CN116829742A - 取向性电磁钢板的制造方法及其使用的退火分离剂 - Google Patents
取向性电磁钢板的制造方法及其使用的退火分离剂 Download PDFInfo
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- 238000000137 annealing Methods 0.000 title claims abstract description 110
- 229910000976 Electrical steel Inorganic materials 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 238000001953 recrystallisation Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000005097 cold rolling Methods 0.000 claims description 6
- 238000005098 hot rolling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 238000000746 purification Methods 0.000 abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 29
- 239000003112 inhibitor Substances 0.000 abstract description 13
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 230000003014 reinforcing effect Effects 0.000 abstract description 6
- 229910000831 Steel Inorganic materials 0.000 description 47
- 239000010959 steel Substances 0.000 description 47
- 239000010955 niobium Substances 0.000 description 29
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 238000005261 decarburization Methods 0.000 description 7
- 229910052715 tantalum Inorganic materials 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000009036 growth inhibition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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Abstract
本发明提出了一种取向性电磁钢板的制造方法,通过退火分离剂的改善促进抑制剂增强元素的纯化,从而能够有效地改善铁损。上述退火分离剂,相对于MgO:100质量份含有1~10质量份的范围的含有分别选自1组:Fe、Mn、Al和Ca以及2组:Zr、Ta、Mo和Nb中的1种或2种以上的元素的复合氧化物。
Description
技术领域
本发明涉及用于变压器及其他电气设备的铁芯等的取向性电磁钢板的制造方法,特别是涉及一种通过对涂布在脱碳退火后的钢板上的退火分离剂进行改良,磁特性和被膜特性优异的取向性电磁钢板的制造方法。
另外,还涉及上述取向性电磁钢板的制造方法中使用的退火分离剂。
背景技术
取向性电磁钢板的制造工序一般是在将钢坯热轧后进行冷轧,接着实施脱碳退火,然后进行最终退火以进行二次再结晶。在这些工序中,最终退火中发生二次再结晶,生成易磁化轴在钢板的轧制方向上对齐的粗大的晶粒。
由于进行长时间的最终退火,为了防止钢板的烧结,通常在退火前在该钢板上涂布以MgO为主体的退火分离剂。该MgO除了起到退火分离剂的作用外,还具有通过与脱碳退火过程中形成的以SiO2为主体的氧化层反应而形成镁橄榄石被膜的作用。
另外,退火分离剂的各种特性对基底铁部分产生影响,如析出物的生成生长行为、晶粒的生长行为等,因此会极大改变取向性电磁钢板的产品特性。例如,如果将退火分离剂浆化时带入的水分过多,则钢板被氧化,磁特性变差,或者被膜产生点状缺陷。另外,还已知退火分离剂所含的杂质在退火中渗入钢中而使二次再结晶行为、被膜形成行为变化等。
但是,近年来,随着节能需求的提高,对于进一步改善取向性电磁钢板的磁特性的要求越来越强烈。作为其对策之一,提出了在钢的成分组成添加增强晶粒生长抑制力的元素如Ti、Nb和Ta等的技术。
然而,如果添加这些元素,则在晶粒生长过程中虽然可以生成取向一致的二次再结晶晶粒,但存在这些元素不能被纯化的问题。通常,在二次再结晶退火后,进行1200℃左右的纯化退火,作为该纯化退火中的抑制剂的AlN、MnS等分解,从钢中被除去。但是,在钢的成分组成包含上述的Ti、Nb和Ta等增强元素的情况下,在该纯化退火中未充分纯化,在钢中作为氮化物、碳化物析出而残留。如果产生这样的残留,则这些析出物会妨碍使用产品时的磁畴壁的移动而铁损增加,不能得到所希望的节能效果。
针对这个问题,提出了许多用于改善抑制剂元素的纯化的技术。例如,专利文献1中提出了在二次再结晶结束后,通过进行湿润气氛中的开卷退火,从而使脱碳顺利进行的方法。
另外,专利文献2中提出了通过降低最终退火的气氛中的氮分压而促进纯化的方法。
专利文献3中公开了将最终退火后钢板冷却时的特定温度区域在氢和惰性气体气氛下进行的方法。
专利文献4中公开了在H2-N2混合气氛中进行纯化退火的方法。
现有技术文献
专利文献
专利文献1:日本特开2008-115421号公报
专利文献2:日本特开平11-158557号公报
专利文献3:日本特开2006-193798号公报
专利文献4:日本特开平9-184017号公报
发明内容
但是,在专利文献1记载的方法中,虽然能够有效地脱碳,但Nb、Ta等元素仍然残留在钢中,这些残留在钢中的元素与钢中的少量的氮、氧、碳等结合,有时会在产品使用中引起磁时效。
在专利文献2记载的方法中,虽然改善了氮的纯化,但Nb、Ta等元素仍然残留在钢中,这些与碳等结合,有时会引起磁时效。
在专利文献3记载的方法中,虽然能够防止最终退火的冷却时的氮化,但Nb、Ta等元素残留,仍然引起磁时效。
在专利文献4记载的方法中,通过将Ti固定在被膜中能够抑制Ti渗入钢中,但由于不能将基底铁中原本存在的Ti、Nb等纯化,因此效果还是有限的。
除了这些以外,虽然设计了各种改善纯化不良来降低铁损的方法,但均不充分,难以得到所希望的特性。
本发明是鉴于上述的情况而完成的,目的在于同时提出通过退火分离剂的改善促进抑制剂增强元素的纯化而可以有效改善铁损的取向性电磁钢板的制造方法、以及上述改善的退火分离剂。
本发明的构成要旨如下。
1.一种取向性电磁钢板的制造方法,其特征在于,将取向性电磁钢板用板坯加热并热轧,实施1次或隔着中间退火的2次以上的冷轧,再实施一次再结晶退火,接着,涂布退火分离剂后进行最终退火,
上述取向性电磁钢板用板坯具有以下成分组成:含有C:0.01~0.09质量%、Si:2.00~4.00质量%、Mn:0.03~0.25质量%,进一步含有合计0.002~0.025质量%的选自Nb、V和Ti中的1种或2种以上,剩余部分为Fe和不可避免的杂质,
上述退火分离剂以MgO为主剂,相对于MgO:100质量份含有1~10质量份的范围的复合氧化物,该复合氧化物含有分别选自从1组:Fe、Mn、Al和Ca以及2组:Zr、Ta、Mo和Nb中的1种或2种以上的元素。
2.根据上述1所述的取向性电磁钢板的制造方法,其中,将上述最终退火的最高到达温度设为1210℃以上。
3.根据1或2所述的取向性电磁钢板的制造方法,其中,上述取向性电磁钢板用板坯除了上述成分组成外进一步含有选自Al:0.004~0.040质量%、N:0.002~0.010质量%、S:0.002~0.030质量%、Se:0.002~0.030质量%、Ni:0.01~1.50质量%、Cr:0.01~0.50质量%、Cu:0.01~0.50质量%、P:0.005~0.100质量%、Sb:0.005~0.100质量%、Sn:0.005~0.100质量%、Bi:0.001~0.050质量%、Mo:0.005~0.100质量%、B:0.0002~0.0025质量%和Te:0.0005~0.0100质量%中的1种或2种以上。
4.一种退火分离剂,其特征在于,是上述1~3中任一项所述的取向性电磁钢板的制造方法中使用的退火分离剂,
该退火分离剂中相对于MgO:100质量份含有1~10质量份的范围的复合氧化物,该复合氧化物含有分别选自1组:Fe、Mn、Al和Ca以及2组:Zr、Ta、Mo和Nb中分别选择1种或2种以上的元素。
根据本发明,由于能够充分纯化抑制剂增强元素,因此能够制造磁特性良好的取向性电磁钢板,从而能够极大地有助于取向性电磁钢板的品质提高。
具体实施方式
本发明人等为了改善使用抑制剂增强元素的取向性电磁钢板的纯化进行了各种实验。其结果新发现通过使用含有特定元素的复合氧化物作为退火分离剂的成分,能够特别明显地改善抑制剂增强元素的纯化。
以下,对完成本发明的实验进行说明。
将含有C:0.07质量%(以下,钢板成分的“质量%(质量%)”简单表示为“%”)、Si:3.3%、Mn:0.07%、Al:0.02%、N:0.008%、Se:0.02%和Nb:0.005%、剩余部分实质上由Fe构成的钢坯在1380℃的温度下加热、均热30分钟后,实施热轧至板厚为2.2mm,然后隔着1050℃、1分钟的中间退火实施2次冷轧,制成0.23mm的最终板厚的冷轧板。
将该冷轧板脱碳退火后,涂布以MgO为主剂的退火分离剂并干燥。此时,在该退火分离剂中,改变各种添加物相对于MgO:100质量份的添加量进行混合。接着,作为最终退火,进行890℃、40小时的二次再结晶退火,进一步进行1210℃、10小时的纯化退火。
然后,将未反应的退火分离剂除去,涂布由磷酸二氢铝和胶态二氧化硅构成的混合液,烧结的同时进行850℃、1分钟的平坦化退火,得到产品的钢板。
对这些钢板按照JIS C 2550的方法实施磁性测定。另外,将得到的钢板的被膜除去,之后进行Nb、N、C的定量分析。作为分析方法,Nb、N采用吸光光度法,碳采用燃烧红外线吸收法(以下的实验、实施例也同样)。
将这样得到的结果示于表1。
[表1]
表1
根据该表可知,在添加MnTa2O6的情况下,钢板中Nb、N、C的各元素有效地降低,得到了优异的纯化效果。另外,伴随于此,磁特性也得到了良好的值。与此相对,在添加氧化Ta、氧化Mn或复合氧化物以外的Mn化合物的情况下,与退火分离剂中不添加任何添加剂的情况差别不大,几乎看不到纯化效果。
这种通过添加含有Mn、Ta等的复合氧化物来改善纯化的原因尚不明确,但本发明人等考虑如下。
Nb在最终退火中与N结合而作为氮化物析出,具有增强晶粒生长抑制力的作用。通过这样的作用,得到在GOSS取向上强烈强聚集的二次再结晶组织。
这里,二次再结晶晶粒在800~900℃左右产生。另外,从超过900℃附近开始,氮化Nb分解而分离成固溶Nb和氮。其中,氮通过扩散至钢板的表层并从那里排出气相而被纯化。另一方面,固溶Nb有望被退火分离剂的MgO的水合水分氧化为Nb2O5,从而纯化,但实际上,由于比Nb离子化倾向高的Si大量存在于钢中,因此优选生成SiO2,而Nb2O5的生成受到抑制。因此,为了纯化Nb,需要采用除氧化以外的方法固定Nb。这是因为如果Nb没有被充分纯化,则在最终退火的冷却中或其后的平坦化退火中N、C再次渗入钢中而形成氮化铌、碳化铌。
这里,对Nb纯化有效的MnTa2O6具有与斜方晶系的MnNb2O6相同的晶体结构。因此,Ta与Nb可以互相置换。MnTa2O6通过固溶为Mn(Ta,Nb)2O6,自由能下降。因此,认为Nb与退火分离剂所含的MnTa2O6中的Ta置换,作为Mn(Ta,Nb)2O6固溶,从钢板表层向退火分离剂中扩散,因此促进纯化。
而且,被置换的Ta不渗入钢中,而是在退火分离剂中作为Ta离子存在,与MnTa2O6、Mn(Ta,Nb)2O6一起通过最终退火被纯化,或者随着未反应的退火分离剂的除去而被除去。
接着,对本发明的取向性电磁钢板用退火分离剂的限定理由进行说明。
[退火分离剂]
本发明中的退火分离剂的主剂为MgO。即,退火分离剂的至少50质量%以上为MgO。
上述退火分离剂中,含有分别从1组:Fe、Mn、Al、Ca以及2组:Zr、Ta、Mo、Nb中各选择至少一种元素的氧化物的复合氧化物。通过使用这样的复合氧化物,即使在钢中添加Nb、Ti、Ta、V等抑制剂增强元素,也可以在最终退火中使其纯化。
应予说明,这样的复合氧化物,如上所述,关键的是具有能够有与Nb、Ti、Ta、V等抑制剂增强元素相互置换的晶体结构。作为具有这样的晶体结构的化合物,从操作和获得的容易性等的观点出发,优选从上述1组和2组中各选择至少一种元素的氧化物。
具体而言,例如(Fex,Mn1-x)MoO4、(Fex,Mn1-x)2Mo3O12、Al2(MoO4)3、(Fex,Mn1-x)(Tay,Nb1-y)O3、(Fex,Mn1-x)2ZrO5、Al2Zr3O9。这里,由于Fe与Mn、Nb与Ta能够相互完全固溶,x和y在0~1的范围内可取任意的值。此外,优选的复合氧化物为容易固溶抑制剂强化物质的(Fex,Mn1-x)(Tay,Nb1-y)2O6、CaZrO3、Al2Mo3O12、CaMoO4。
上述复合氧化物在退火分离剂中的含量相对于MgO:100质量份为1~10质量份,优选为2质量份以上,更优选为3质量份以上,另外优选为9质量份以下,更优选为8质量份以下。相对于MgO:100质量份小于1质量份时得不到纯化效果,若超过10质量份,则MgO比率下降,被膜形成不良。
在本发明的退火分离剂中,从磁特性、被膜特性等其他观点出发,可以进一步使用以下记载的添加剂。
具体而言,以往公知的Li、Na、K、Mg、Sr、Ca、Ba、Ti、V、Cr、Mn、Fe、Co、Ni、Zn、Si、Cu、Sb、Pb、Sn、Al、Bi、Nb、Mo、W和镧系元素的硼酸盐、碳酸盐、硫酸盐、氧化物、氢氧化物、硝酸盐、卤化物和磷酸盐等。可以只使用它们的1种,也可以将2种以上并用。应予说明,上述添加剂的添加量相对于MgO:100质量份,优选为0.01~15质量份。这是因为如果过少则效果不足,另一方面,如果过多则过度促进被膜形成,或仅表层的抑制剂被过度增强,反而容易使磁特性、被膜变差。
在本发明的制造方法中,上述退火分离剂按照常规方法涂布在钢板表面。作为最普通的方法,用适量的水将退火分离剂浆料化,采用辊涂机进行涂布、干燥的方法。除此之外,还可以使用例如静电涂装的方法、喷涂、模涂等用涂布机涂布的方法。
退火分离剂的涂布量可以按照常规方法,例如,以不含水的状态的重量计,每两面为0.5~30g/m2左右即可。
应予说明,本说明书中的退火分离剂的涂布量以不含水的状态的每两面的重量来表示。
接着,对钢坯材的成分组成和制造条件,说明限定理由和优选条件等。
[钢坯的成分组成]
C:0.01~0.09%
C是促进织构改善的元素,含量在上述范围之外均不能形成良好的织构。所以,其含量为0.01%~0.09%,优选为0.02%以上,更优选为0.03%以上,还优选为0.08%以下,更优选为0.07%以下。
Si:2.00~4.00%
Si是改善磁特性的元素,含量小于2.00%时,铁损的降低效果减弱,如果超过4.00%,则损害冷轧性。所以,其含量为2.00%~4.00%,优选为2.30%以上,更优选为2.50%以上,还优选为3.80%以下,更优选为3.50%以下。
Mn:0.03~0.25%
Mn是为了改善钢的热加工性所需的元素。含有小于0.03%时,上述效果不充分,另一方面,如果超过0.25%,产品板的磁通密度下降。因此,Mn的含量为0.03~0.25%的范围,优选为0.06%以上,更优选为0.08%以上,还优选为0.22%以下,更优选为0.20%以下。
Nb、V、Ti:任意一种或多种的合计为0.002~0.025%
Nb、V、Ti是用于增强抑制剂的元素。如果它们的含量的合计小于0.002%,则没有效果,如果超过0.025%,则即使应用本发明也难以使这些元素充分纯化。它们的含量的合计优选为0.005%以上,更优选为0.010%以上,还优选为0.020%以下,更优选为0.018%以下。
除了这些成分外,作为通常的抑制剂形成成分,众所周知AlN、MnS和MnSe等。在本发明中可以使用这些中的任意一种,也可以将2种以上并用。
另外,在本发明中,作为辅助抑制剂,可以使用Ni、Cr、Cu、P、Sb、Sn、Bi、Mo、B和Te中的任意1种以上。这些元素是不形成析出物而不需要纯化或容易纯化的元素。
以上的元素的含量分别为Al:0.004~0.040%、N:0.002~0.010%、S:0.002~0.030%、Se:0.002~0.030%、Ni:0.01~1.50%、Cr:0.01~0.50%、Cu:0.01~0.50%、P:0.005~0.100%、Sb:0.005~0.100%、Sn:0.005~0.100%、Bi:0.001~0.050%、Mo:0.005~0.100%、B:0.0002~0.0025%、Te:0.0005~0.0100%。应予说明,Mn的含量如上。
如果它们的含量均比上述记载范围少,则没有效果,另一方面,如果比记载范围多,则抑制力过强二次再结晶变得不稳定。因此,设为上述范围。
钢坯的成分组成的剩余部分为Fe和不可避免的杂质,本说明书中也记载为“实质上由Fe构成”。
[制造条件]
按照公知的方法将具有上述优选的成分组成的钢坯加热进行热轧,再通过1次或隔着中间退火的多次冷轧制成最终板厚的最终冷轧板。应予说明,根据需要,还可以在热轧后进行热轧板退火。
最终冷轧板进行一次再结晶退火,接着,涂布本发明的退火分离剂后进行最终退火。最终退火可以采用由二次再结晶退火和随后的更高温下的纯化退火构成的公知的方法进行即可。例如,二次再结晶退火可以在800℃~1100℃的温度保持5~200小时。如果在上述温度范围内保持上述时间,则为了之后的纯化退火,也可以边升温边进行二次再结晶退火。纯化退火通常可以在1200℃左右的最高到达温度下进行,但如果将最高到达温度设为1210℃、优选1230℃以上,则能够进一步促进纯化。纯化退火时间在1200℃以上的时间优选为1小时以上,进一步优选为3小时以上。最高到达温度的上限没有特别限定,但从防止卷材形状不良的观点出发,优选小于1250℃。纯化退火时间的上限也同样是达到1200℃以上的时间优选为30小时以下,更优选为20小时以下。
然后,还可以进一步涂布含有胶态二氧化硅等的绝缘涂层,实施同时进行平坦化退火和烧结的绝缘张力涂布处理。通过这样的处理工序能够得到具有优异磁特性和被膜特性的取向性电磁钢板。应予说明,根据需要,还可以利用激光、电子束等进行磁畴细化处理。
此外,在本发明的制造方法中,本说明书中未记载的制造条件都可以使用常规的方法。
实施例
[实施例1]
将含有C:0.06%、Si:3.40%、Mn:0.08%、Al:0.006%、Sb:0.020%、Ti:0.010%、N:0.003%和Cr:0.03%、剩余部分实质上由Fe构成的钢坯在1250℃下加热40分钟后,进行热轧制成2.0mm的板厚,然后进行1000℃、60秒的热轧板退火,接下来,通过连轧机进行冷轧,制成最终板厚为0.23mm的钢板。将该钢板脱碳退火后,涂布退火分离剂并干燥,卷绕成卷状。
使用的退火分离剂相对于主剂的MgO:100质量份添加2质量份氧化钛、1质量份硫酸镁,或者,进一步以3级的浓度添加复合氧化物MnTa2O6或各种氧化物,以13g/m2涂布在钢板的两面。
然后,作为最终退火,以10℃/h从800℃升温至1100℃进行二次再结晶退火,然后在1200℃以上进行10小时的最高到达温度为1230℃的纯化退火。接下来,涂布绝缘涂层,进行热平坦化的同时在900℃下烧结60秒后,利用电子束照射进行磁畴细化处理。
将上述的产品的磁特性示于表2。另外,在除去该钢板的被膜后,对Ti、N、C进行定量分析,结果一并记在该表中。
[表2]
表2
由该表可知,如上所述,在含有适量适合于本发明的复合氧化物的退火分离剂中,有效地进行Ti、N的纯化,其结果,磁特性也得到了改善。
[实施例2]
将含有C:0.07%、Si:3.28%、Mn:0.07%、Al:0.02%、N:0.008%、S:0.02%和V:0.01%、剩余部分实质上由Fe构成的板坯加热至1400℃的温度,之后热轧制成板厚为2.2mm,进行隔着1100℃、1分钟的中间退火的2次冷轧,制成0.23mm的最终板厚。在该冷轧板脱碳退火后,将相对于MgO:100质量份添加了5质量份的CaMoO4和0.2质量份的硼酸钾的退火分离剂以11g/m2涂布在钢板的两面。应予说明,作为比较例,也同时进行除了不使用CaMoO4外,同样的钢板的制造。然后,作为最终退火,在820℃的温度下保持50小时的二次再结晶退火之后,在干燥的H2气氛中进行最高到达温度各种改变后的纯化退火5小时。接下来,涂布绝缘涂层,进行热平坦化的同时在900℃烧结60秒。将上述的产品的磁特性示于表3。另外,在去除该钢板的被膜后,对V、N、C进行定量分析,结果一并记在该表中。
[表3]
表3
由该表可知,通过将纯化的最高到达温度提高到1210℃以上,V的纯化被进一步促进。
[实施例3]
将由表4所示的各成分构成的板坯加热到1400℃的温度之后,热轧至板厚:2.2mm,进行隔着1050℃、2分钟的中间退火的2次冷轧,制成0.23mm的最终板厚。在该冷轧板脱碳退火后,将相对于MgO:100质量份添加了3质量份的(Fe,Mn)Nb2O6、3质量份的氧化锡和2质量份的氧化钛的退火分离剂以10g/m2涂布在钢板的两面并干燥。应予说明,作为比较例,也同时实施除了不使用(Fe,Mn)Nb2O6外同样的钢板的制造。然后,作为最终退火,在820℃的温度下保持50小时的二次再结晶退火之后,在干燥的H2气氛中分别进行1230℃、5小时的纯化退火。接下来,涂布绝缘涂层,进行热平坦化的同时在900℃下烧结60秒。将上述的产品的磁特性记在表4中。另外,将该钢板的被膜除去后,对Nb、V、Ti、N、C进行定量分析,结果一并记在该表中。
由该表可知,具有本申请规定范围内的成分组成的任何钢板,在使用含有规定量的(Fe,Mn)Nb2O6的退火分离剂的条件下,都充分进行了纯化,磁特性也获得了良好的值。
Claims (4)
1.一种取向性电磁钢板的制造方法,其特征在于,将取向性电磁钢板用板坯加热,进行热轧,实施1次或隔着中间退火的2次以上的冷轧,实施一次再结晶退火,接着,涂布退火分离剂后进行最终退火,
所述取向性电磁钢板用板坯具有以下成分组成:含有C:0.01~0.09质量%、Si:2.00~4.00质量%、Mn:0.03~0.25质量%,进一步含有合计0.002~0.025质量%的选自Nb、V和Ti中的1种或2种以上,剩余部分为Fe和不可避免的杂质,
所述退火分离剂以MgO为主剂,相对于MgO:100质量份含有1~10质量份的范围的复合氧化物,该复合氧化物含有分别选自1组:Fe、Mn、Al和Ca以及2组:Zr、Ta、Mo和Nb中的1种或2种以上的元素。
2.根据权利要求1所述的取向性电磁钢板的制造方法,其中,将所述最终退火的最高到达温度设为1210℃以上。
3.根据权利要求1或2所述的取向性电磁钢板的制造方法,其中,所述取向性电磁钢板用板坯除了所述成分组成外进一步含有选自Al:0.004~0.040质量%、N:0.002~0.010质量%、S:0.002~0.030质量%、Se:0.002~0.030质量%、Ni:0.01~1.50质量%、Cr:0.01~0.50质量%、Cu:0.01~0.50质量%、P:0.005~0.100质量%、Sb:0.005~0.100质量%、Sn:0.005~0.100质量%、Bi:0.001~0.050质量%、Mo:0.005~0.100质量%、B:0.0002~0.0025质量%和Te:0.0005~0.0100质量%中的1种或2种以上。
4.一种退火分离剂,其特征在于,是权利要求1~3中任一项所述的取向性电磁钢板的制造方法中使用的退火分离剂,
该退火分离剂中相对于MgO:100质量份含有1~10质量份的范围的复合氧化物,该复合氧化物含有分别选自1组:Fe、Mn、Al和Ca以及2组:Zr、Ta、Mo和Nb中的1种或2种以上的元素。
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