CN104884676B - 表面处理钢板及其制造方法 - Google Patents
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Abstract
本发明涉及一种表面处理钢板及其制造方法,具体涉及一种耐蚀性和导热性优异的表面处理钢板。在本发明中为达到所述目的,通过将含有导电性等物理性质非常优异的石墨烯(graphene)的高分子树脂组合物涂覆于基础钢板表面,从而能够提供不仅能确保因高分子树脂组合物而具有的耐蚀性,而且还能确保石墨烯固有的特性的表面处理钢板。
Description
技术领域
本发明涉及一种表面处理钢板及其制造方法,具体涉及一种耐蚀性和导热性优异的表面处理钢板。
背景技术
一般来说,适用于汽车车体等的钢板会在汽车公司组装车体后经过磷酸盐处理和涂装。此时组装的车体中会出现几处钢板重叠的部位,磷酸盐或涂料很难侵入该重叠的部位,因此存在耐蚀性变脆弱的问题。
为了解决这种问题,之前是采用了通过对钢板重叠的部位进行封闭(sealing)处理来阻断腐蚀因子接近该部位的方案。但是,这种方案导致最终产品的生产率降低的同时成本上升的问题,其结果是如今需要既能省去封闭处理环节,又具有耐蚀性优异的表面处理钢板。
近来,作为省略了封闭处理的表面处理钢板,广泛地研究在基础钢板上涂布有机薄膜的钢板,实际上普遍使用具有一定厚度的有机薄膜层的表面处理钢板。
这种包括有机薄膜层的表面处理钢板具有在即使没有经过磷酸盐处理和涂装的部位也能够确保耐蚀性的优点,但由于有机薄膜层厚,因此进行电阻焊接时存在焊接性降低的问题。
因此,需要一种能够有效确保耐蚀性的同时,在之后进行电阻焊接时也具有优异的焊接性的表面处理钢板。
发明内容
(一)要解决的技术问题
本发明的一个方面,其目的在于提供一种因耐蚀性和高导热性,确保优异的焊接性的表面处理钢板及其制造方法。
(二)技术方案
本发明的一个方面,提供一种表面处理钢板,包括基础钢板及所述基础钢板上部的含有石墨烯的高分子树脂层,所述石墨烯在所述高分子树脂层内排列。
本发明的另一方面,提供一种表面处理钢板的制造方法,包括以下步骤:准备基础钢板;在所述基础钢板的上部涂覆含有石墨烯的高分子树脂组合物;以及对已涂覆的基础钢板进行干燥及固化,以形成含有石墨烯的高分子树脂层;其中,在进行所述干燥时,在所述已涂覆的基础钢板的下部施加电场或磁场,使所述石墨烯被排列在所述高分子树脂层内。
(三)有益效果
根据本发明,在基础钢板上形成含有石墨烯的高分子树脂层,从而与现有的有机薄膜处理等相比,能够更有效地确保耐蚀性,同时也能够确保导热性。
并且,根据本发明的另一个方面,能够制造包括高分子树脂层的已经过表面处理的钢板,其中,所述高分子树脂层含有一定厚度的均匀的石墨烯。
具体实施方式
对于适用于汽车车身等的表面处理钢板,本发明人为了得到与现有的表面处理钢板相比具有优异的耐蚀性、且在之后进行电阻焊接时也能够确保焊接性的表面处理钢板,而进行了深入的研究,结果发现通过将包括导电性、机械强度等的物理性质非常优异的石墨烯(graphene)的高分子树脂组合物涂布于钢板表面而使其具有一定的厚度时,因均匀形成的石墨烯,能够提供确保耐蚀性、导热性的同时能够确保石墨烯所具有的各种固有物理性质的表面处理钢板,从而完成了本发明。
石墨烯由碳原子构成,是以一个原子的厚度形成的薄膜,且为碳元素以六角形形状连接的蜂窝形状的二维平面结构的物质,被知晓为强度和导电性、导热性、电性等的物理性质非常优异。
目前,产业界等各领域活跃进行应用这种石墨烯的物理性质的研究,举一个例子,正在应用在基板等上涂覆基于溶液的石墨烯溶液的技术。但是,虽然基于溶液涂覆石墨烯的技术具有能够通过简单的方法涂覆石墨烯的优点,但仍存在石墨烯片(sheet)无法向一定的方向均匀地被涂覆的问题。
在本发明中,通过将所述石墨烯排列在基础钢板与树脂层的界面附近或树脂层的表层附近,而解决上述问题,从而提供新概念的表面处理钢板。
即,根据本发明的发明人的研究结果,石墨烯属于碳基材料,是SP2结构,由六角形碳原子形成板状结构,因此能够有效地抑制形成在冷轧钢板表面的微细的氧化铁皮的生长,且具有紧凑结构的石墨烯层,在腐蚀环境中也能够有效阻断水分等的穿透,因此能够使钢板具有耐蚀性。
因此,本发明中提出一种耐蚀性和导热性优异的表面处理钢板,该钢板包括基础钢板及所述基础钢板上部的含有石墨烯的高分子树脂层,所述石墨烯在所述高分子树脂层内按一定方向排列。
此时,形成在所述基础钢板上部的,含有石墨烯的高分子树脂层的平均厚度优选为0.5~5.0μm,更优选为1~3μm。当形成在基础钢板上部的含有石墨烯的高分子树脂层的平均厚度小于0.5μm时,由于所述高分子树脂层中含有的石墨烯的含量不充分,因此具有不仅难以赋予石墨烯的固有特性,而且难以确保高分子树脂层自身的耐蚀性的问题。相反,当含有石墨烯的高分子树脂层的平均厚度超过5.0μm而形成厚厚的高分子树脂层时,虽能够充分确保石墨烯的特性,但高分子树脂层本身有可能不均匀地形成,之后加工时也会出现加工精度降低的现象,因此不优选。
本发明的有利的表面处理钢板的制造方法,只要是能够在基础钢板的上部形成含有石墨烯的高分子树脂层的方法,就不作特别的限定。只是,按照通常能够制定的方法,事先制备石墨烯溶液,然后将制备好的石墨烯溶液涂布于基础钢板的表面上,以便在基础钢板的表面形成层,但这种方法有可能在工序效率或粘贴强度等方面存在问题。
因此,本发明的一个方面,提出一种将石墨烯片(sheet)在基础钢板上镀敷,使具有均匀的方向的优选方法。即,在本发明中,当将含有石墨烯的高分子树脂组合物涂覆于基础钢板表面时,利用电磁场(电场或磁场)将包含在所述组合物内的石墨烯片排列成在高分子树脂层内具有一定的方向,从而能够提高与基础钢板的粘着性。
即,根据本发明的发明人的研究结果,由于石墨烯的边缘(edge)部分中存在的羟基(OH)的溶解度(solubility)高,因此当利用溶液工艺时,可形成大面积的薄膜,且通过均匀地排列石墨烯的羟基(OH)来提高与基础钢板的粘着性,与此同时,具有能够有效赋予石墨烯固有的特性的优点。
下面,对本发明的一个方面的表面处理钢板的制造方法的具体实施例进行详细说明。只是,本发明的思想并不限定于所提出的实施例,虽然,理解本发明的思想的普通技术人员能够通过在相同的思想范围内增加、变更、删除其他组件等,能够容易地提出落后的其他发明或包括在本发明的思想范围内的其他实施例,而且这也包含在本发明的思想范围内。
下面,对本发明的一个方面的包括含有石墨烯的高分子树脂层的表面处理钢板的制造方法进行详细说明。
作为制造本发明的表面形成有含有石墨烯的高分子树脂层的表面处理钢板的一个优选实施例,包括以下步骤:准备基础钢板;将含有石墨烯的高分子树脂组合物涂覆在所述基础钢板的上部;以及,对所述已涂覆的基础钢板进行干燥及固化,在进行所述干燥时,在所述已经过涂覆的基础钢板的下部施加电场或磁场。
对本发明的适用于表面处理钢板的制造方法的基础钢板不作特别的限定,可使用普通的钢铁材料或非钢铁材料。
如上所述,如果准备好基础钢板,就可以将含有石墨烯的高分子树脂组合物涂覆在该基础钢板的上部。
此时,所使用的含有石墨烯的高分子树脂组合物是在普通的高分子树脂组合物中含有石墨烯的组合物,所述高分子树脂组合物只要是通常使用的粘合剂树脂都可以使用,但是,可优选地使用从由聚氨酯树脂、丙烯酸树脂、环氧树脂、酯树脂、烯烃树脂组成的组中选择的一种或两种以上的树脂。更为优选地使用聚氨酯树脂。除所述粘合剂树脂以外,所述高分子树脂组合物还可包括固化剂、耐蚀性增强剂等。
此时,以重量份计,所述粘合剂树脂的使用量优选为整个树脂组合物的10~90重量份,此时,若小于10重量份,则粘合剂树脂,例如聚氨酯树脂对腐蚀离子的耐盐水性及对化学物质渗透的耐化学性无法被发挥出来,导致耐化学性及抗碱性降低。由此,当利用pH10以上的碱性溶液在60℃的温度下进行五分钟的脱脂时,会出现树脂薄膜变色或剥离的问题。相反,当超过90重量份时,不仅因凝结现象而导致溶液稳定性降低,而且由于价格的上升,具有在经济方面上不利的缺点。因此,粘合剂树脂在整个树脂组合物内的含量优选为10~90重量份,其余的成分可由水组成。
可用作所述粘合剂树脂的聚氨酯树脂的耐水性、耐化学性、耐酸性及抗碱性强,由此形成的涂膜即柔软又坚硬,因此,会用在通过涂装钢板或铝板等来防止表面出现划痕的情况,或者为了赋予耐化学性而被广泛使用。因此,只要是为实现这种目的而使用的本领域的普通聚氨酯树脂,就不作特别的限定。只是,单独使用这种聚氨酯树脂时,在实现柔软又坚硬的性质的方面上存在局限性,因此,在本发明中,可将软质聚氨酯树脂和硬质聚氨酯树脂混合在一起来作为聚氨酯树脂使用。
在这种情况下,以聚氨酯树脂的固体含量的浓度为基准,软质聚氨酯树脂优选为5~95重量份,当所述软质聚氨酯树脂的固体含量的浓度小于5重量份时,虽提高加工性能,但耐热性及耐水劣化性会降低,相反,若超过95重量份,则不具有加工性能的提高效果,反而,会出现耐蚀性大幅降低的问题。
所述软质聚氨酯树脂可使用如聚氨酯水分散树脂、聚乙烯改性聚氨酯树脂等的异戊二烯二异氰酸酯;用二元酸和多元醇制造的聚氨酯树脂或聚氨酯丙烯酸树脂;如聚乙烯丙烯酸改性聚氨酯树脂等的丙烯酸多元醇或用聚亚安酯制造的聚氨酯树脂。在此,所述多元醇可使用丙烯酸多元醇、聚酯多元醇、聚醚多元醇、聚烯烃多元醇或其混合物。而且,所述软质聚氨酯树脂的分子量优选为5000至300000,当分子量小于5000时,加工性能大幅降低,相反,若超过300000,则存在溶液的稳定性降低的问题。
并且,硬质聚氨酯树脂可使用聚己内酯多元醇或聚碳酸酯多元醇和二异氰酸盐,特别是可使用,用对亚苯基二异氰酸酯制造的聚氨酯树脂或用4,4'-双(ω-羟基氧化烯)联苯和甲基-2,6-二异氰酸酯己酸盐制造的聚氨酯树脂或者具有缩醛键的聚氨酯树脂等,此时所述硬质聚氨酯树脂的分子量优选为200000到2000000。当所述硬质聚氨酯树脂的分子量小于200000时,不具有加工性能的提高效果,当超过2000000时,溶液的稳定性就会降低,且由于树脂溶液的粘度的增加,因此存在可加工性降低的问题。这种硬质聚氨酯树脂在制造干膜时,肖氏(Shore)A硬度优选为40至90。若肖氏A硬度小于40,则不具有加工性能的提高效果,相反,若超过90,则涂膜、树脂层变得很结实,加工时会被破碎,因此不具有加工性能的提高效果,因此优选具有所述范围的硬度。
另一方面,所述粘合剂树脂也可利用丙烯酸树脂,所述丙烯酸树脂的耐高温高湿性、抗寒性及加工性优异,且价格低廉,因此广泛使用在金属表面处理工艺上。可使用在本发明中的丙烯酸树脂有,含有可水溶性羧基的、由普通的单体组合方式合成的丙烯酸树脂。此时,丙烯酸树脂单体可使用丙烯酸甲酯(甲基)、丙烯酸乙酯(甲基)、丙烯酸异丙酯(甲基)、丙烯酸正丁酯(甲基)、丙烯酸异丁酯(甲基)、丙烯酸2-乙基己酯(甲基)、丙烯酸羟基丙酯(甲基)、丙烯酸十八酯(甲基)、丙烯酸羟基丁酯(甲基),但并不限定于此。
所述丙烯酸树脂的分子量优选为50000至2000000,当所述丙烯酸树脂的分子量小于50000时,不具有加工性能的提高效果,相反,当超过2000000时,溶液的稳定性会降低,树脂溶液的粘度增加,由此存在可加工性降低的问题。
并且,所述粘合剂树脂可利用环氧树脂,所述环氧树脂的粘着性,耐蚀性、上涂涂装性等优异,因此广泛用作金属原材料的涂层材料。在本发明中可使用的环氧树脂为双酚A型树脂、双酚F型树脂、酯醛树脂等。
所述环氧树脂的分子量优选为500至25000,当所述环氧树脂的分子量小于500时,由于交联密度的变大,难以确保加工性能,相反,当超过25000时,难以实现水溶性,且固化膜的交联密度变小,由此存在耐蚀性降低的问题。
并且,所述粘合剂树脂可利用酯树脂,所述酯树脂的硬化性优异,且耐化学性、耐热性、塑性优异,且与有机物形成的粘着性优异,因此广泛用作金属表面处理的材料。在本发明中可使用的酯树脂为用马来酸酐、异酞酸、对苯二酸、四氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、己二酸、庚二酸制造的聚酯树脂或乙二醇改性酯树脂、丙二醇改性酯树脂、新戊二醇改性酯树脂。
所述酯树脂的分子量优选为2000至20000,当所述酯树脂的分子量小于2000时,由于交联密度变大,加工性能变脆弱,相反,当超过20000时,不仅价格上升,而且因交联密度变大而具有耐盐水性变脆弱,耐蚀性降低的问题。
并且,所述粘合性树脂可利用烯烃树脂,所述烯烃树脂的耐水性、耐酸性及耐盐水性强,且涂膜坚硬,因此在进行金属表面处理后,有效防止涂装面被划伤。在本发明中可使用的烯烃树脂为水溶性聚烯烃树脂,优选地使用聚乙烯、乙烯基改性聚乙烯树脂、聚乙烯丁烯树脂、氯乙烯共聚物、乙烯-乙酸乙烯酯共聚物或聚乙烯醇树脂。
所述烯烃树脂的分子量优先为50000至2000000,当所述烯烃树脂的分子量小于50000时,由于交联密度变大,难以确保加工性能,相反,当分子量超过2000000时,难以实现水溶性,且发生树脂的沉淀,固化膜的交联密度也会变小,因此具有耐蚀性降低的问题。
如上所述,本发明的含有石墨烯的高分子树脂组合物,优选地,包括所述粘合剂树脂而形成的高分子树脂组合物中包含0.01~20重量%的石墨烯,更为优选地,包含1.0~20重量%的石墨烯。
如上所述,高分子树脂组合物起到利于确保基础钢板耐蚀性的作用,所述高分子树脂组合物中的石墨烯是为了使基础钢板具有石墨烯的固有特性而添加的,通过添加所述石墨烯,不仅能够极好地确保基础钢板的耐蚀性,而且还能极好地确保导热性,因此能够确保加工时的焊接性。
如上所述,为使基础钢板具有石墨烯固有的特性,用于涂覆基础钢板的高分子树脂组合物中应含有一定含量的石墨烯,此时,优选地,将粉末状的石墨烯添加后与高分子树脂组合物混合一起。
此时,包含在所述高分子树脂组合物的石墨烯优选为0.01~20重量%,此时,当石墨烯的含量小于0.01重量%,难以有效确保所要达到的石墨烯的物理性质,相反,当石墨烯的含量超过20重量%时,虽然在确保石墨烯的物理性质方面不存在问题,但有可能会出现大量的石墨烯不均匀地被涂覆在基础钢板表面上的问题,因此不优选。
对于如上所述的将含有石墨烯的高分子树脂组合物涂覆在基础钢板的上部的方法,并不作特别的限定,但可采用例如棒式涂布机、辊式涂布机、幕帘式涂布机等方法。举一个例子,当使用利用辊式涂布机的辊涂方法时,首先将所要涂覆的组合物,即本发明中的石墨烯溶液倒入混合(mixing)槽中,并将其充分地搅拌后,通过循环管道移送到涂布机盘(coater pan),然后在涂布机盘上用辊式涂布机(roll coater)将组合物涂覆在涂覆层上。
优选地,基础钢板上的所述含有石墨烯的高分子树脂组合物的涂覆工序结束后,对其进行干燥及硬化。此时,干燥方法可使用本技术领域中普遍为人所知的方法,例如,可使用热风加热方式、红外线加热方式、感应加热方式等方法。然后,优先地,进行硬化处理,使被涂覆的溶液按层(layer)变得很牢固。
另一方面,在本发明中,对所述已涂覆的基础钢板进行干燥的同时,可在已涂覆的基础钢板的下部施加电场或磁场。
如上所述,对已涂覆的基础钢板进行干燥的同时施加电场或磁场,是为了提高已涂覆的溶液中含有的,即,高分子树脂组合物中含有的石墨烯的粘着力。更具体地,在将含有石墨烯的高分子树脂组合物涂覆于基础钢板上后,石墨烯排列不均匀,是分散在高分子树脂组合物上的形态。这种石墨烯在边缘(edge)部分包含官能团(羟基(OH)),若在这里施加电场或磁场,则能够将石墨烯的官能团拉动或排出,从而能够在基础钢板与树脂组合物的界面即被涂覆的高分子树脂组合物内,将分散的石墨烯密集到下部或上部。
作为一个例子,可对已涂覆的基础钢板进行干燥的同时施加-200~+200V(0除外)电压。由于石墨烯的羟基(OH)带负电荷,因此若在所述基础钢板上施加正电压,则所述石墨烯的羟基向基础钢板的方向排列,若施加负电压,则所述石墨烯的羟基向基础钢板的反方向排列,从而能够提高粘着力。此时,石墨烯能够以板状(sheet)形式存在或通过形成浓缩层来存在,其中,板状形式的存在是,使具有石墨烯固有特性的最有利的形式。
为了得到上述效果而施加到基础钢板上的电压会根据使用的基础钢板的不同而变化,因此不作特别的限定,但优选地施加-200~+200V(0除外)范围内的电压。
因此,将含有石墨烯的树脂组合物涂布在基础钢板上,然后进行干燥时,若施加-200~小于0V的电压,则之后形成的高分子树脂层内的石墨烯会向基础钢板的反方向,即,向所述高分子树脂层的表层的方向存在,若施加超过0~+200V的电压,之后形成的高分子树脂层内的石墨烯会向基础钢板的方向,即,向所述高分子树脂层的下部方向存在。
因此,如上所述,为了对已涂覆的基础钢板进行干燥的同时施加电压,优选地利用设置有DC电压装置的干燥装置。
通过所述本发明的一个实施例来制造的表面处理钢板不仅能够具有优异的耐蚀性,而且还具有优异的石墨烯的固有特性,即,导热性等特性。因此,在后续的工序中,对本发明的表面处理钢板进行焊接时,能够确保焊接性的优点。
下面,通过实施例对本发明进行更为具体的说明。只是,以下的实施例只是为了说明本发明而示例的,并不是为了限定本发明的权利要求范围。因为,本发明的权利要求范围是由权利要求书中记载的事项和从所述记载的事项合理地推导的事项决定。
(实施例)
将普通碳钢作为基础钢板,利用棒式涂布机(Bar-coater)在基础钢板上涂覆粘合剂,所述粘合剂为在包含聚氨酯树脂的高分子树脂组合物中含有1重量%的石墨烯的溶液,然后,通过热风加热方式对已涂覆的基础钢板进行干燥,同时从所述基础钢板下部施加-200、0或+200V的电压,从而制造出已经过表面处理的钢板。
为了在通过改变所述施加电压来制造出的各表面处理钢板上,评价基础钢板与含有石墨烯的高分子树脂层之间的粘着力,将所述各表面处理钢板以1mm的间距沿横向和竖向进行10次交叉切割(Cross Hatch Cut)后,通过粘贴和揭开胶带的方法,实施粘着力的评价,然后将其结果表示在表1中。
评价粘着力的标准是从100个正四边形部位揭开的胶带中含有多少高分子树脂层。此时,因粘着力好而树脂层不会被剥离时,评价为100/100,因粘着力差而树脂层全部被剥离时,评价为0/100。
而且,对上述各表面处理钢板同时进行耐蚀性的评价,并将其结果一同表示在表1中。
耐蚀性评价是通过将已制造的钢板进行盐雾试验来进行的,而且是根据白锈出现面积达到试片表面积的5%为止所需的时间来评价的。
表1
施加电压 | -200V | 0V | +200V |
粘着力评价 | 90/100 | 95/100 | 100/100 |
耐蚀性评价 | 72Hr | 48Hr | 72Hr |
如上述表1所示,将本发明的含有石墨烯的高分子树脂组合物涂布在基础钢板上,然后向基础钢板施加电压时,不仅能确认基础钢板与树脂层之间的粘着力优异,而且还能确认耐蚀性优异。
Claims (8)
1.一种表面处理钢板,其包括基础钢板和所述基础钢板上部的含有石墨烯的高分子树脂层,所述石墨烯在边缘部具有羟基,并且所述石墨烯的羟基在高分子树脂层内向基础钢板的方向排列或向高分子树脂层的表层的方向排列,并且所述高分子树脂层包含1.0~20重量%的所述石墨烯。
2.根据权利要求1所述的表面处理钢板,所述石墨烯在所述高分子树脂层内以浓缩层的形式存在,或以板状形式存在。
3.根据权利要求1所述的表面处理钢板,所述含有石墨烯的高分子树脂层的平均厚度为0.5~5.0μm。
4.根据权利要求1所述的表面处理钢板,其中,所述含有石墨烯的高分子树脂层由高分子树脂组合物中含有1.0~20重量%的石墨烯的组合物形成,所述高分子树脂组合物,包括:粘合剂树脂和其余的水,其中,粘合剂树脂是从由聚氨酯树脂、丙烯酸树脂、环氧树脂、烯烃树脂组成的组中选择的一种或两种以上的树脂,以整个树脂组合物为100重量份计,其含量为10~90重量份。
5.一种表面处理钢板的制造方法,包括以下步骤:
准备基础钢板;
在所述基础钢板的上部涂覆含有1.0~20重量%的石墨烯的高分子树脂组合物;以及
对所述已涂覆的基础钢板进行干燥及固化,以形成含有石墨烯的高分子树脂层,
其中,在进行所述干燥时,在所述已涂覆的基础钢板的下部施加-200~200V且0除外的电压,从而使所述石墨烯排列在高分子树脂层内。
6.根据权利要求5所述的表面处理钢板的制造方法,其中,所述含有石墨烯的高分子树脂组合物是高分子树脂组合物中含有1.0~20重量%的石墨烯的组合物,所述高分子树脂组合物,包括:粘合剂树脂和其余的水,其中,粘合剂树脂是从由聚氨酯树脂、丙烯酸树脂、环氧树脂、烯烃树脂组成的组群中选择的一种或两种以上的树脂,以整个树脂组合物为100重量份计,其含量为10~90重量份。
7.根据权利要求5所述的表面处理钢板的制造方法,若在进行所述干燥时,在所述已涂覆的基础钢板的下部施加-200~小于0V的电压之后进行固化,则所述石墨烯在高分子树脂层内向表层的方向存在。
8.根据权利要求5所述的表面处理钢板的制造方法,若在进行所述干燥时,在所述已涂覆的基础钢板的下部施加大于0~+200V的电压之后进行固化,则所述石墨烯在高分子树脂层内向基础钢板的方向存在。
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