CN109563626A - 带无铬绝缘张力被膜的取向性电磁钢板及其制造方法 - Google Patents
带无铬绝缘张力被膜的取向性电磁钢板及其制造方法 Download PDFInfo
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Abstract
本发明提供具有耐吸湿性和被膜张力优异的无铬绝缘张力被膜的取向性电磁钢板和其制造方法。带无铬绝缘张力被膜的取向性电磁钢板在取向性电磁钢板的表面具有含有磷酸盐和二氧化硅的绝缘张力被膜,被膜内部存在通式(1)表示的结晶性的化合物。MII 3MIII 4(XVO4)6···(1)式(1)中,MII、MIII各自独立地为选自Sc、Ti、V、Mn、Fe、Co、Ni、Cu、Mg中的1种或2种以上,XV为选自P、V、Mo中的1种或2种以上。带无铬绝缘张力被膜的取向性电磁钢板的制造方法是在最终退火后的取向性电磁钢板的表面涂布将含有磷酸盐和金属元素M的化合物以特定的配合比配合于胶体状二氧化硅的绝缘张力被膜用处理液,进行至少1次在使用非氧化性的气体且使露点为0℃以下的气氛下加热到900℃以上的热处理。
Description
技术领域
本发明涉及解决在取向性电磁钢板的绝缘张力被膜中不使用铬时作为课题的耐吸湿性和被膜张力的劣化的、具有这些被膜性能优异的无铬绝缘张力被膜的取向性电磁钢板。
背景技术
一般为了确保绝缘性、加工性和防锈性等而在取向性电磁钢板的表面形成有被膜。作为其中一个例子有如下被膜,其由以在最终退火(二次再结晶目的的退火)中形成的镁橄榄石为主体的基底被膜和形成于其上的磷酸盐系的绝缘张力被膜构成。这些的被膜由于在高温下形成而且具有较低的热膨胀率,因此在温度降低到室温的钢板和被膜之间热膨胀率产生较大差异,对钢板赋予张力,因而对减少铁损有效。因此,期望被膜具有对钢板赋予尽可能高的张力的功能。
为了满足这样的诸多性能,一直以来提出有各种被膜。
例如,在专利文献1中提出了一种由含有磷酸镁、胶体状二氧化硅和铬酸酐的处理液形成的被膜,另外,在专利文献2中提出了一种由含有磷酸铝、胶体状二氧化硅和铬酸酐的涂覆液形成的被膜。
随着近年来对环境保护的关心的提高,迫切期待开发出一种不含有对环境影响大的铬的绝缘张力被膜。专利文献1、2中记载的被膜因含有铬而对环境的负荷较大。因此,期待不含有铬的被膜。
然而,在无铬(不含铬的)被膜的情况下,会产生明显的耐吸湿性的降低、张力赋予不足的问题,因此一直无法制成无铬。
作为解决上述问题的方法,在专利文献3中提出了一种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的被膜形成方法。然而,仅使用该方法时,与形成含有铬的被膜的情况相比,无法说铁损和耐吸湿性的改善效果充分。
此外,作为无铬的被膜形成方法,例如在专利文献4中公开了一种添加硼化合物来代替铬化合物的方法,在专利文献5中公开了一种添加氧化物胶体状物质的方法,在专利文献6中公开了一种添加金属有机酸盐的方法。
然而,不论使用哪种技术,均没有使耐吸湿性和因赋予张力所致的铁损减少效果这两者达到与形成含有铬的被膜的情况相同的水平,不能成为完全的解决方案。
另外,在专利文献7中公开了如下技术:不是对绝缘张力被膜本身,而是在形成以镁橄榄石为主体的基底被膜时,通过利用形成镁橄榄石基底被膜来控制氧单位面积量,从而在不含有铬的绝缘张力被膜中得到耐吸湿性、被膜张力。由此,即使在不含有铬时也能够实现耐吸湿性、被膜张力优异的绝缘被膜张力。
然而,近年来,如专利文献8所公开的那样,有时应用通过在退火分离剂中添加硫酸盐并将该退火分离剂涂布于最终退火前的钢板而提高钢板的磁特性的技术。这样的情况下,难以形成适于形成不含有铬的绝缘张力被膜的基底被膜。
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57-9631号公报
专利文献4:日本特开2000-169973号公报
专利文献5:日本特开2000-169972号公报
专利文献6:日本特开2000-178760号公报
专利文献7:日本专利第4682590号公报
专利文献8:日本专利第4321120号公报
发明内容
本发明是鉴于如上所述的背景而进行的,目的在于提供具有耐吸湿性和被膜张力优异的无铬绝缘张力被膜的取向性电磁钢板及其制造方法。
本发明人等对在无铬绝缘张力被膜中改善耐吸湿性和被膜张力的方法反复进行深入研究,结果得到了以下新见解:通过在绝缘张力被膜中使下述通式(1)表示的结晶性的化合物存在而可改善这两种性能。
MII 3MIII 4(XVO4)6···(1)
通式(1)中,MII、MIII各自独立地为选自Sc、Ti、V、Mn、Fe、Co、Ni、Cu、Mg中的1种或2种以上,XV为选自P、V、Mo中的1种或2种以上。
通式(1)中的MII的个数为3,例如,MII由2种以上的上述原子构成的情况下,其合计数为3。同样,通式(1)中的MIII的个数为4、MIII由2种以上的上述原子构成的情况下,其合计数为4。通式(1)中的(XVO4)的个数为6、(XVO4)由2种以上构成的情况下,其合计数为6。
以下,对用于得到该见解的实验进行说明。
对含有Si:3.25质量%、由公知的方法制造的板厚0.23mm的最终退火(二次再结晶目的的退火)后的取向性电磁钢板用磷酸溶液进行酸洗,将相对于以固体成分换算计20质量份的胶体状二氧化硅,磷酸二氢镁40质量份(固体成分换算)、氢氧化铁(III)5质量份(FeO换算)的配合比例的绝缘张力被膜用处理液涂布成以干燥质量计两面合计为10g/m2,装入干燥炉(300℃,1分钟),进行干燥。对由此得到的钢板进行以下的任一种处理。
记号A:在露点-20℃的N2气氛中实施800℃×2分钟的加热处理。
记号B:在露点-20℃的N2气氛中进行800℃×2分钟的加热处理之后,在露点-20℃的N2气氛中实施850℃×30秒的加热处理作为第2次的加热处理。
记号C:在露点-20℃的N2气氛中进行800℃×2分钟的加热处理之后,在露点-20℃的N2气氛中实施900℃×30秒的加热处理作为第2次的加热处理。
记号D:在露点-20℃的N2气氛中进行800℃×2分钟的加热处理之后,在露点-20℃的N2气氛中实施950℃×30秒的加热处理作为第2次的加热处理。
记号E:在露点-20℃的N2气氛中进行800℃×2分钟的加热处理之后,在露点-20℃的N2气氛中实施1000℃×30秒的加热处理作为第2次的加热处理。
记号F:在露点-20℃的N2气氛中进行800℃×2分钟的加热处理之后,在露点-20℃的N2气氛中实施1050℃×30秒的加热处理作为第2次的加热处理。
记号G:在露点20℃的N2气氛中进行800℃×2分钟的加热处理之后,在露点-20℃的N2气氛中实施900℃×30秒的加热处理作为第2次的加热处理。
记号H:在露点-20℃的N2气氛中进行800℃×2分钟的加热处理之后,在露点-10℃的N2气氛中实施900℃×30秒的加热处理作为第2次的加热处理。
记号I:在露点-20℃的N2气氛中进行800℃×2分钟的加热处理之后,在露点0℃的N2气氛中实施900℃×30秒的加热处理作为第2次的加热处理。
记号J:在露点-20℃的N2气氛中进行800℃×2分钟的加热处理之后,在露点20℃的N2气氛中实施900℃×30秒的加热处理作为第2次的加热处理。
记号K:在露点-20℃的N2气氛中进行800℃×2分钟的加热处理之后,在露点-20℃的含有氧的N2气氛中实施900℃×30秒的加热处理作为第2次的加热处理。
其中,上述N2气氛中的氧浓度(体积浓度)为1000ppm以下,含有氧的N2气氛中的氧浓度为2000ppm。
对如上所述得到的带绝缘张力被膜的取向性电磁钢板,按照以下示出的方法进行铁损、被膜张力和耐吸湿性的评价。
对于铁损,利用JIS C 2550中规定的方法,使用由带绝缘张力被膜的取向性电磁钢板制作的宽度30mm×长度280mm的试验片进行测定。
对于被膜张力σ,从由带绝缘张力被膜的取向性电磁钢板制作的宽度30mm×长度280mm的试验片的一侧面,使用碱、酸等来除去绝缘张力被膜,接着将上述试验片的一端30mm固定,将试验片250mm的部分作为测定长度进行翘曲度的测定,由以下公式求出。应予说明,钢板杨氏模量为121520MPa。
σ(MPa)=钢板杨氏模量(MPa)×板厚(mm)×翘曲度(mm)/(测定长度(mm))2
对于耐吸湿性,将由带绝缘张力被膜的取向性电磁钢板制作的50mm×50mm的试验片3张在100℃的蒸馏水中浸渍煮沸5分钟而从绝缘张力被膜表面溶出磷,根据其溶出量[μg/150cm2]来判断绝缘张力被膜的在水中溶解的容易性。将溶出量为150[μg/150cm2]以下评价为良好。P(磷)的溶出量测定方法没有特别限定,本申请中利用ICP发射光谱法进行定量分析。
将得到的结果示于表1。
[表1]
*)氧浓度2000ppm
如表1所示,加热处理的温度越高,被膜张力越提高,铁损越减少。另外,P溶出量减少,耐吸湿性提高。进一步在作为平坦化退火的800℃×2分钟的热处理时的气氛露点为20℃的情况下,还在以结晶化为目的的第2次的加热处理时为非氧化性气氛且露点为-20℃的情况下P溶出量减少,耐吸湿性提高(记号G)。另外,使以结晶化为目的的热处理的气氛为含有氧的N2气氛(氧浓度2000ppm)时,即便在900℃以上的温度下P溶出量也不降低(记号K)。
此外,对这些钢板使用Cu靶以20kV、250mA的条件进行X射线衍射分析。进一步使用X射线衍射图案解析软件JADE(Rigaku公司制),根据除去衍射图案的背景而观测到的衍射峰,进行晶系的鉴定。峰搜索的条件使用初期条件(阈值σ=3.0)。其结果,在性能良好的记号C、D、E、F、G、H、I的钢板中观测到Fe7(PO4)6的衍射峰。根据以上结果,认为通过在被膜内部形成Fe7(PO4)6、即MII 3MIII 4(XVO4)6而使被膜性能提高。
其机理尚不明确,但发明人等认为如下:由于在被膜内部形成具有三维结构的结晶性的Fe7(PO4)6,被膜内的P被牢固地引入,耐吸湿性提高,防止了被膜张力的降低。
本发明的要旨构成如下。
[1]一种带无铬绝缘张力被膜的取向性电磁钢板,其特征在于,在取向性电磁钢板的至少一方的表面具有含有磷酸盐和二氧化硅的绝缘张力被膜,且上述被膜内部存在下述通式(1)表示的结晶性的化合物。
MII 3MIII 4(XVO4)6···(1)
其中,通式(1)中,MII、MIII各自独立地为选自Sc、Ti、V、Mn、Fe、Co、Ni、Cu、Mg中的1种或2种以上,XV为选自P、V、Mo中的1种或2种以上。
[2]根据[1]所述的带无铬绝缘张力被膜的取向性电磁钢板,其特征在于,上述通式(1)中,MIII为Fe,XV为P。
[3]根据[1]或[2]所述的带无铬绝缘张力被膜的取向性电磁钢板,其特征在于,上述通式(1)表示的结晶性的化合物为Fe7(PO4)6。
[4]根据[1]~[3]中任一项所述的带无铬绝缘张力被膜的取向性电磁钢板,其特征在于,上述磷酸盐由选自Mg、Fe、Al、Ca、Mn和Zn的磷酸盐中的1种或2种以上构成。
[5]一种带无铬绝缘张力被膜的取向性电磁钢板的制造方法,是[1]~[4]中任一项所述的带无铬绝缘张力被膜的取向性电磁钢板的制造方法,其特征在于,在最终退火后的取向性电磁钢板的至少一方的表面涂布如下绝缘张力被膜用处理液,进行至少1次在使用非氧化性的气体且使露点为0℃以下的气氛下加热到900℃以上的热处理,其中,所述绝缘张力被膜用处理液是在以固体成分换算计20质量份的胶体状二氧化硅中配合有10~80质量份的磷酸盐和以氧化物换算计5~10质量份的含有金属元素M的化合物(其中,上述金属元素M为选自Sc、Ti、V、Mn、Fe、Co、Ni、Cu、Mg中的1种或2种以上)。
[6]一种带无铬绝缘张力被膜的取向性电磁钢板的制造方法,是[1]~[4]中任一项所述的带无铬绝缘张力被膜的取向性电磁钢板的制造方法,其特征在于,在最终退火后的取向性电磁钢板的至少一方的表面涂布如下绝缘张力被膜用处理液,在非氧化性气氛下进行至少1次加热处理,其中,所述绝缘张力被膜用处理液是在以固体成分换算计20质量份的胶体状二氧化硅中配合有磷酸盐10~80质量份和上述通式(1)表示的结晶性的化合物的。
根据本发明,能够提供具有耐吸湿性和被膜张力优异的无铬绝缘张力被膜的取向性电磁钢板及其制造方法。
根据本发明,为了形成无铬绝缘张力被膜,即便不将基底被膜优化或者将在最终退火前涂布的退火分离剂优化,也能够得到具有耐吸湿性和被膜张力优异的无铬绝缘张力被膜的取向性电磁钢板。
具体实施方式
接下来,对本发明的各构成要件的限定理由进行叙述。
首先,本发明中作为对象的钢板只要是取向性电磁钢板,就不特别考虑钢种。通常,这样的取向性电磁钢板通过如下方式进行制造:利用公知的方法对含硅钢坯进行热轧,通过1次或夹着中间退火的多次冷轧,精轧成最终板厚之后,实施一次再结晶退火,接着涂布退火分离剂,之后进行最终退火。此时,一般的取向性电磁钢板在最终退火后钢板表面具有镁橄榄石基底被膜,但也存在如下的情况:根据情况作为退火分离剂使用氧化铝或者使用在氧化镁中添加了氯化物的粉体,使表面几乎不形成基底被膜而提高冲裁性、磁特性。或者,还存在对表面具有镁橄榄石被膜的取向性电磁钢板,利用化学研磨等除去基底被膜的情况。
本发明对在这样的不具有基底被膜的情况下的取向性电磁钢板,也能有效形成耐吸湿性和被膜张力优异的被膜。
由本发明得到的耐水性和被膜张力优异的绝缘张力被膜,只要在含有磷酸盐和二氧化硅的绝缘张力被膜内部存在上述的通式(1)表示的结晶性的化合物即可,其形成方法没有限定。此外,在上述的通式(1)中MIII为Cr、XV为As的化合物等情况下,也能够得到同样的晶体结构,但它们为环境负荷物质,因此从本发明中除去。
应予说明,例如,通过进行表1中示出的X射线衍射分析而能够容易地确认在绝缘张力被膜内部是否存在通式(1)表示的结晶性的化合物。
另外,本发明中,作为使绝缘张力被膜内部存在通式(1)表示的结晶性的化合物的方法,例如可举出如下方法:在最终退火后的取向性电磁钢板的表面涂布如下的绝缘张力被膜用处理液,在非氧化性气氛中且将露点控制为0℃以下而进行至少1次900℃以上的加热处理的方法,其中,所述绝缘张力被膜用处理液是在以固体成分换算计20质量份的胶体状二氧化硅中配合有磷酸盐10~80质量份和以氧化物换算计5~10质量份的含有金属元素M的化合物(其中,上述金属元素M为选自Sc、Ti、V、Mn、Fe、Co、Ni、Cu、Mg中的1种或2种以上)。该情况下,含有金属元素M的化合物的形态没有特别限定,为了优选得到绝缘张力被膜用处理液内的良好的分散状态,有效的是水溶性的化合物或不易凝聚的化合物。作为含有金属元素M的化合物,例如优选硫酸铁(II)、氢氧化铁(III)、硫酸锰(II)、硫酸铜(II)、硝酸镁等。另外,氧化物换算是指将含有金属元素M的化合物换算为MIIO(即,含有Sc的化合物时换算为ScO,含有Ti的化合物时换算为TiO,含有V的化合物时换算为VO,含有Mn的化合物时换算为MnO,含有Fe的化合物时换算为FeO,含有Co的化合物时换算为CoO,含有Ni的化合物时换算为NiO,含有Cu的化合物时换算为CuO,含有Mg的化合物时换算为MgO)。应予说明,常常将非氧化性气氛下的第1次加热处理兼作取向性电磁钢板的制造工序中的平坦化退火,由于在平坦化退火所需的温度下有时不进行结晶化,因此该情况下可以以结晶化为目的而进一步进行900℃以上的加热处理。MII 3MIII 4(XVO4)6的结晶化所需的温度根据种类而不同,因此只要进行适当的调整即可,但大多时,900℃以上即可,优选为950℃以上,更优选为1000℃以上。另外,非氧化性气氛下是指例如氧浓度(体积浓度)为1000ppm以下的氮、氩等非活性气体气氛下,或含有氢、一氧化碳等还原性气体的还原性气体气氛下等。而且在此需要将非氧化性气氛的露点控制为0℃以下。虽然机理尚不明,但认为对形成MII 3MIII 4(XVO4)6结构的化学反应而言,气氛为氧化性时会对反应造成影响,阻碍MII 3MIII 4(XVO4)6结构的形成。非氧化性气氛的露点优选-10℃以下。另外,非氧化性气氛的露点的下限没有特别限定,非氧化性气氛的露点优选-40℃以上。这是由于即便从-40℃进一步降低露点温度也不会对被膜的品质造成不良影响,但会没有意义地增加气氛控制成本。非氧化性气氛的露点更优选-30℃以上。
另外,本发明中,作为使绝缘张力被膜内部存在通式(1)表示的结晶性的化合物的另一方法,可举出通过在最终退火后的取向性电磁钢板的表面涂布如下绝缘张力被膜用处理液,在非氧化性气氛下进行至少1次加热处理而形成被膜的方法,其中,所述绝缘张力被膜用处理液是在以固体成分换算计20质量份的胶体状二氧化硅中配合有磷酸盐10~80质量份和通式(1)表示的结晶性的化合物。该情况下,因为配合了结晶化后的MII 3MIII 4(XVO4)6,所以在非氧化性气氛下进行至少1次加热处理,可以发挥作为被膜的烧结的作用,可以为以往的方法,例如在N2气氛下以700~900℃进行5~60秒左右的处理等。此时,作为通式(1)表示的结晶性的化合物,优选使用平均粒径为1.0μm以下的结晶性化合物,更优选使用平均粒径为0.5μm以下的结晶性化合物。如果通式(1)表示的结晶性的化合物的平均粒径超过1.0μm,则会对被膜的表面性状造成不良影响,由此在变压器中使用时容易在钢板彼此之间产生空隙,因此占空系数降低,导致变压器的性能降低。应予说明,上述平均粒径的测定方法没有特别限定,本申请中,以由激光衍射散射法测定的粒径分布中的体积基准的累积50%的粒径(D50)进行测定。
应予说明,绝缘张力被膜中的二氧化硅是用于对钢板赋予张力而减少铁损所必需的成分。另外,磷酸盐通过作为二氧化硅的粘结剂发挥作用来提高涂覆的成膜性,对被膜密合性的提高有效。
另外,在上述绝缘张力被膜用处理液中,相对于以固体成分换算计20质量份的胶体状二氧化硅,使磷酸盐为10质量份以上,这是由于如果磷酸盐不足10质量份,则被膜的裂纹变大,对于上涂被膜而言重要的耐吸湿性并不充分。另一方面,相对于以固体成分换算计20质量份的胶体状二氧化硅,使磷酸盐为80质量份以下,这是由于如果磷酸盐超过80质量份,则胶体状二氧化硅相对变少,因此张力降低而铁损减少效果变小。更优先相对于以固体成分换算计20质量份的胶体状二氧化硅,磷酸盐15~40质量份的范围。另外,作为上述磷酸盐,优选选自Mg、Fe、Al、Ca、Mn、Zn的磷酸盐中的1种或2种以上。另外,在上述绝缘张力被膜用处理液中,相对于以固体成分换算计20质量份的胶体状二氧化硅,优选将通式(1)表示的结晶性的化合物配合5~10质量份。
本发明的绝缘张力被膜的P溶出量为150[μg/150cm2]以下。本发明的绝缘张力被膜的P溶出量优选小于100[μg/150cm2],更优选为90[μg/150cm2]以下,进一步优选为80[μg/150cm2]以下,特别优选为70[μg/150cm2]以下。上述P溶出量是利用上述的耐吸湿性试验而测得的值。另外,本发明的绝缘张力被膜的被膜张力优选为5.5MPa以上,更优选为6.0MPa以上,进一步优选为7.0MPa以上,特别优选为7.5MPa以上,最优选为8.0MPa以上。上述被膜张力是利用上述的被膜张力试验而测得的值。应予说明,上述P溶出量和被膜张力可以通过调整绝缘张力被膜中的磷酸盐、二氧化硅和通式(1)表示的结晶性的化合物的配合比而进行调整。
另外,制造由本发明得到的带绝缘张力被膜的取向性电磁钢板时,对减少铁损有效的是通过在任意的工序中使用蚀刻、齿形轧辊或激光等在表面以一定间隔形成槽或者在绝缘张力被膜形成后对钢板照射激光、等离子火焰等而导入热应变来实施磁畴细分化处理。
实施例
(实施例1)基于结晶化加热处理的发明例
在最终退火后的取向性电磁钢板的表面将表2中示出的配比的绝缘张力被膜用处理液涂布成两面合计为10g/m2,预先用干燥炉以250℃×120秒进行干燥,在露点-20℃的N2气氛中实施800℃×2分钟的加热处理。
然后,在露点-20℃的N2气氛中实施1000℃×15秒的加热处理。应予说明,这些N2气氛中的氧浓度为1000ppm以下。
按照以下方法进行如上得到的带绝缘张力被膜的取向性电磁钢板的铁损、被膜张力和耐吸湿性的评价。
对于铁损,利用JIS C 2550中规定的方法,使用由带绝缘张力被膜的取向性电磁钢板制作的宽度30mm×长度280mm的试验片进行测定。
对于被膜张力σ,从由带绝缘张力被膜的取向性电磁钢板制作的宽度30mm×长度280mm的试验片的一侧面,使用碱、酸等而除去绝缘张力被膜,接着将上述试验片的一端30mm固定,将试验片250mm的部分作为测定长度而测定翘曲度,由以下公式而求出。应予说明,钢板杨氏模量为121520MPa。
σ(MPa)=钢板杨氏模量(MPa)×板厚(mm)×翘曲度(mm)/(测定长度(mm))2
对于耐吸湿性,将由带绝缘张力被膜的取向性电磁钢板制作的50mm×50mm的试验片3张在100℃的蒸馏水中浸渍煮沸5分钟而从绝缘张力被膜表面溶出磷,根据其溶出量[μg/150cm2]来判断绝缘张力被膜的在水中溶解的容易性。将溶出量为150[μg/150cm2]以下评价为良好。P的溶出量测定方法没有特别限定,本申请中,利用ICP发射光谱法进行定量分析。
将评价结果集中示于表2。
如表2所示,使用在以固体成分换算计20质量份的胶体状二氧化硅中添加了磷酸盐40~80质量份、以氧化物换算计为5~10质量份的含有金属元素M的化合物的绝缘张力被膜用处理液时,得到被膜张力和耐吸湿性优异的被膜性能。此外,利用X射线衍射所鉴定的产物为Fe7(PO4)6时,特别是P溶出量降低,即得到耐吸湿性优异的绝缘张力被膜。
另一方面,在比较例中得不到足够的被膜张力。另外,使用相对于以固体成分换算计20质量份的胶体状二氧化硅,磷酸盐的添加量小于10质量份的绝缘张力被膜用处理液时,发生被膜的剥离。
(实施例2)添加有MII 3MIII 4(XVO4)6表示的结晶性的化合物的发明例
制备在以固体成分换算计20质量份的胶体状二氧化硅中添加有磷酸二氢铝40质量份和表3中示出的MII 3MIII 4(XVO4)6表示的结晶性的化合物5质量份的绝缘张力被膜用处理液。应予说明,表3中示出的上述结晶性的化合物分别通过按以下顺序进行制备,对得到的粉末进行X射线衍射分析并根据衍射峰而确认其存在。另外,得到的粉末的平均粒径通过激光衍射散射法进行测定,确认平均粒径为1.0μm以下。应予说明,对于X射线衍射分析,使用Cu靶以20kV、250mA的条件进行测定,利用X射线衍射图案解析软件JADE(Rigaku公司制)除去衍射图案的背景,根据观测到的衍射峰而进行晶系的鉴定。
记号甲:使氧化铁(III)溶解于磷酸,加入氨而析出粉末(共沉淀法)。
记号乙、记号丙、记号丁:在溶解有硝酸镁(II)四水合物和硝酸锰(II)六水合物、硝酸铁(III)九水合物的磷酸中加入氨而析出粉末(共沉淀法)。
记号戊:使混合有氧化铜(II)、氧化铁(III)、五氧化钒的粉末的物质在900℃反应48小时而得到粉末(固相反应法)。
记号己:使混合有氧化钴(II)、氧化铁(III)、五氧化钒的粉末的物质在800℃反应20小时而得到粉末(固相反应法)。
记号庚:使混合有氧化锰(III)、氧化铁(III)、五氧化钒的粉末的物质在700℃反应20小时而得到粉末(固相反应法)。
应予说明,在上述的所有的制法中,各成分都是通过配合在化学计量上与产物(结晶性的化合物)对应的量而生成。应予说明,由共沉淀法得到的晶体粉在干燥炉中以100℃保持10小时而进行干燥。
充分搅拌上述绝缘张力被膜用处理液之后,在最终退火后的取向性电磁钢板的表面将绝缘张力被膜用处理液涂布成两面为10g/m2,预先在干燥炉中以250℃×120秒干燥之后,在露点-20℃的N2气氛中实施800℃×2分钟的烧结。应予说明,上述N2气氛中的氧浓度为1000ppm以下。对由此得到的带绝缘张力被膜的取向性电磁钢板与实施例1同样地进行铁损、被膜张力和耐吸湿性的评价。将评价结果集中示于表3。
[表3]
如表3所示,不论添加哪种结晶性的化合物,均得到了被膜张力和耐吸湿性优异的被膜性能。
Claims (6)
1.一种带无铬绝缘张力被膜的取向性电磁钢板,其特征在于,在取向性电磁钢板的至少一方的表面具有含磷酸盐和二氧化硅的绝缘张力被膜,并且,在所述被膜内部存在下述通式(1)表示的结晶性的化合物,
MII 3MIII 4(XVO4)6···(1)
通式(1)中,MII、MIII各自独立地为选自Sc、Ti、V、Mn、Fe、Co、Ni、Cu、Mg中的1种或2种以上,XV为选自P、V、Mo中的1种或2种以上。
2.根据权利要求1所述的带无铬绝缘张力被膜的取向性电磁钢板,其特征在于,所述通式(1)中,MIII为Fe,XV为P。
3.根据权利要求1或2所述的带无铬绝缘张力被膜的取向性电磁钢板,其特征在于,所述通式(1)表示的结晶性的化合物为Fe7(PO4)6。
4.根据权利要求1~3中任一项所述的带无铬绝缘张力被膜的取向性电磁钢板,其特征在于,所述磷酸盐由选自Mg、Fe、Al、Ca、Mn和Zn的磷酸盐中的1种或2种以上构成。
5.一种带无铬绝缘张力被膜的取向性电磁钢板的制造方法,是权利要求1~4中任一项所述的带无铬绝缘张力被膜的取向性电磁钢板的制造方法,其特征在于,
在最终退火后的取向性电磁钢板的至少一方的表面涂布如下绝缘张力被膜用处理液,进行至少1次在使用非氧化性的气体且使露点为0℃以下的气氛下加热到900℃以上的热处理,其中,所述绝缘张力被膜用处理液是在固体成分换算计20质量份的胶体状二氧化硅中配合有10~80质量份的磷酸盐和氧化物换算计5~10质量份的含金属元素M的化合物,所述金属元素M为选自Sc、Ti、V、Mn、Fe、Co、Ni、Cu、Mg中的1种或2种以上。
6.一种带无铬绝缘张力被膜的取向性电磁钢板的制造方法,是权利要求1~4中任一项所述的带无铬绝缘张力被膜的取向性电磁钢板的制造方法,其特征在于,
在最终退火后的取向性电磁钢板的至少一方的表面涂布如下绝缘张力被膜用处理液,在非氧化性气氛下进行至少1次加热处理,其中,所述绝缘张力被膜用处理液是在固体成分换算计20质量份的胶体状二氧化硅中配合有磷酸盐10~80质量份和所述通式(1)表示的结晶性的化合物。
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54143737A (en) * | 1978-04-28 | 1979-11-09 | Kawasaki Steel Co | Formation of chromiummfree insulating top coating for directional silicon steel plate |
JPS5675579A (en) * | 1979-11-22 | 1981-06-22 | Kawasaki Steel Corp | Method of forming top coating insulation film of tension addition type without containing chromium oxide on directional silicone steel plate |
JP2008240080A (ja) * | 2007-03-28 | 2008-10-09 | Jfe Steel Kk | 方向性電磁鋼板用絶縁被膜処理液および方向性電磁鋼板の製造方法 |
RU2371518C2 (ru) * | 2007-07-02 | 2009-10-27 | Закрытое акционерное общество "ФК" | Способ и состав для получения электроизоляционного покрытия |
JP2010059513A (ja) * | 2008-09-05 | 2010-03-18 | Kaisui Kagaku Kenkyusho:Kk | 電磁鋼板用絶縁被膜剤 |
CN101790599A (zh) * | 2007-08-30 | 2010-07-28 | 杰富意钢铁株式会社 | 方向性电磁钢板用绝缘覆膜处理液以及具有绝缘覆膜的方向性电磁钢板的制造方法 |
JP2012158800A (ja) * | 2011-01-31 | 2012-08-23 | Jfe Steel Corp | クロムレス張力被膜付き方向性電磁鋼板 |
CN103221556A (zh) * | 2010-10-07 | 2013-07-24 | 蒂森克虏伯电工钢有限公司 | 用于在晶粒取向的电工钢板产品上制造绝缘涂层的方法以及涂有这样的绝缘涂层的电工钢板产品 |
JP2015509994A (ja) * | 2011-12-28 | 2015-04-02 | ポスコ | 無方向性電磁鋼板の絶縁被膜組成物、その製造方法および絶縁被膜組成物が適用された無方向性電磁鋼板 |
WO2015162837A1 (ja) * | 2014-04-24 | 2015-10-29 | Jfeスチール株式会社 | 方向性電磁鋼板用のクロムフリー絶縁被膜処理液およびクロムフリー絶縁被膜付き方向性電磁鋼板 |
CN105733430A (zh) * | 2014-12-11 | 2016-07-06 | 宝山钢铁股份有限公司 | 一种热镀铝锌钢板用表面处理剂、热镀铝锌钢板及其制造方法 |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE789262A (fr) | 1971-09-27 | 1973-01-15 | Nippon Steel Corp | Procede de formation d'un film isolant sur un feuillard d'acierau silicium oriente |
JPS5652117B2 (zh) | 1973-11-17 | 1981-12-10 | ||
ZA765233B (en) | 1975-09-11 | 1977-08-31 | J Rogers | Steel metal web handling method apparatus and coil construct |
JPS5328375A (en) | 1976-08-11 | 1978-03-16 | Fujitsu Ltd | Inspecting method |
JPS5934604B2 (ja) | 1980-06-19 | 1984-08-23 | 富士通株式会社 | 粉体回収装置 |
JPS6287764A (ja) | 1985-10-14 | 1987-04-22 | 株式会社日立製作所 | 空気調和機 |
JP2664325B2 (ja) * | 1993-03-31 | 1997-10-15 | 新日本製鐵株式会社 | 低鉄損方向性電磁鋼板 |
JP2000169972A (ja) | 1998-12-04 | 2000-06-20 | Nippon Steel Corp | クロムを含まない方向性電磁鋼板用表面処理剤及びそれを用いた方向性電磁鋼板の製造方法 |
JP2000169973A (ja) | 1998-12-04 | 2000-06-20 | Nippon Steel Corp | クロムを含まない方向性電磁鋼板用表面処理剤及びそれを用いた方向性電磁鋼板の製造方法 |
JP2000178760A (ja) | 1998-12-08 | 2000-06-27 | Nippon Steel Corp | クロムを含まない表面処理剤及びそれを用いた方向性電磁鋼板の製造方法 |
JP4321120B2 (ja) | 2003-05-29 | 2009-08-26 | Jfeスチール株式会社 | 磁気特性に優れた方向性電磁鋼板の製造方法 |
JP4264362B2 (ja) * | 2004-01-15 | 2009-05-13 | 新日本製鐵株式会社 | クロムを含まない方向性電磁鋼板用絶縁皮膜剤及びクロムを含まない絶縁皮膜を有する方向性電磁鋼板 |
JP4682590B2 (ja) | 2004-11-10 | 2011-05-11 | Jfeスチール株式会社 | クロムレス被膜付き方向性電磁鋼板およびその製造方法 |
JP4878788B2 (ja) * | 2005-07-14 | 2012-02-15 | 新日本製鐵株式会社 | クロムを含有しない電磁鋼板用絶縁被膜剤 |
PL2022874T3 (pl) | 2006-05-19 | 2012-12-31 | Nippon Steel Corp | Teksturowana elektrotechniczna blacha stalowa mająca film izolacyjny o wysokiej wytrzymałości na rozciąganie i sposób obróbki filmu izolacyjnego |
JP4835326B2 (ja) * | 2006-08-28 | 2011-12-14 | Jfeスチール株式会社 | 方向性電磁鋼板の製造方法 |
JP5098466B2 (ja) * | 2007-07-04 | 2012-12-12 | Jfeスチール株式会社 | クロムレス張力被膜用処理液およびクロムレス張力被膜の形成方法ならびにクロムレス張力被膜付き方向性電磁鋼板 |
JP5181571B2 (ja) * | 2007-08-09 | 2013-04-10 | Jfeスチール株式会社 | 方向性電磁鋼板用クロムフリー絶縁被膜処理液および絶縁被膜付方向性電磁鋼板の製造方法 |
JP5194641B2 (ja) * | 2007-08-23 | 2013-05-08 | Jfeスチール株式会社 | 方向性電磁鋼板用絶縁被膜処理液および絶縁被膜付方向性電磁鋼板の製造方法 |
JP5309735B2 (ja) * | 2008-07-03 | 2013-10-09 | 新日鐵住金株式会社 | 絶縁被膜処理剤と該被膜処理剤を塗布した方向性電磁鋼板及びその絶縁被膜処理方法 |
JP5328375B2 (ja) | 2009-01-06 | 2013-10-30 | 大森機械工業株式会社 | 粘着シートの分離供給装置及び方法 |
EP2902509B1 (en) | 2014-01-30 | 2018-08-29 | Thyssenkrupp Electrical Steel Gmbh | Grain oriented electrical steel flat product comprising an insulation coating |
JP5900705B2 (ja) * | 2014-01-31 | 2016-04-06 | Jfeスチール株式会社 | クロムフリー張力被膜用処理液、クロムフリー張力被膜の形成方法およびクロムフリー張力被膜付き方向性電磁鋼板の製造方法 |
-
2017
- 2017-09-08 CN CN201780048841.1A patent/CN109563626B/zh active Active
- 2017-09-08 MX MX2019001739A patent/MX2019001739A/es unknown
- 2017-09-08 EP EP17850804.0A patent/EP3476976B1/en active Active
- 2017-09-08 RU RU2019103127A patent/RU2698234C1/ru active
- 2017-09-08 CA CA3032648A patent/CA3032648C/en active Active
- 2017-09-08 KR KR1020197003769A patent/KR102189461B1/ko active IP Right Grant
- 2017-09-08 WO PCT/JP2017/032406 patent/WO2018051902A1/ja active Application Filing
- 2017-09-08 JP JP2017557219A patent/JP6299938B1/ja active Active
- 2017-09-08 US US16/324,211 patent/US11756713B2/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54143737A (en) * | 1978-04-28 | 1979-11-09 | Kawasaki Steel Co | Formation of chromiummfree insulating top coating for directional silicon steel plate |
JPS5675579A (en) * | 1979-11-22 | 1981-06-22 | Kawasaki Steel Corp | Method of forming top coating insulation film of tension addition type without containing chromium oxide on directional silicone steel plate |
JP2008240080A (ja) * | 2007-03-28 | 2008-10-09 | Jfe Steel Kk | 方向性電磁鋼板用絶縁被膜処理液および方向性電磁鋼板の製造方法 |
RU2371518C2 (ru) * | 2007-07-02 | 2009-10-27 | Закрытое акционерное общество "ФК" | Способ и состав для получения электроизоляционного покрытия |
CN101790599A (zh) * | 2007-08-30 | 2010-07-28 | 杰富意钢铁株式会社 | 方向性电磁钢板用绝缘覆膜处理液以及具有绝缘覆膜的方向性电磁钢板的制造方法 |
JP2010059513A (ja) * | 2008-09-05 | 2010-03-18 | Kaisui Kagaku Kenkyusho:Kk | 電磁鋼板用絶縁被膜剤 |
CN103221556A (zh) * | 2010-10-07 | 2013-07-24 | 蒂森克虏伯电工钢有限公司 | 用于在晶粒取向的电工钢板产品上制造绝缘涂层的方法以及涂有这样的绝缘涂层的电工钢板产品 |
JP2012158800A (ja) * | 2011-01-31 | 2012-08-23 | Jfe Steel Corp | クロムレス張力被膜付き方向性電磁鋼板 |
JP2015509994A (ja) * | 2011-12-28 | 2015-04-02 | ポスコ | 無方向性電磁鋼板の絶縁被膜組成物、その製造方法および絶縁被膜組成物が適用された無方向性電磁鋼板 |
WO2015162837A1 (ja) * | 2014-04-24 | 2015-10-29 | Jfeスチール株式会社 | 方向性電磁鋼板用のクロムフリー絶縁被膜処理液およびクロムフリー絶縁被膜付き方向性電磁鋼板 |
CN105733430A (zh) * | 2014-12-11 | 2016-07-06 | 宝山钢铁股份有限公司 | 一种热镀铝锌钢板用表面处理剂、热镀铝锌钢板及其制造方法 |
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RU2698234C1 (ru) | 2019-08-23 |
KR102189461B1 (ko) | 2020-12-11 |
US11756713B2 (en) | 2023-09-12 |
MX2019001739A (es) | 2019-05-09 |
US20210287834A1 (en) | 2021-09-16 |
KR20190027871A (ko) | 2019-03-15 |
JP6299938B1 (ja) | 2018-03-28 |
CN109563626B (zh) | 2021-04-13 |
WO2018051902A1 (ja) | 2018-03-22 |
JPWO2018051902A1 (ja) | 2018-09-20 |
EP3476976B1 (en) | 2021-04-14 |
EP3476976A4 (en) | 2019-06-05 |
CA3032648C (en) | 2021-02-02 |
EP3476976A1 (en) | 2019-05-01 |
CA3032648A1 (en) | 2018-03-22 |
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