CN106232870A - 取向性电磁钢板用无铬绝缘被膜处理液和带无铬绝缘被膜的取向性电磁钢板 - Google Patents
取向性电磁钢板用无铬绝缘被膜处理液和带无铬绝缘被膜的取向性电磁钢板 Download PDFInfo
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Abstract
通过使用具有如下组成的无铬绝缘被膜处理液,在极力减少钛螯合物等高价钛的使用量或者不使用高价钛的情况下就能够低廉地得到兼具长时间优异的耐吸湿性和充分的铁损减少效果的无铬绝缘被膜,上述无铬绝缘被膜处理液含有选自Mg、Ca、Ba、Sr、Zn、Al和Mn的磷酸盐中的1种或2种以上,相对于上述磷酸盐100质量份,含有以SiO2固体成分换算计为50~120质量份的胶体状二氧化硅,并且,含有Mg、Ca、Ba、Sr、Zn、Al和Mn的水溶性金属盐,将处理液中的金属元素的M2+(=Mg、Ca、Ba、Sr、Zn、Mn)和/或M3+(=Al)与P的摩尔比调整为0.6≤(M2++1.5×M3+)/P≤1.0的范围。
Description
技术领域
本发明涉及取向性电磁钢板用无铬绝缘被膜处理液,特别涉及在取向性电磁钢板的表面被覆无铬被膜时能够有效防止以往不可避免地产生的耐吸湿性下降而能够确保与含铬绝缘被膜同等优异的耐吸湿性的无铬绝缘被膜处理液。
另外,本发明涉及具备使用上述的无铬绝缘被膜处理液形成的无铬绝缘被膜的带无铬绝缘被膜的取向性电磁钢板。
背景技术
一般,在取向性电磁钢板中,为了赋予绝缘性、加工性和防锈性等而在钢板的表面设置被膜。该表面被膜由以最终成品退火时形成的镁橄榄石为主体的基底被膜和在其上形成的磷酸盐系的上涂被膜构成。
由于这些被膜在高温下形成,而且具有低的热膨胀率,所以具有利用钢板温度下降至室温时的钢板与被膜的热膨胀率差对钢板赋予张力而减少铁损的效果。因此,期望能够对钢板赋予尽量高的张力。
为了满足这样的期望,一直以来提出有各种被膜。
例如专利文献1中,提出了以磷酸镁、胶体状二氧化硅和无水铬酸为主体的被膜。另外,专利文献2中,提出了以磷酸铝、胶体状二氧化硅和无水铬酸为主体的被膜。
另一方面,近年来随着对环保的关心的提高,对不含铬、铅等有害物质的制品的期望越来越强烈,在取向性电磁钢板中也期待开发出无铬被膜。然而,无铬被膜的情况下,由于产生耐吸湿性明显下降、张力赋予不足等问题,所以难以制成无铬被膜。
作为解决上述问题的方法,专利文献3、专利文献4中提出了使用由胶体状二氧化硅、磷酸铝、硼酸和硫酸盐构成的处理液形成被膜的方法。由此,改善了耐吸湿性以及基于赋予张力的铁损减少效果,但是仅靠该方法,与形成含铬被膜的情况相比,无法说得到了充分的改善铁损和耐吸湿性效果。
因此,为了解决这个问题,例如尝试了将处理液中的胶体状二氧化硅增量等。由此,消除了张力赋予不足,增加了铁损减少效果,但是耐吸湿性反而发生了下降。另外,还尝试了增加硫酸盐的添加量,但这种情况下,耐吸湿性虽被改善,却变得张力赋予不足,铁损减少效果不充分,不论哪种情况都未能同时满足两个特性。
除这些方法以外,作为无铬被膜的形成方法,例如专利文献5中提出了添加硼化合物代替铬化合物的方法。另外,专利文献6中提出了添加氧化物胶体的方法。此外,专利文献7中提出了添加金属有机酸盐的方法。
然而,不论使用上述哪一种技术,都不能实现使耐吸湿性和基于赋予张力的铁损减少效果这两者达到与形成含铬被膜的情况同等级,不是完全的解决对策。
另外,作为与本发明接近的技术,可举出专利文献8、9中记载的技术。专利文献8中,公开了为防止吸湿而含有包含Fe、Al、Ga、Ti、Zr等金属元素的胶体状化合物的技术。另外,专利文献9中公开了通过使用Ti螯合物改善耐吸湿性的技术。
现有技术文献
专利文献
专利文献1:日本特公昭56-52117号公报
专利文献2:日本特公昭53-28375号公报
专利文献3:日本特公昭54-143737号公报
专利文献4:日本特公昭57-9631号公报
专利文献5:日本特开2000-169973号公报
专利文献6:日本特开2000-169972号公报
专利文献7:日本特开2000-178760号公报
专利文献8:日本特开2007-23329号公报
专利文献9:日本特开2009-57591号公报
发明内容
然而,专利文献8的技术中,长期的耐吸湿性存在问题。另外,专利文献9的技术中,存在使用钛螯合物成本高这样的问题。
本发明是鉴于上述的实际情况而开发的,其目的在于提供在不使用高价钛螯合物的情况下,利用最小量必要的廉价Ti源或者不利用就能够同时实现优异的耐吸湿性和基于充分的张力赋予的高铁损减少效果的取向性电磁钢板用无铬绝缘被膜处理液。
另外,本发明的目的在于提供具备使用上述的无铬绝缘被膜处理液形成的无铬绝缘被膜的带无铬绝缘被膜的取向性电磁钢板。
于是,本发明人等为了解决上述的课题,利用无铬绝缘被膜得到所需的耐吸湿性和基于赋予张力的铁损减少效果,进行了深入调查研究。
其结果,发现了即便采用专利文献8的技术其长期的耐吸湿性也较差的原因是Fe、Al、Ga、Ti、Zr等金属元素的含量不充分。另外,如果绝缘被膜中的含量相同则Ti的耐吸湿性改善效果仅次于Cr,较高,因此在专利文献8公开的技术中尝试了增加Ti量的结果,判明了其发生结晶化,由绝缘被膜产生的张力下降或绝缘被膜的色调发生白浊化。
因此,本发明人等着眼于目前已知的以磷酸盐为基础的绝缘被膜大多数为偏磷酸盐组成(即M=2价金属的情况下,M/P=0.5),对在M/P比大于0.5的区域的涂布特性进行了深入研究。
其结果,得到了如下见解:通过使磷酸盐中的金属M与磷的比(M/P)成为M多,能够提高绝缘被膜的耐吸湿性,因此即使Ti的含量少或不含有Ti也能够实现上述目的。
本发明是基于上述的见解进一步反复研究而最终完成的。
即,本发明的主旨构成如下。
1.一种取向性电磁钢板用无铬绝缘被膜处理液,含有选自Mg、Ca、Ba、Sr、Zn、Al和Mn的磷酸盐中的1种或2种以上,相对于所述磷酸盐100质量份含有以SiO2固体成分换算计为50~120质量份的胶体状二氧化硅,并且,含有Mg、Ca、Ba、Sr、Zn、Al和Mn的水溶性金属盐,将处理液中的金属元素的M2+(=Mg、Ca、Ba、Sr、Zn、Mn)和/或M3+(=Al)与P的摩尔比调整为0.6≤(M2++1.5×M3+)/P≤1.0的范围。
2.一种取向性电磁钢板用无铬绝缘被膜处理液,含有选自Mg、Ca、Ba、Sr、Zn、Al和Mn的磷酸盐中的1种或2种以上,相对于所述磷酸盐100质量份,含有以SiO2固体成分换算计为50~120质量份的胶体状二氧化硅,并且,含有Mg、Ca、Ba、Sr、Zn、Al和Mn的水溶性金属盐,将处理液中的金属元素的M2+(=Mg、Ca、Ba、Sr、Zn、Mn)和/或M3+(=Al)与P的摩尔比调整为0.6≤(M2++1.5×M3+)/P≤1.0的范围,进一步含有以TiO2换算计为25质量份以下的Ti。
3.根据上述1或2所述的取向性电磁钢板用无铬绝缘被膜处理液,其中,上述水溶性金属盐为选自硝酸盐、硫酸盐、乙酸盐和氯化物中的1种或2种以上。
4.根据上述2或3所述的取向性电磁钢板用无铬绝缘被膜处理液,其中,使用TiO2溶胶作为Ti源。
5.根据上述4所述的取向性电磁钢板用无铬绝缘被膜处理液,其中,在TiO2溶胶中,相对于TiO2含有以固体质量比率计为0.1~50%的磷酸钛。
6.一种带无铬绝缘被膜的取向性电磁钢板,是在最终成品退火后的取向性电磁钢板的表面涂布上述1~5中任一项所述的处理液,并在800℃~1000℃的温度进行10秒~300秒的烧结处理而得到的。
根据本发明,能够在极力减少钛螯合物等高价钛的使用量或者不使用高价钛的情况下,低廉地得到兼具长时间优异的耐吸湿性和充分的铁损减少效果的无铬绝缘被膜。
具体实施方式
以下,对作为本发明基础的实验结果进行说明。
首先,如下制作试样。
将用公知方法制造的板厚:0.23mm的完成成品退火的取向性电磁钢板剪切成300mm×100mm的大小,除去未反应的退火分离剂之后,在N2气氛中实施800℃、2小时的去应力退火。
接下来,用5%磷酸进行轻微酸洗之后,涂布下述绝缘被膜处理液。
首先,将以固体成分换算计为100质量份的磷酸镁水溶液、以固体成分换算计为66.6质量份胶体状二氧化硅以及硝酸镁,以成为表1中记载的M(=Mg2+)/P(摩尔比)的方式添加,将其以干燥后单位面积质量为10g/m2(两面)的方式涂布。接下来,装入干燥炉(300℃,1分钟),其后实施兼作平坦化退火和绝缘被膜的烧结的热处理(800℃,2分钟,N2:100%)。其后,进一步进行第二次去应力退火(800℃,2小时,N2气氛)。
对如此得到的试样进行基于赋予张力的铁损减少效果和耐吸湿性分析。
铁损减少效果是用SST试验器(单板磁性试验器)测定的磁特性来评价的。磁特性的测定是针对各试样分别在涂布绝缘被膜处理液之前、烧结绝缘被膜之后和第二次去应力退火之后进行的。
耐吸湿性是利用磷的溶出试验来评价的。该试验如下进行,即,从绝缘被膜被烧结后的钢板切出3片50mm×50mm的试件,通过将它们在100℃的蒸馏水中沸腾5分钟使磷从绝缘被膜表面溶出,根据其溶出量判断绝缘被膜在水中溶解的容易程度。
表1中示出对磁特性、磷溶出量和被膜外观分析而得的结果。
应予说明,表中的各项目如下。
·涂布前B8(R):涂布绝缘被膜处理液之前的磁通密度
·涂布后ΔB=B8(C)-B8(R)其中,B8(C):烧结绝缘被膜之后的磁通密度
·去应力退火后ΔB=B8(A)-B8(R)其中,B8(A):第二次去应力退火之后的磁通密度
·W17/50(R):涂布绝缘被膜处理液之前的铁损
·涂布后ΔW=W17/50(C)-W17/50(R)其中,W17/50(C):烧结绝缘被膜之后的铁损
·去应力退火后ΔW=W17/50(A)-W17/50(R)其中,W17/50(A):第二次去应力退火之后的铁损
·磷的溶出量:在烧结绝缘被膜后立刻测定
·被膜外观:目视观察判定去应力退火后的绝缘被膜的透明度
由表1的实验结果可知通过使M/P成为镁多的情况(M/P>0.50),能够兼得铁损改善和耐吸湿性,但是,如果镁过量则由于结晶化使被膜外观白浊化,由于张力劣化导致去应力退火后的铁损劣化。
接下来,对本发明的各构成要件的限定理由进行叙述。
本发明中作为对象的钢板只要是取向性电磁钢板即可,对钢种类没有特别要求。通常,这样的取向性电磁钢板是通过如下制造的:用公知的方法对含硅钢坯进行热轧,通过1次或者夹带中间退火的多次冷轧加工成最终板厚,之后实施一次再结晶退火,接下来涂布退火分离剂后,进行最终成品退火。
绝缘被膜处理液成分中,首先,作为磷酸盐,使用选自Mg、Ca、Ba、Sr、Zn、Al和Mn的磷酸盐中的1种或2种以上。一般使用选自上述磷酸盐中的任1种,但通过混合2种以上使用能够精密地控制绝缘被膜的物性值。作为磷酸盐的种类,磷酸二氢盐(重磷酸盐)容易得到,因而优选。应予说明,碱金属(Li、Na等)的磷酸盐因使耐吸湿性非常差而不适合。
相对于上述的磷酸盐100质量份,含有以SiO2固体成分换算计为50~120质量份的胶体状二氧化硅。低于50质量份时,绝缘被膜的热膨胀系数减少效果小,无法对钢板赋予充分的张力,因此得不到形成绝缘被膜带来的铁损改善效果。另一方面,如果比120质量份多则不仅在烧结时绝缘被膜容易结晶化,耐吸湿性也劣化。
本发明中,重要的是以处理液中的金属元素的2价元素M2+(=Mg、Ca、Ba、Sr、Zn、Mn)和/或3价元素M3+(=Al)与P的摩尔比成为0.6≤(M2++1.5×M3+)/P≤1.0的方式含有该金属元素的水溶性金属盐。上述式中,对于M,为了与2价金属对应,3价金属的情况下换算成相当于1.5倍。
如果该M/P低于0.6,则磷的溶出量多,耐吸湿性劣化。另一方面,如果M/P大于1.0,则绝缘被膜结晶化,对钢板赋予的张力下降而导致铁损的劣化。
作为M/P的调整中使用的金属盐,由于绝缘被膜处理液为水溶液,所以适合使用水溶性金属盐。此外,由于使用硝酸盐、硫酸盐、乙酸盐和氯化物等作为金属盐时试剂容易获得且低廉,因而优选。
此外,为了进一步改善耐吸湿性,在上述绝缘被膜处理液中,可以相对于磷酸盐100质量份含有以TiO2换算计为25质量份以下的Ti。如果超过25质量份则改善效果饱和,从制造成本的观点考虑反而不利。此外,如果含有5质量份以上则Ti的效果变明显,因而更优选。
绝缘被膜处理液中含有Ti时,从获得的容易性和成本等观点考虑,优选使用TiO2溶胶。TiO2溶胶的pH可以为酸性、中性、碱性中的任一种,优选pH:5.5~12.5之间。
另外,在TiO2溶胶中,为了提高TiO2粒子的分散性以及提高与磷酸盐的相溶性而提高绝缘被膜处理液稳定性,优选相对于TiO2含有以固体质量比率计为0.1%~50%的磷酸钛。磷酸钛的含量低于0.1%时提高相溶性的效果不足,另一方面如果比50%多则成本增高。
另外,由于二氧化硅、氧化铝等无机矿物粒子对改善防黏连性有效,可以一并使用。但是,关于添加量,为了不降低填充系数,相对于胶体状二氧化硅20质量份,最多优选为1质量份。
将上述的处理液涂布在电磁钢板的表面并烧结而形成绝缘被膜。被膜的单位面积质量两面总计优选为4~15g/m2。这是由于如果单位面积质量比4g/m2少则层间电阻下降,如果比15g/m2多则填充系数下降。
上述绝缘被膜的烧结处理可以兼作平坦化退火来进行,在800~1000℃的温度范围设为10~300秒的均热时间。如果温度过低或者时间过短,则平坦化不充分,形状不良,因而导致合格率下降。另一方面,如果温度过高,则平坦化退火的效果太强,发生蠕变变形而使磁特性劣化。
实施例
(实施例1)
准备板厚:0.23mm的完成最终成品退火的取向性电磁钢板。此时的取向性电磁钢板的磁通密度B8为1.912T。将该取向性电磁钢板用磷酸进行酸洗后,在两面涂布总计为10g/m2的表2所示的各种无铬绝缘被膜处理液之后,在N2:100%的气氛中,在850℃、30秒的条件下进行烧结处理。其后,在N2:100%的气氛中,在800℃实施2小时的去应力退火。
磷酸盐分别使用磷酸二氢盐水溶液,其量表示经过固体成分换算的量。调整M/P时分别使用六水合硝酸镁、一水合乙酸钙、一水合乙酸钡、氯化锶、氯化锌、硫酸铝(无水盐)、六水合硝酸锰,使来自磷酸盐的金属元素的摩尔比不发生变化(例如,来自磷酸Mg和磷酸Ca的Mg与Ca的摩尔比为1∶1时,以来自硝酸镁和乙酸钙的Mg与Ca的摩尔比也成为1∶1的方式添加)。
将对如此得到的取向性电磁钢板的各特性进行分析而得的结果示于表3。
应予说明,各特性的评价如下进行。
·W17/50(R):涂布绝缘被膜处理液之前的铁损
·涂布后ΔW=W17/50(C)-W17/50(R)其中,W17/50(C):烧结绝缘被膜之后的铁损
·去应力退火后ΔW=W17/50(A)-W17/50(R)其中,W17/50(A):去应力退火之后的铁损
·磷的溶出量:使3片50mm×50mm的试件在100℃的蒸馏中沸腾5分钟后,分析
·被膜外观:目视观察判定去应力退火后的绝缘被膜的透明度
表2
表3
如表2、3所示,通过将M/P比调整成0.6~1.0的范围,且含有以SiO2固体成分换算计为50~120质量份的胶体二氧化硅,从而得到了磷溶出量少、耐吸湿性优异且外观良好的无铬绝缘被膜。
(实施例2)
准备板厚:0.23mm的完成成品退火的取向性电磁钢板。此时的取向性电磁钢板的磁通密度B8为1.912T。将该取向性电磁钢板用磷酸进行酸洗后,在两面涂布总计为12g/m2的表4所示的各种的无铬绝缘被膜处理液之后,在N2:100%的气氛中,在900℃、60秒的条件下进行烧结处理。其后,在N2:100%的气氛中,在800℃实施2小时的去应力退火。
应予说明,作为磷酸盐,使用磷酸镁水溶液,其量以固体成分换算计采用100g。调整M/P时使用四水合乙酸镁。另外,作为Ti源,使用以固体成分换算计为表4所示的量的Tayca(株)制的二氧化钛溶胶TKS-203。
将对如此得到的取向性电磁钢板的各特性进行分析而得的结果一并记在表4中。
应予说明,各特性的评价与实施例1的情况相同。
由表4可知通过将M/P比调整成0.6~1.0的范围,且含有以SiO2固体成分换算计为50~120质量份的胶体二氧化硅,能够得到磷溶出量少、耐吸湿性优异且外观良好的无铬绝缘被膜。并且,通过含有以TiO2换算计为25质量份以下的Ti,能够进一步减少磷溶出量。
产业上的可利用性
在用于取向性电磁钢板的绝缘被膜中,针对不含有Cr时出现的耐吸湿性劣化(P的溶出量增大)问题,通过将M/P比调整成M多(P少,能够在极力减少高价钛的使用量或者不使用高价钛的情况下就得到耐吸湿性和铁损改善效果优异的无铬绝缘被膜。
Claims (6)
1.一种取向性电磁钢板用无铬绝缘被膜处理液,含有选自Mg、Ca、Ba、Sr、Zn、Al和Mn的磷酸盐中的1种或2种以上,相对于所述磷酸盐100质量份含有以SiO2固体成分换算计为50~120质量份的胶体状二氧化硅,并且含有Mg、Ca、Ba、Sr、Zn、Al和Mn的水溶性金属盐,将处理液中的金属元素的M2+和/或M3+与P的摩尔比调整为0.6≤(M2++1.5×M3+)/P≤1.0的范围,其中,M2+时,M=Mg、Ca、Ba、Sr、Zn、Mn,M3+时,M=Al。
2.一种取向性电磁钢板用无铬绝缘被膜处理液,含有选自Mg、Ca、Ba、Sr、Zn、Al和Mn的磷酸盐中的1种或2种以上,相对于所述磷酸盐100质量份,含有以SiO2固体成分换算计为50~120质量份的胶体状二氧化硅,并且,含有Mg、Ca、Ba、Sr、Zn、Al和Mn的水溶性金属盐,将处理液中的金属元素的M2+和/或M3+与P的摩尔比调整为0.6≤(M2++1.5×M3+)/P≤1.0的范围,进一步含有以TiO2换算计为25质量份以下的Ti,其中,M2+时,M=Mg、Ca、Ba、Sr、Zn、Mn,M3+时,M=Al。
3.根据权利要求1或2所述的取向性电磁钢板用无铬绝缘被膜处理液,其中,所述水溶性金属盐为选自硝酸盐、硫酸盐、乙酸盐和氯化物中的1种或2种以上。
4.根据权利要求2或3所述的取向性电磁钢板用无铬绝缘被膜处理液,其中,使用TiO2溶胶作为Ti源。
5.根据权利要求4所述的取向性电磁钢板用无铬绝缘被膜处理液,其中,在TiO2溶胶中,相对于TiO2含有以固体质量比率计为0.1~50%的磷酸钛。
6.一种带无铬绝缘被膜的取向性电磁钢板,是在最终成品退火后的取向性电磁钢板的表面涂布权利要求1~5中任一项所述的处理液,并在800℃~1000℃的温度进行10秒~300秒的烧结处理而得到的。
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- 2015-03-02 US US15/118,428 patent/US20170137633A1/en not_active Abandoned
- 2015-03-02 CN CN201580020584.1A patent/CN106232870A/zh active Pending
- 2015-03-02 RU RU2016145432A patent/RU2656433C2/ru active
- 2015-03-02 WO PCT/JP2015/001087 patent/WO2015162837A1/ja active Application Filing
- 2015-03-02 JP JP2015551922A patent/JPWO2015162837A1/ja active Pending
- 2015-03-02 EP EP15783783.2A patent/EP3135793B1/en active Active
- 2015-03-02 KR KR1020187001901A patent/KR101867257B1/ko active IP Right Grant
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CN112567073A (zh) * | 2018-08-17 | 2021-03-26 | 杰富意钢铁株式会社 | 绝缘覆膜形成用处理液的制造方法和带有绝缘覆膜的钢板的制造方法以及绝缘覆膜形成用处理液的制造装置 |
CN112567073B (zh) * | 2018-08-17 | 2022-05-27 | 杰富意钢铁株式会社 | 绝缘覆膜形成用处理液的制造方法和制造装置以及带有绝缘覆膜的钢板的制造方法 |
CN112771203A (zh) * | 2018-09-28 | 2021-05-07 | 杰富意钢铁株式会社 | 无铬绝缘被膜形成用处理剂、带绝缘被膜的方向性电磁钢板及其制造方法 |
CN112771203B (zh) * | 2018-09-28 | 2023-10-17 | 杰富意钢铁株式会社 | 无铬绝缘被膜形成用处理剂、带绝缘被膜的方向性电磁钢板及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR101867257B1 (ko) | 2018-06-12 |
JPWO2015162837A1 (ja) | 2017-04-13 |
KR20160134781A (ko) | 2016-11-23 |
RU2016145432A3 (zh) | 2018-05-24 |
KR20180011349A (ko) | 2018-01-31 |
EP3135793A4 (en) | 2017-05-03 |
EP3135793A1 (en) | 2017-03-01 |
RU2016145432A (ru) | 2018-05-24 |
EP3135793B1 (en) | 2020-01-29 |
WO2015162837A8 (ja) | 2016-08-25 |
US20170137633A1 (en) | 2017-05-18 |
RU2656433C2 (ru) | 2018-06-05 |
WO2015162837A1 (ja) | 2015-10-29 |
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