CN102453793B - 用于具有优良磁性能的镜面取向硅钢制备的退火隔离剂 - Google Patents
用于具有优良磁性能的镜面取向硅钢制备的退火隔离剂 Download PDFInfo
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- 229910000976 Electrical steel Inorganic materials 0.000 title claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 22
- 238000002955 isolation Methods 0.000 title abstract 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 6
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- 238000002360 preparation method Methods 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
- C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
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Abstract
用于具有优良磁性能的镜面取向硅钢制备的退火隔离剂,其成分重量百分比为:Al2O3粉末77~98%,碱土金属氧化物粉末1~8%,碱金属氯化物或/和碱土金属氯化物1~15%。本发明的退火隔离剂使高温退火过程中钢板表面不形成玻璃膜底层,同时利用氯化物的腐蚀反应移除基板近表面的嵌入式氧化物,从而获得表面光洁和磁性能稳定的产品。
Description
技术领域
本发明涉及取向硅钢制造方法,特别涉及用于具有优良磁性能的镜面取向硅钢制备的退火隔离剂。
背景技术
取向硅钢在经过热轧、常化及冷轧处理后,要在H2-N2气氛保护下进行脱碳退火,消除轧制应力,形成初次再结晶,同时向炉内通湿气,将钢带中碳含量控制在30ppm以下,以防止成品发生磁时效。脱碳退火时钢带表面会发生氧化,形成以SiO2和Fe2SiO4为主的氧化层,对进一步脱碳造成不利影响。在后续高温退火过程中,氧化层与钢带表面涂覆的退火隔离剂发生化学反应,生成以Mg2SiO4为主的玻璃膜底层,该玻璃膜底层在高温退火时可以防止钢带粘结并起到净化钢质的作用。
取向硅钢表面硅酸镁玻璃膜底层具有较高的硬度,造成钢板冲片性能较差,往往只有几千次;并且玻璃膜底层与钢板基体的嵌入式结合会阻碍磁畴壁的运动,增加磁滞损耗。
为了提高晶粒取向硅钢的冲片性能和进一步提高磁性能,日本人开发出无玻璃膜底层的晶粒取向硅钢。日本专利JP49096920通过酸洗的方法去掉取向硅钢表面玻璃膜底层,但要完全洗掉约10μm厚度的玻璃膜底层(包括与钢板以嵌入式相结合的氧化物),需要在强酸中长时间浸泡,带来制造成本高,药剂污染环境等问题。
日本专利JP05156362A采用Al2O3做高温退火隔离剂,Al2O3与氧化层和钢板基体均不发生反应,可直接获得无玻璃膜底层的取向硅钢,但该法不能移除在脱碳退火过程中形成的氧化层及嵌入式氧化物,因而不利于改善磁性。
为解决这一问题,日本专利JP2003247024采用控制PH2O/PH2的比例,形成低氧化度气氛,不形成Fe系氧化物,之后再涂布以Al2O3为主的隔离剂,从而获得表面光洁的晶粒取向硅钢,但脱碳过程中过低的氧化度会造成脱碳困难。日本专利JP05156364A在脱碳退火结束后,采用酸洗将钢板表面氧化层去除,而后再涂布以Al2O3为主的隔离剂。
美国专利US554719使用MgO+SiO2作为退火隔离剂,在二次再结晶退火过程中钢板表面形成疏松的硅酸镁,然后通过刷洗将其去除,获得无玻璃膜底层产品。
日本专利JP2000038615使用添加氯化物的氧化镁和氧化铝作为退火隔离剂,通过界面反应:(2/3)MCl3+Fe+(3/2)O2→M2O3+FeCl2↑,将形成的玻璃膜底层去除,从而获得无玻璃膜底层产品。
日本JFE公司使用不与钢板表面反应的Al2O3等作为高温退火隔离剂,直接获得无玻璃膜底层的晶粒取向硅钢。此方法要完全消除钢板近表面氧化物夹杂需要严格控制脱碳露点使钢板表面不形成铁氧化物,但这势必会带来脱碳、渗氮等问题。
美国Armco公司(现AK公司)在氧化镁中添加SiO2作为退火隔离剂,二次再结晶退火过程中钢板表面形成的疏松硅酸镁有利于退火保护气体进入钢板层间净化钢质。但此方法往往难以将表面硅酸镁完全刷洗掉,也不能将钢板近表面的嵌入式氧化物完全消除,对降低铁心损耗效果有限。
日本NSC公司在氧化镁中添加氯化物作为退火隔离剂,添加大量的氯化物在二次再结晶退火过程中对钢板表面造成一定的腐蚀,影响表面抑制剂,造成二次再结晶不稳定。
表1
发明内容
本发明的目的在于提供一种用于具有优良磁性能的镜面取向硅钢制备的退火隔离剂,使高温退火过程中钢板表面不形成玻璃膜底层,同时利用氯化物的腐蚀反应移除基板近表面的嵌入式氧化物,从而获得表面光洁和磁性能稳定的产品。
为达到上述目的,本发明的技术方案是,
用于具有优良磁性能的镜面取向硅钢制备的退火隔离剂,其成分重量百分比为:Al2O3粉末77~98%,碱土金属氧化物粉末1~8%,碱金属氯化物或/和碱土金属氯化物1~15%。
进一步,所述的碱土金属氧化物包括BeO、MgO、CaO、SrO、或BaO。
又,所述的碱金属氯化物包括LiCl、NaCl、KCl、或RbCl。
所述的碱土金属氯化物包括BeCl2、MgCl2、CaCl2、SrCl2、BaCl2或ZnCl2。
通过实验研究发现,在高温退火中使用不与基板氧化层发生反应的物质作为退火隔离剂,并在其中添加少量的碱土金属氧化物,以带入不高于2.5Wt%的水分,另外添加一定的氯化物,水分与氯化物添加剂中氯离子相互作用形成具有一定酸性的腐蚀液,对消除基板近表面氧化层是十分有效的。
本发明镜面取向硅钢退火隔离剂,通过加水搅拌形成一定浓度的涂液,继而在脱碳板表面进行涂覆得以施行。涂覆结束后在不高于300℃的温度下烘烤30s以上时间以驱除隔离剂中的自由水分,此时隔离剂形成一种具有微孔状物质,其主要成分为Al2O3、Ca(OH)2以及一种或几种氯化物的混合物,具有良好的透气性。该水解过程发生的主要化学反应为:
CaO+H2O=Ca(OH)2 ①
在高温退火前期,Ca(OH)2在温度高于580℃即发生分解反应,重新生产CaO,释放出水分。水分的存在一方面提供了一定的溶解液,另一方面也和氯离子共同作用形成一定腐蚀作用的酸性物质HCl,高温退火过程中依次发生的化学反应如下:
Ca(OH)2=CaO+H2O ②
HCl以气相形式透过隔离剂,与基板氧化层物质发生化学反应,并推动化学平衡式③持续不断地向右移动,继续发生反应。HCl与氧化层物质发生的化学反应如下:
2HCl+FeO=FeCl2+H2O↑ ④
4HCl+Fe2SiO4=2FeCl2+SiO2+2H2O↑ ⑤
经HCl腐蚀的氧化层,蜕化成为疏松多孔状物质,与基体的结合力显著下降,在高温退火后经过轻酸洗和刷洗,便可轻易将该氧化层去除,最终经过热拉伸平整工艺形成表面光洁的镜面取向硅钢。
传统晶粒取向硅钢高温退火过程中形成的玻璃膜底层具有较高的硬度,降低硅钢片的冲片性能,加工时会对模具造成一定程度损伤。并且,氧化物在基体中钉扎结构阻碍了磁畴壁的运动,对磁性能造成不利的影响。无底层晶粒取向硅钢可以大幅提高硅钢片的加工性能,磁性能也可因钉扎结构的消失而进一步提高,从而获得超低铁心损耗产品。
本发明之前,获得镜面取向硅钢的专利主要以MgO和氯化物或Al2O3为主,前者会造成磁性能的不稳定,后者不能移除在脱碳退火过程中形成的嵌入式氧化物。有人采用在Al2O3隔离剂中同样添加氯化物,但氯化物本身需要辅以一定的水分才能与嵌入式氧化物发生反应,从而将其移除。
本发明创造性的引入了碱土金属氧化物,根据碱土金属氧化物本身的水溶性特征可以很容易的控制高温退火中带入到水分,方法便捷,能够稳定获得优质的镜面取向硅钢产品。所用设备为取向硅钢的常规生产设备,具有极佳的实用性和推广性,因而具有良好的推广前景。
附图说明
图1为比较例1的钢板光学截面照片(隔离剂:MgO 65Wt%+SiO2 35Wt%);
图2为比较例2的钢板光学截面照片(隔离剂:MgO 90Wt%+CaCl2 Wt%份);
图3为比较例3的钢板光学截面照片(隔离剂:Al2O3 100Wt%);
图4为本发明实施例钢板的光学截面照片(隔离剂:Al2O3 86 Wt%+CaO 4Wt%+MgCl2 10Wt%)。
具体实施方式
下面结合实施例对本发明做进一步说明。
用500kg真空炉炼钢,板坯化学成分(Wt%)为:0.045%C、3.25%Si、0.006%S、0.027%Als、0.006%N、0.15%Cu、0.012%Mn其余为Fe及不可避免的杂质。钢坯在1150℃下加热后,热轧成2.6mm厚的热轧板。热轧板经1150℃常化退火1分钟后,酸洗并冷轧成最终板厚0.285mm。冷轧板在835℃进行120秒的脱碳退火处理,表面氧含量为0.8和1.6g/m2两个水平;经渗氮处理后,钢板的氮含量为250ppm。脱碳退火板涂布退火隔离剂(配比见表2),成卷后在干的氮、氢保护性气氛中进行1200℃、保温20小时的高温退火;开卷后经过涂绝缘涂层及拉伸平整退火。
表2 单位:重量百分比
成品的电磁性能平均值和表面质量见表3。
表3
从图1~图4及表3,可以看出,涂布本发明隔离剂的硅钢板表面残余氧化物很少,并且磁性能优良。由此可见,本发明通过对取向硅钢表面的有效精加工,可以制造出优良磁性能的镜面取向硅钢板。
本发明高温退火隔离剂可以有效净化钢质并防止钢卷发生粘结,另一方面又可以在高温退火时形成腐蚀性气氛,将近表面氧化层移除,因此能够形成磁性能优良的镜面取向硅钢。
Claims (3)
1.用于具有优良磁性能的镜面取向硅钢制备的退火隔离剂,其成分重量百分比为:
Al2O3粉末 77~98%,
碱土金属氧化物粉末 1~8%,
碱金属氯化物或/和碱土金属氯化物 1~15%;
所述的碱土金属氧化物包括BeO、MgO、CaO、SrO、或BaO。
2.如权利要求1所述的用于具有优良磁性能的镜面取向硅钢制备的退火隔离剂,其特征是,所述的碱金属氯化物包括LiCl、NaCl、KCl、或RbCl。
3.如权利要求1所述的用于具有优良磁性能的镜面取向硅钢制备的退火隔离剂,其特征是,所述的碱土金属氯化物包括BeCl2、MgCl2、CaCl2、SrCl2或BaCl2。
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