CN1291661A - 覆膜特性优良的取向性电工钢板及其制造方法 - Google Patents

覆膜特性优良的取向性电工钢板及其制造方法 Download PDF

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CN1291661A
CN1291661A CN00128416A CN00128416A CN1291661A CN 1291661 A CN1291661 A CN 1291661A CN 00128416 A CN00128416 A CN 00128416A CN 00128416 A CN00128416 A CN 00128416A CN 1291661 A CN1291661 A CN 1291661A
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steel sheet
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竹田和年
山崎修一
小林英之
藤井浩康
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Abstract

一种比现有技术的方法赋予张力的效果大,粘合性与磁特性优异,还在实用的耐蚀性上优异的高占空因数取向性电工钢板及其绝缘覆膜的制造方法,上述钢板在表面具有二价或三价金属的磷酸氢盐和氧化硅为主要成分的层作为第一层和表面粗糙度Ra(中心线平均粗糙度)0.1—0.35μm的硼酸铝为主要成分的层作为第二层构成的绝缘覆膜的取向性电工钢板。

Description

覆膜特性优良的取向性电工钢板及其制造方法
本发明涉及粘合性与耐蚀性等覆膜特性良好，占空因数良好、并保持赋予张力大的绝缘覆膜的铁损显著小的取向性电工钢板及其制造方法。
钢板的易磁化轴在轧制方向上一致，铁损低的取向性电工钢板在变压器等电工仪器上广泛使用。已知在取向性电工钢板的轧制方向上赋予张力并更加降低铁损，如在特开昭48-39338号公报和特开昭50-79442号公报中所公开的那样，提出在钢板表面涂敷烘烤磷酸铝和胶体氧化硅为主要成分的涂液，并利用与钢板的热膨胀差赋予张力以改善铁损的方法。
另外，最近在特开平6-65755号公报中公开了：由于在钢板表面上形成硼酸铝为主要成分的绝缘覆膜，可赋予钢板更大的张力，得到保持优异磁特性的取向性电工钢板的方法。
但是，形成硼酸铝为主要成分的绝缘覆膜的取向性电工钢板与保持磷酸铝和胶体氧化硅为主要成分的绝缘覆膜的取向性电工钢板比较说明，赋予张力的效果优异，而粘合性与耐蚀性，占空因数差。
关于粘合性，特开平7-207453号公报中公开了：在保持镁橄榄石覆膜为主体的绝缘覆膜的取向性电工钢板上形成硼酸铝系绝缘覆膜时，进行简易酸洗后，每面形成0．5g／m2以上，3．0g／m2以下的磷酸盐或磷酸盐与胶体氧化硅为主体的覆膜，接着涂敷烘烤氧化铝溶胶与硼酸为主体的涂液的方法。
该技术的目的是在镁橄榄石为主体的最终退火覆膜上形成硼酸铝覆膜那样的赋予大张力的粘合性良好的绝缘覆膜，对于由于酸洗机械强度降低的镁橄榄石覆膜，由于涂敷烘烤磷酸盐或磷酸盐与胶体氧化硅为主体的涂液，由于可发挥修补材料的效果，修补腐蚀龟裂的镁橄榄石覆膜，以谋求改善粘合性。为此，涂敷烘烤磷酸盐或磷酸盐与胶体氧化硅为主体的涂液的条件没办法解决，以使不能期待改善耐蚀性与占空因数。
另外，关于耐蚀性特开平9-272982号公报中公开了：在钢板上具有含硼酸铝覆膜的第一层和在其上含有磷酸铝的第二层构成的覆膜为特征的技术。
该技术的目的是由第一层的硼酸铝覆膜赋予钢板附加张力，第二层的目的主要是改善耐蚀性。即，在耐蚀性差的硼酸铝薄膜上施以第二层来改进其缺点。
但是，由于在硼酸铝覆膜中含有剩余的氧化硼，在涂敷烘烤并形成含磷酸铝的第二层时，第一层的硼酸铝覆膜部分溶解，说明其耐蚀性恶化，因此，由于形成硼酸铝覆膜，在其上涂敷并形成磷酸铝覆膜在工业上是非常难的，由于要求高的技术，因而也存在成本变高的问题。
另外，在通常的电工钢板上施加的磷酸铝覆膜上，不控制涂敷烘烤条件而形成硼酸铝覆膜的场合，为改善耐蚀性，如增加涂敷量，不仅有占空因数，而且有粘合性变差的情况，另外，如减少涂敷量，有得不到充分耐蚀性的问题，上述公报中公开的技术，改善耐蚀性的效果是在50℃、91RH％的恒温恒温槽中放置一周评价的程度，关于卷材的输送还有装船的情况，所以在恒温恒湿槽中的评价是不完全的，以盐水喷雾试验评价水平的耐蚀性是需要的。
其次，在特开平9-235679号公报中公开了：由于规定了氧化铝溶胶的颗粒形状，平滑性、粘合性良好，保持含有变压器制造时作业性良好的硼酸铝的氧化物覆膜的低铁损取向性电工钢板的有关技术。
该技术表明氧化铝溶胶的颗粒形状对含有硼酸铝的氧化物覆膜的表面状态有影响，保持良好的外观和优异的粘合性，表明得到了具有赋予张力效果大的覆膜的取向性电工钢板的制造方法。即，保持氧化铝颗粒形状可改善薄膜表面性质。但是，该方法谋求占空因数的改善及耐蚀性方面不完全。
本发明的目的是提供比过去的覆膜赋予张力效果优异，且具有保持良好粘合性与完全满足实用要求的耐蚀性的覆膜的取向性电工钢板，以及具有保持良好占空因数的覆膜的取向性电工钢板。
本发明基于如下发现：在取向性电工钢板上施用硼酸铝为主要成分的张力效果优异的绝缘薄膜之前，进行涂敷烘烤磷酸盐或磷酸盐与胶体二氧化硅为主要成分的涂液时，通过控制其烘烤条件，制成皮膜表面粗糙度与皮膜耐蚀性优异的取向性电工钢板。
即，本发明构成如下：
(1)在钢板表面上具有二价或三价金属的磷酸氢盐和二氧化硅为主要成分的第一层和硼酸铝为主要成分的第二层构成的绝缘覆膜为特征的覆膜特性优异的取向性电工钢板。
(2)第一层的磷酸氢盐为磷酸二氢铝、磷酸二氢镁、磷酸二氢钙中的一种或二种以上的混合物为特征的上述(1)记载的覆膜特性优异的取向性电工钢板。
(3)在第一层中还含有游离磷酸为特征的上述(1)或(2)记载的覆膜特性优异的取向性是电工钢板。
(4)在第一层中还含有氧化铬为特征的上述(1)至(3)的任一项记载的覆膜特性优异的取向性电工钢板。
(5)在钢板表面上具有二价或三价金属的磷酸氢盐和二氧化硅为主要成分的第一层和硼酸铝为主要成分的第二层构成的，表面粗糙度Ra(中心线平均粗糙度)0．1-0．50μm的绝缘覆膜为特征的覆膜特性优异的取向性电工钢板。
(6)第一层的磷酸氢盐为磷酸二氢铝、磷酸二氢镁、磷酸二氢钙中的一种或二种以上的混合物为特征的上述(5)记载的覆膜特性优异的取向性电工钢板。
(7)在第一层中还含有游离磷酸为特征的上述(5)或(6)记载的覆膜特性优异的取向性电工钢板。
(8)在第一层中还含有氧化铬为特征的上述(5)至(7)的任一项记载的覆膜特性优异的取向性电工钢板。
(9)在形成含有磷酸氢盐与二氧化硅为主要成分的第一层时，在钢板上涂敷该组成构成的涂液，在200-600℃干燥烘烤，然后在形成硼酸铝为主要成分的第二层时，涂敷该组成构成的涂液，在800-1200℃干燥烘烤为特征的覆膜特性优异的取向性电工钢板的制造方法。
(10)在第二层干燥烘烤时，到400℃的升温速度为15-25℃／秒为特征的上述(9)记载的覆膜特性优异的取向性电工钢板的制造方法。
以下的实施的具体形式说明本发明
本发明使用磷酸氢盐，由于在化合物中含有离解性氢原子，且金属原子保持二价或三价的价数。作为这样磷酸氢盐的例子有磷酸二氢铝、磷酸二氢镁、磷酸二氢钙等。
作为磷酸氢盐的形式，按磷酸的离解状态存在第一盐、第二盐、第三盐三种形式，关于本发明有使用所谓第一盐和第二盐的磷酸氢盐的必要。
作为第一盐的例子是磷酸二氢镁(Mg(H2PO4)2)、磷酸二氢铝(Al(H2PO4)3)；作为第二盐的例子是磷酸氢镁(MgHPO4)等。通常，由于第一盐在水中是可溶的，在涂敷处理的场合，可使用第一盐状态的水溶液，在本发明中希望使用磷酸二氢盐。
作为本发明使用的磷酸氢盐的金属元素，必须是二价或三价的，作为二价的金属原子希望为镁、钙等碱土类，作为三价的金属原子希望为铝、铁等，对这些元素没有特别地限定。在过渡元素中不仅存在二价或三价的价数状态的元素，而且也存在其它价数状态的元素。这样的金属元素二价或三价的价数在常温常压下是稳定的，没有任何问题。
本发明人等发现，在第一层中存在磷酸氢盐的场合，在涂敷烘烤第二层的硼酸铝覆膜的场合，可保持盐水喷雾试验评价的充分的耐蚀性，且由于磷酸氢盐产生的游离的磷酸的影响，硼酸铝覆膜的结晶过程受到影响，抑制由于结晶覆膜表面的细小凹凸生成，并得到良好的占空因数，而完成了本发明。
在本明的第一层，除特定金属原子的磷酸氢盐以外，必须含有氧化硅。从该氧化硅覆膜的均一性观点和占空因数的观点看，希望使用胶体状氧化硅，特别是4-30nm程度的粒径比较小的合适。该氧化硅的详细作用不明确，推断可促进磷酸氢盐的缩合反应，同时由于该覆膜的形成能使形成致密覆膜。
另外，由于胶体状氧化硅是非晶态，推断可影响硼酸铝覆膜形成时的结晶过程。磷酸氢盐与二氧化硅的混合比例按固体部分比例为5-60％为好，进一步为35-55％的范围最合适。
本发明在第一层中含有含特定金属原子的磷酸氢盐与氧化硅，第二层形成硼酸铝为主要成分的层是必需的，作为第一层只干燥烘烤含有氧化硅与含特定金属原子的磷酸氢盐的涂敷液还不完全，在第一层中有必要残存磷酸氢盐。
在特公昭53-28375号公报中公开的技术中写明涂敷烘烤或涂敷烘烤后的工序是在约800-900℃的温度进行热处理。
但是，将该涂敷液在这样的高温下烘烤的场合，磷酸氢盐的缩合反应进行过剩，在第二层形成时不仅与硼酸铝的反应性降低，而且游离的过剩磷酸由于第二层形成时的加热而汽化，有成为覆膜缺陷原因的危险。
另外，在特开平9-272982号公报中公开的技术中写明，将作为第二层的磷酸二氢铝在含氢的氮气氛中在800℃烘烤5分钟，由X-射线衍射可确认氧化硅由非晶态构成。
但是，本发明人等确认，在第二层的磷酸二氢铝覆膜表面上析出细小的结晶，在800℃加热5分钟，存在极微量，推断为磷酸铝结晶的，在第一层硼酸铝最表层部分在钢板侧面将第二层磷酸二氢铝上下转换涂敷的场合，已清楚在第二层磷酸铝表面上将析出的结晶作为核，由于第一层硼酸铝覆膜进行结晶，覆膜表面上发生凹凸，引起占空因数降低。
由于在第一层中生成磷酸氢盐，按照使用的磷酸氢盐的种类、氧化硅最适合的温度不同，第一层的烘烤温度比通常取向性电工钢板的绝缘覆膜的形成温度低，有必要保持在200-600℃的范围内。如不到200℃，覆膜形成不完全，有过剩的水分残存并有产生气孔的危险，如超过600℃，有磷酸氢盐进行缩合反应达不到本发明效果的危险。进一步希望在220-380℃的范围内。
其次，对于本发明作为第二层使用硼酸铝，其目的是对钢板赋予张力。
本发明使用的硼酸铝具有化学式Al4B2O9与Al18B4O33等，可单独或混合使用，实际上可进一步生成准稳定状态的硼酸铝等，这没有特别的限制。另外，从赋予张力的观点看，生成晶态的硼酸铝是希望的，但非晶态的硼酸铝或非晶态与晶态的混合物也没有任何问题。
在本发明中硼酸铝覆膜表面平滑，由于使表面粗糙度降低，在改进占空因数方面，特别希望使用特开平9-235679号公报中公开的氧化铝溶胶。由于使用了上述公报中公开的特定颗粒形状的氧化铝溶胶，本发明可得到表面粗糙度降低效果与相乘效果。
由于在硼酸铝中引入铁化合物，可改善耐水性。作为添加的铁化合物，硼酸铁、硝酸铁等为好，添加量1-10％可得到特别良好的结果。
在本发明中表面粗糙度Ra(中心线平均粗糙度)限制在0．1～0．50μm。由于不到0．1μm，必须规定钢板表面的粗糙度，在此使轧辊的维持管理上产生很大成本是不现实的。另外，如超过0．50μm，占空因数的恶化不可忽视。它希望的是0．35μm以下。
第二层的干燥烘烤温度在800-1200℃范围内可得到良好的覆膜特性。如烘烤温度不到800℃，有赋予张力效果小并得不到磁特性改善效果的危险，如超过1200℃，有钢板的机械强度变小并产生缺陷的危险。
还有，第二层的干燥烘烤时的升温速度，如达到400℃在15-25℃／秒的范围是必要的。如升温速度不到15℃／秒，有赋予张力效果变小的危险，如超过25℃／秒，有涂敷液漰沸的危险。
本发明使用的取向性电工钢板一般认为是已最终退火的状态，在表面上形成镁橄榄石为主体的覆膜层(通常叫一次覆膜)，此外，用酸洗将一次覆膜除去，添加氧化铝粉与氯化物等添加剂，使用退火分离剂，在不生成一次覆膜的条件下进行最终退火，使钢板表面成为所谓镜面状态为宜。
再者，使用在上述钢板上用激光和形成槽等的处理进行磁区细分的取向性电工钢板为宜。
本发明的第一层和第二层的厚度分别是：第一层为0．1-2．0μm，第二层为2．0-5．0μm是适当的，更希望第一层为0．5-1．0μm，第二层为2．0-3．0μm。
关于本发明的作用还不明其详，可认为其作用机理大概如下所示。
在本发明的第一层中必须使用含有特定金属原子的磷酸氢盐。这些磷酸氢盐的特征是通过高温烘烤可进行脱水反应并形成缩合磷酸盐。例如在磷酸二氢镁的场合，通过加热按下式成为磷酸氢镁：
    (1)
通过将磷酸氢盐再加热可能成为磷酸盐。例如磷酸氢镁的场合：
    (2)
这些化学反应不仅强烈受到烘烤温度，而且强烈受到使用的磷酸氢盐的种类、与金属原子的比例或各种反应促进剂等的影响。反应的最终状态不用说产生很大的差别，无论使用那一种磷酸氢盐也得通过加热来进行。
本发明人等注目通过将磷酸氢盐加热放出的游离磷酸。在钢板表面上涂敷含有磷酸氢盐的涂液，并加热干燥的场合，如达到对应使用的磷酸氢盐种类的反应温度，从磷酸氢盐放出游离的磷酸。例如，在磷酸二氢镁的场合，可推断首先按上述反应式(1)每一个分子可放出一个磷酸。由于本发明极积地利用了这些游离的磷酸，可确保有高的耐蚀性。
再者，由于产生了这些游离的磷酸，在硼酸铝覆膜结晶的场合，使表面平坦那样作用于第一层与第二层的界面，因而，可推断也使第二层硼酸铝覆膜表面平坦化并对硼酸铝的结晶给予影响，减小表面粗糙度。
即，在本发明中使用的第二层中存在硼酸铝为主要成分的赋予张力的层，由于在第二层加热干燥时，从第一层中的磷酸氢盐中游离的磷酸与铝的亲和性高，因此也与第二层中使用的硼酸铝很好地亲和。由于第一层与第二层之间的粘合性高，同时形成致密强的涂膜，可推断会有优异的耐蚀性。
再者，由于本发明第一层的磷酸氢盐为非晶态，第二层的硼酸铝覆膜结晶成核与生长的场所变少，因而结晶生长不大，表面粗糙度小，占空因数改善。
在本发明中，为进一步改善耐蚀性，可在第一层中添加氧化铬。另外，作为从第一层中的磷酸氢盐中游离的磷酸的补助，可在第一层中添加游离的磷酸。另外，如过多地添加游离磷酸，第一层中的磷酸成分剩余，与氧化铬并用不仅可改善耐蚀性，而且由于有剩余的磷酸可防止消除应力退火时的烧结，所谓的粘附。
实施例1
将具有含Si3．1％，板厚0．23mm的最终退火过的一次覆膜的取向性电工钢板与最终退火时使用分离剂氧化铝粉末并镜面化的取向性电工钢板作为试样，将表1所示组成的水溶液制成1μm厚的膜，以表2所示的板温烘烤20秒钟。此后，将保持表3组成的水溶液涂敷制成3μm厚的膜，在950℃的炉中烘烤1分钟。
关于这样得到的取向性电工钢板的磁特性、覆膜特性的结果示于表4。还有，在测定磁特性时，为了消除试样制作时的影响，进行800℃×2小时的应力消除退火。
另外，作为现有例(表4中的序号11)，将保持表3组成的水溶液涂敷3μm厚的膜作为第一层并在950℃的炉中烘烤1分钟后，将表1中的水溶液序号2组成的水溶液制成1μm厚的膜作为其上的第二层并在400℃烘烤20秒钟。
还有，作为现有例(表4中的序号12)，以特开昭50-79442号公报中公开的磷酸铝、铬酸、胶体二氧化硅为主要成分的涂液制成4μm厚的膜并在850℃的炉中烘烤1分钟。
从表中可清楚地看出，本发明钢板的磁特性、耐蚀性、粘合性、占空因数都优异。
表1
溶液序号   磷酸盐的种类(重量份) 胶体二氧化硅(重量份)     磷酸(重量份)     铬酸(重量份)
    1 磷酸二氢Al(30)     20
    2 磷酸二氢Mg(20)     20     0.1     3
    3 磷酸二氢Al(20)磷酸二氢Ca(10)     15
    4 磷酸二氢Al(20)磷酸二氢Mg(5)     20     5
    5 磷酸二氢Na(20)     10
    6 磷酸Al(20)     20     5
表2
  序  号     溶液序号     烘烤板温(℃)     试样     备注
    1     1     400   有一次覆膜     本发明
    2     2     250   有一次覆膜     本发明
    3     3     450   有一次覆膜     本发明
    4     3     350   有一次覆膜     本发明
    5     4     400   有一次覆膜     本发明
    6     1     250     镜面化     本发明
    7     3     100   有一次覆膜     比较例
    8     4     700   有一次覆膜     比较例
    9     5     900   有一次覆膜     比较例
    10     6     300   有一次覆膜     比较例
表3
原料名 重量份(固体部分)
硼 酸 30
勃姆石溶胶 50
表4
  序号   铁损(w17/50)   耐蚀性(a) 粘合性(b) 表面粗糙度(c) 占空因数(％)     备注
    1     0.75     8     ○     0.22     97.1   本发明
    2     0.74     9     ○     0.22     97.2   本发明
    3     0.75     7     ○     0.19     97.5   本发明
    4     0.75     7     ○     0.20     97.2   本发明
    5     0.77     8     ○     0.21     97.2   本发明
    6     0.67     8     ○     0.24     98.1   本发明
    7     0.78     5     ×     0.18     97.3   比较例
    8     0.81     5     ○     0.35     97.2   比较例
    9     0.77     1     ○     0.31     97.1   比较例
    10     0.78     1     ○     0.70     96.7   比较例
    11     0.80     3     △     0.38     96.5   现有例
    12     0.83     8     ○     0.22     97.1   现有例
(注)a：5％盐水喷雾5小时、50℃、按目视10点评价法、7点以上合格
b：用透明胶带的剥离性◎无粘合○有少量粘合△多的粘合×剥离
c：Ra(中心线平均粗糙度、μm、试样L方向和C方向的平均值)
如上所述，本发明比现有方法赋予张力的效果大，可获得保持优异粘合性、磁特性和完全实用耐蚀性的高占空因数的取向性电工钢板。

Claims (10)

1．一种覆膜特性优异的取向性电工钢板，其特征在于在钢板表面具有二价或三价金属的磷酸氢盐和二氧化硅为主要成分的第一层和硼酸铝为主要成分的第二层构成的绝缘覆膜。
2．权利要求1记载的覆膜特性优异的取向性电工钢板，其特征在于第一层的磷酸氢盐为磷酸二氢铝、磷酸二氢镁、磷酸二氢钙的一种或二种以上的混合物。
3．权利要求1或2记载的覆膜特性优异的取向性电工钢板，其特征在于在第一层中还含有游离的磷酸。
4．权利要求1-3的任一项记载的覆膜特性优异的取向性电工钢板，其特征在于在第一层中还含有氧化铬。
5．一种覆膜特性优异的取向性电工钢板，其特征在于在钢板表面具有二价或三价金属的磷酸氢盐和二氧化硅为主要成分的第一层和硼酸铝为主要成分的第二层构成的，表面粗糙度Ra(中心线平均粗糙度)0．1-0．50μm的绝缘覆膜。
6．权利要求5记载的覆膜特性优异的取向性电工钢板，其特征在于第一层的磷酸氢盐为磷酸二氢铝、磷酸二氢镁、磷酸二氢钙的一种或二种以上的混合物。
7．权利要求5或6记载的覆膜特性优异的取向性电工钢板，其特征在于在第一层中还含有游离的磷酸。
8．权利要求5-7任一项记载的覆膜特性优异的取向性电工钢板，其特征在于在第一层中还含有氧化铬。
9．一种覆膜特性优异的取向性电工钢板的制造方法，其特征在于在形成含有磷酸氢盐和二氧化硅为主要成分的第一层时，在钢板上涂敷该组成构成的涂液，在200-600℃干燥烘烤，然后在形成硼酸铝为主要成分的第二层时，涂敷该组成构成的涂液，并在800-1200℃干燥烘烤。
10．权利要求9记载的覆膜特性优异的取向性电工钢板的制造方法，其特征在于在第二层干燥烘烤时，到400℃的升温速度为15-25℃／秒。
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