIN EN 1465标准重新评估粘合性。
获得的结果示于图5中,其中各列表示在初始阶段(H0)和在泥敷剂测试中7天后(H7)的内聚破坏百分比(呈黑色)。
如所示出的,仅样品D在初始阶段呈现良好的粘合性,并且在泥敷剂测试中7天后呈现低的性能下降。
测试件的临时保护通过如DIN EN ISO 6270-2所规定的,在湿度和温度受控的腐蚀测试室中进行的测试,随后是在层13上以约1g/m2的涂覆重量施加保护油Fuchs(注册商标)3802-39S来评估。
在根据DIN EN ISO 6270-2在湿度和温度受控的腐蚀测试室中进行的测试中,使测试件在湿度和温度受控的腐蚀测试室(即,具有受控的气氛和温度的外壳)中经历24小时的两个老化循环。这些循环模拟带卷或切割成片的带在储存期间的腐蚀条件。每个循环包括:
-在40℃±3℃和约98%相对湿度下8小时的第一阶段,随后是
-在21℃±3℃和小于98%的相对湿度下16小时的第二阶段。
在4次循环之后,必须看不到任何劣化。
在10次循环之后,必须目视改变小于10%的测试件的表面。
在测试件上进行的测试证实了根据本发明的表面处理在临时保护方面的良好行为。
Claims (9)
1.一种用于移动金属带的处理方法,包括根据以下的步骤:
-(i)提供在其至少一个面上涂覆有基于锌或其合金的金属涂层的钢带,
-(ii)通过简单接触将包含至少0.01mol/L硫酸锌的水性处理溶液施加至所述金属涂层以形成湿膜,
-(iii)随后将所述水性处理溶液在干燥器中在高于170℃的空气干燥温度下干燥,将所述水性处理溶液施加在所述金属涂层上与离开所述干燥器之间的时间小于4秒,其中带速度、湿膜厚度、初始带温度和空气流量适合于在所述金属涂层上形成既不包含游离水分子也不包含游离羟基的基于硫酸锌的层,所述基于硫酸锌的层中的硫的表面密度大于或等于0.5mg/m2。
2.根据权利要求1所述的处理方法,其中在熔融锌浴中通过热浸镀工艺获得所述金属涂层,所述熔融锌浴最终包含以下中的至少一种元素:至多10重量%含量的镁、至多20重量%含量的铝、至多0.3重量%含量的硅。
3.根据权利要求1或2中任一项所述的处理方法,其中在施加所述水性处理溶液之前对所述金属涂层进行脱脂。
4.根据权利要求1或2中任一项所述的处理方法,其中所述水性处理溶液包含20g/L至160g/L的七水合硫酸锌。
5.根据权利要求1或2中任一项所述的处理方法,其中所述带速度为60m/分钟至200m/分钟。
6.根据权利要求1或2中任一项所述的处理方法,其中所述湿膜厚度为0.5μm至4μm。
7.根据权利要求1或2中任一项所述的处理方法,其中所述初始带温度为20℃至50℃。
8.根据权利要求1或2中任一项所述的处理方法,其中所述空气流量为5000Nm3/小时至50000Nm3/小时。
9.根据权利要求1或2中任一项所述的处理方法,其中以小于2g/m2的涂覆重量将油膜施加在所述基于硫酸锌的层上。
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US20200216964A1 (en) | 2020-07-09 |
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WO2019073273A1 (en) | 2019-04-18 |
ZA202000837B (en) | 2020-12-23 |
US11319631B2 (en) | 2022-05-03 |
PL3695021T3 (pl) | 2024-04-15 |
CA3073252A1 (en) | 2019-04-18 |
MX2020003633A (es) | 2020-07-29 |
UA125239C2 (uk) | 2022-02-02 |
JP2020537044A (ja) | 2020-12-17 |
EP3695021B1 (en) | 2024-01-17 |
EP3695021A1 (en) | 2020-08-19 |
JP6979125B2 (ja) | 2021-12-08 |
BR112020004038B1 (pt) | 2023-11-28 |
BR112020004038A2 (pt) | 2020-09-01 |
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WO2019073319A1 (en) | 2019-04-18 |
RU2755907C1 (ru) | 2021-09-22 |
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