CN1152982C - 防止退火时粘接的镀镍钢板及其制造方法 - Google Patents
防止退火时粘接的镀镍钢板及其制造方法 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 38
- 229910000831 Steel Inorganic materials 0.000 title abstract description 38
- 239000010959 steel Substances 0.000 title abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000009792 diffusion process Methods 0.000 claims abstract description 24
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 23
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010960 cold rolled steel Substances 0.000 claims abstract description 18
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- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- 229910003271 Ni-Fe Inorganic materials 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- NBXQTKPAYIDBGR-UHFFFAOYSA-J silicon(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Si+4] NBXQTKPAYIDBGR-UHFFFAOYSA-J 0.000 claims description 6
- 238000007743 anodising Methods 0.000 claims description 3
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- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 abstract 1
- 239000002075 main ingredient Substances 0.000 abstract 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 abstract 1
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- 238000005868 electrolysis reaction Methods 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
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- 150000001875 compounds Chemical class 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
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- 125000006850 spacer group Chemical group 0.000 description 2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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Abstract
本发明的目的在于防止镀镍钢板的相互粘接,在退火炉中热处理镀镍钢板使镍进行扩散时钢板容易发生粘接。镀镍钢板具有厚度为0.5~10μm的镍-铁扩散层、在该扩散层上的其厚度为0.5~10μm的镀镍层以及在镀镍层上的氧化硅层,该氧化硅层至少形成在冷轧钢板的一个表面,该层上的硅量为0.1~2.5mg/m2。在冷轧钢板上镀镍之后,在以原硅酸钠为主要成分的槽液中用浸渍法或电解处理法在镀镍钢板上沉积一层氢氧化硅,然后进行热处理。
Description
技术领域
本发明涉及镀镍钢板及其制造方法,目的在于防止钢板的彼此粘接,在制造钢板(以下被说明是镍扩散的镀镍钢板)期间即在退火炉中热处理镀镍钢板使镍扩散期间便容易发生这种粘接作用。
背景技术
一般地,镍扩散的镀镍钢板在镀镍之后被重新卷成紧密的板卷,然后放入温度约500~700℃的封闭退火炉中进行热处理,从而获得需要的加工性。但是,这种热处理会产生一些问题,因为镍的扩散在钢板表面上进行,所以重新卷绕的叠层钢板会彼此粘接。通常,为防止在退火期间钢板彼此粘接,使钢板以松卷的状态退火,即用金属丝等作间隔器卷绕钢板,该间隔器在卷绕的钢板之间形成间隙,或者预先在钢板上涂布一层在高温下稳定的释放剂例如氧化物、碳化物或氮化物,然后再进行退火。
但是,在钢板上叠加金属丝进行再卷绕然后再退火的方法不是有效的,因为这样作容易擦伤钢板,而且增加了重新卷绕和除去金属丝的额外工作。另外,在钢板上涂一层释放剂的退火方法也产生一些问题,例如由于使用释放剂而增加了成本,难于除去释放剂以及钢板表面变得难看,因而两种方法在工业上均缺乏实用性。
已提出在钢板表面上涂一层释放剂例如钛或铝的氧化物来防止冷轧钢板退火时的粘接,这是不针对镀镍钢板提出的(公开的日本专利昭63-235427等)。
然而在退火之后这些氧化物仍保留在钢板表面上,所以其缺点是,色调改变,损害了钢板的外观。为此在加热处理镀镍钢板时采用上述金属丝,而从来不用氧化物。
发明内容
本发明的技术目的是提供一种经过预防粘接处理的镀镍钢板,以防止热处理镀镍钢板时该镀镍钢板彼此粘接。
本发明的镀镍钢板不需要加金属丝进行重新卷绕或涂布释放剂防止粘接,该镀镍钢板在热处理后具有极好的外观。
本发明的镀镍钢板的特征在于,它具有其厚度在0.5~10μm的镍-铁扩散层、在扩散层上的其厚度在0.5~10μm的镀镍层以及在镀镍层上的氧化硅层,至少在冷轧钢板的一个表面上形成氧化硅层,该层上硅的量为0.1~2.5mg/m2。
本发明的镀镍钢板其特征还在于,它具有其厚度在0.5~10μm的镍-铁扩散层以及在扩散层上的氧化硅层,至少在冷轧钢板的一个表面上形成该氧化硅层,该层上硅的量为0.1~2.5mg/m2。
另外,本发明的镀镍钢板的制造方法的特征在于,先在冷轧钢板上电镀镍,然后在一个以原硅酸钠为主要成分的槽液中进行浸渍处理或电解处理,沉积氢氧化硅,最后进行热处理。
另外,也可用这样的方法生产镀镍钢板,即在冷轧钢板上镀上镍,然后在一个以原硅酸钠为主要成分的电解液中沉积氢氧化硅,沉积用的电流密度为0.1~20A/dm2,总电量为0.1~1000C/dm2(Coulomb/dm2),最后进行热处理。
在这些镀镍层上形成氢氧化硅层的处理时最好交替进行阳极化(A)处理和阴极化(C)处理。
在一个冷轧钢板上镀镍之后,于一个原硅酸钠槽液中于特定的条件进行浸渍或电解处理,用这种方法可以获得一种镀镍钢板,这种钢板在热处理之后具有极好的外观,并且在热处理期间可以防止钢板的彼此粘接。
附图说明
图1是示意图,示出在镀镍钢板上形成氢氧化硅的制造过程;
图2是透视图,示出以恒定压力固定和紧压镀镍钢板的方法;
图3是透视图,示出两个粘接的测试钢片的强迫剥离状态。
具体实施方式
下面用实例详细说明本发明。
本发明的镀镍钢板具有厚度为0.5~10μm的镍-铁扩散层,在该扩散层上的厚度为0.5~10μm的镀镍层以及在镀镍层上的氧化硅层,该氧化硅层至少形成在冷轧钢板的一个表面上,该层上的硅量为0.1~2.5mg/m2。
上述镀镍层最好按防腐蚀要求形成。但也不一定形成。在这种情况下,镀镍钢板最好具有厚度为0.5~10μm的镍-铁扩散层以及在该层上的氧化硅层,该氧化硅层至少形成在冷轧钢板的一个表面上,该层上的硅量为0.1~2.5mg/m2。
该氧化硅层上的硅量为0.1~2.5mg/m2,因为在低于0.1mg/m2下限时,它不能充分地防止热处理时的粘接,而在大于2.5mg/m2则又不是最好的,因为由于二氧化硅的存在镀镍钢板的外观变成白色,这损害了镀镍层的特有的色调。
另外,因为氢氧化硅是通过本发明中的原硅酸钠电解槽液沉积上去的,所以它是极细的,因而可以保持镀镍层原来特有的色调。
通过原硅酸钠电解槽液沉积的氢氧化硅经随后的加热处理被脱水,转变成二氧化硅。
在本发明中,沉积的氧化硅量由于氧化硅的分析设备原因而被折算为硅量,即氧化硅中的硅量由X射线荧光分析法测定。
形成氢氧化硅层的方法是,在镀镍之后将冷轧钢板放在以原硅酸钠为主要成分的槽液中进行浸渍,或者将其放在以原硅酸钠为主要成分的电解槽液中进行电解处理,在沉积氢氧化硅之后再进行热处理。然而,电解法的涂层效果优于浸渍法的效果。
图1是示意图,示出在以原硅酸钠为主要成分的电解槽液中进行电解处理而在镀镍钢板表面上沉积氢氧化硅的形成方法。
对于上述电解处理,可以采用任何处理槽,例如如图1(a)或(b)所示的水平式处理槽或如图1(c)或1(d)所示的垂直式处理槽。
在镀镍钢板上形成氢氧化硅层的方法包括一种方法,在这种方法中,首先进行C处理(钢板一方是阴极),随后在接着的处理中用A处理(钢板一方是阳极),如图1(a)或1(c)。
也可以采用先进行A处理然后进行C处理的方法,如图1(b)或(d)所示。
因为在这些处理中均清洗镀镍钢板的表面,所以上述任何一种处理均可有效地在镀镍钢板表面上沉积大量的氢氧化硅。
从在镀镍钢板表面上沉积氢氧化硅的效率看,首先进行C处理然后再进行A处理的方法是最有效的。
另外,可以通过配置大量处理槽和电极的方式重复多次地进行C处理→A处理,或A处理→C处理。
而且,对于上述多次重复处理,可使开始处理和结束处理时的极性相同,例如C处理→A处理→C处理,或A处理→C处理→A处理。
饱和铝的低碳钢板一般适合作冷轧钢板。另外,也可以用加有铌、硼和钛的无时效低碳钢轧制的冷轧钢板。一般采用冷轧之后用电解清洗、退火和硬化冷轧的钢板作电镀底衬,也可以直接用冷轧之后的钢板作电镀底衬。在这种情况下,可以在冷轧和镀镍之后同时进行钢底衬的重新结晶退火和镀镍层的热扩散处理。
至少在冷轧钢板的一个表面上形成厚度为0.5~10μm的镀镍层。低于0.5μm的镀镍层厚度在通常大气应用中时不能形成充分的抗腐蚀性。而超过10μm的厚度,则抗腐蚀性的增加已达到饱和,而且也不经济。作为本发明中的镍电解槽可以用任何已知的电解槽,例如瓦特槽(Watts bath)、氨基磺酸盐电解槽和氯化物电解槽。在电镀方式方面虽然有毛面电镀、半光滑表面电镀和光滑表面电镀,但在本发明中最好采用除光滑表面电镀以外的毛面电镀或半光滑表面电镀,光滑表面电镀需加入含硫的有机化合物。对于本发明,光滑表面电镀不太合适,因为用光滑表面电镀形成的镀膜中存在硫,所以在下述的热处理期间,该镀膜将变脆,同时也降低了腐蚀性。
然后将如此镀镍的钢板放在原硅酸钠溶液中进行浸渍或电解处理。原硅酸钠的浓度在1%~7%比较好,最好在2%~4%。
浓度低于1%时,只有少量氢氧化硅沉积在钢板上,通过随后的热处理不能达到不小于0.1mg/m2氧化硅的必需量,这种情况容易造成在热处理时镀镍钢板的相互粘接。另外在进行电解处理时,还造成需要增加处理电压的问题。
另一方面,超过7%的浓度是不经济的,因为随着钢板的移动从处理电解槽中带出的原硅酸钠溶液的量增加。另外,太大的浓度也危及处理电解槽的操作,这不是可取的。
进行沉积氢氧化硅层电解处理的总电量最好为0.1~1000C/dm2,
在总电量低于0.1C/dm2时,在镀镍钢板上沉积氢氧化硅的效率差,不能达到不低于0.1mg/m2氧化硅的必需量,这易于使钢板在热处理期间彼此粘接。
另一方面,如果总电量增加到不低于1000C/dm2,则有剩余量的氧化硅不能沉积在钢板上,这造成浪费。
镍-铁扩散层的厚度在0.5~10μm之间,可以在此范围内形成各种厚度的镍-铁扩散层,方法是,将镀镍钢板用上述原硅酸钠溶液处理,然后重绕成板卷,并用封闭退火方法在不超过500~700℃范围内的温度下加热该镀镍钢板,加热时间不低于几个小时。改变热处理温度和处理时间便可控制扩散层的厚度。
通过形成镍-铁扩散层可以获得钢底衬和镍镀层以及钢底衬和镍-铁扩散层之间极好的粘接性。低于0.5μm的镍-铁扩散层厚度不能充分地使钢底衬与该扩散层粘合,因而镀层在镀镍钢板进行重加工例如进行深拉时便容易脱落。另一方面,超过10μm的镍-铁扩散层则使粘合作用的增加达到饱和,因而不经济。
下面举例说明。
将0.3mm厚的冷轧钢板切成100mm×100mm的片,并用电解法去油脂和在稀硫酸中清洗表面,然后在下述条件下在其一个表面上镀镍。并使镀镍钢板具有不同厚度的镀镍层。然后在原硅酸钠溶液中以各种条件对该镀镍钢板进行浸渍或电解处理。
电镀镍的条件:
电镀液成分:硫酸镍,300g/L;
氯化镍,40g/L;
硼酸,30g/L;
十二烷基硫酸钠,0.5g/L;
半光滑表面电镀剂,1g/L;
pH:4.1~4.6;
电镀液温度:55±2℃;
电流密度:10A/dm2。
采用上述条件改变电镀时间便可以形成具有不同镀镍层厚度的镀镍钢板。
原硅酸钠溶液中电沉积氢氧化硅条件:
处理电解液:原硅酸钠,30g/L;
电解液温度:50±5℃;
采用以下两种方法中之一控制沉积量:
浸渍处理:改变浸渍时间可以获得具有不同氧化硅沉积量的处理钢板;
电解处理:电流密度5A/dm2,改变电量以及极性可以获得具有不同氧化硅沉积量的处理钢板。
将按上述方法得到的已处理钢板切成100mm×30mm的样片,并将其叠置成叠置件1,使得在同一处理条件下处理的两片样片的处理表面接触,如图2所示,然后用刚性板2以及紧固紧压板3固定和紧压该叠置件,该刚性板和紧压板通过用转矩扳手拧动的四个螺栓4和螺帽5而与叠置件上、下接触,因而可在每个测试片上均匀地施加相同的34千克力/mm2紧固压紧力。然后将此紧固压紧的测试片放在由6.5%的氢和主体氮气组成的保护气氛中在不同的处理温度(550~700℃)和处理时间(1~10h)的条件下进行热处理。在热处理之后,将两个粘接测试片的两片粘接表面的端部分强制剥离,如图3所示,并将两个剥离的端部分弯曲成T字形,作成拉力测试片,以便固定在拉力测试仪的两个卡盘部分上。用拉力测试仪剥离该拉力测试片,因此可以测量粘接强度,所谓粘接强度是剥离开始时的强度,并可以根据以下标准评估由热处理造成的测试片的粘接程度(即预防粘接的能力):
良好:剥离拉力小于3kg;
差:剥离拉力大于3kg。
各样片的处理条件和评价结果示于表1。
表1
试样编号No | 原硅酸钠溶液中硅酸盐的沉积条件 | 热处理条件 | 防止钢板在热处理期间彼此粘接的结果 | |||||
沉积方法 | 电解顺序 | 总电量(C/dm2) | Si量(mg/m2) | 温度℃ | 时间h | |||
本发明 | 1 | 浸渍法 | - | - | 0.38 | 550 | 10 | 良好 |
2 | 电解法 | A处理→C处理 | 100 | 1.07 | 650 | 8 | 良好 | |
3 | 电解法 | C处理→A处理 | 100 | 1.17 | 650 | 8 | 良好 | |
4 | 电解法 | C处理 | 15 | 0.51 | 600 | 8 | 良好 | |
5 | 电解法 | A处理 | 250 | 1.70 | 650 | 8 | 良好 | |
6 | 电解法 | C处理→A处理→C处理 | 250 | 1.84 | 700 | 1 | 良好 | |
7 | 电解法 | C处理→A处理→C处理→A处理 | 1000 | 2.48 | 700 | 1 | 良好 | |
8 | 电解法 | A处理→C处理→A处理→C处理 | 1000 | 2.30 | 700 | 1 | 良好 | |
比较例 | 9 | - | - | - | 0 | 550 | 10 | 差 |
10 | - | - | - | 0 | 650 | 8 | 差 | |
11 | - | - | - | 0 | 700 | 1 | 差 |
如表1所示,本发明的镀镍钢板在热处理期间基本上不相互粘接。
然而在比较例中,其上没有形成氧化硅层的镀镍钢板则在热处理期间造成彼此粘接。
本发明的镀镍钢板在热处理期间具有极好的防粘接能力。即镀镍钢板在使镍扩散到钢板中去的热处理期间不会彼此粘接,即使在镀镍钢板被再卷成板卷的情况下。
Claims (6)
1.一种镀镍钢板,具有厚度为0.5~10μm的镍-铁扩散层、在该扩散层上的厚度为0.5~10μm的镍镀层以及在该镍镀层上的氧化硅层,该氧化硅层至少形成在冷轧钢板的一个表面上,该层上的硅量为0.1~2.5mg/m2。
2.一种镀镍钢板,具有厚度为0.5~10μm的镍-铁扩散层以及在该扩散层上的氧化硅层,该氧化硅层至少形成在冷轧钢板的一个表面上,该层上的硅量为0.1~2.5mg/m2。
3.一种制造预防退火期间发生粘接的镀镍钢板的方法,其特征在于,先在冷轧钢板上电镀镍,随后在以原硅酸钠为主要成分的槽液中用浸渍法或电解处理法在镀镍层上沉积一层氢氧化硅,最后进行热处理。
4.如权利要求3所述的镀镍钢板的制造方法,其特征在于,在上述镀镍层上形成氢氧化硅层时交替进行阳极化处理和阴极化处理。
5.一种制造预防退火期间发生粘接的镀镍钢板的方法,其特征在于,先在冷轧钢板上镀镍,然后在以原硅酸钠为主要成分的槽液中在电流密度为0.1~20A/dm2和总电量为0.1~1000C/dm2的条件下,在镀镍层上沉积一层氢氧化硅,最后进行热处理。
6.如权利要求5所述的镀镍钢板的制造方法,其特征在于,在上述镀镍层上形成氢氧化硅层时交替进行阳极化处理和阴极化处理。
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JP7159851A JP2971366B2 (ja) | 1995-06-01 | 1995-06-01 | 焼鈍時の密着防止処理を施したニッケルめっき鋼板およびその製造法 |
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US20060130940A1 (en) * | 2004-12-20 | 2006-06-22 | Benteler Automotive Corporation | Method for making structural automotive components and the like |
CN102732936B (zh) * | 2012-06-05 | 2015-04-22 | 沈阳理工大学 | 一种在钢铁件上用电泳沉积法制备氧化硅陶瓷涂层的方法 |
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US4363677A (en) * | 1980-01-25 | 1982-12-14 | Nippon Steel Corporation | Method for treating an electromagnetic steel sheet and an electromagnetic steel sheet having marks of laser-beam irradiation on its surface |
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US4746453A (en) * | 1986-11-07 | 1988-05-24 | China Steel Corporation | Cleaning composition for electrocleaning cold-rolled steel |
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JPH04154973A (ja) * | 1990-10-12 | 1992-05-27 | Sumitomo Metal Ind Ltd | 線材焼鈍時の密着防止方法 |
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JP2762328B2 (ja) * | 1992-07-16 | 1998-06-04 | 東洋鋼鈑株式会社 | インナーシールド用素材およびその製造法 |
JP2786578B2 (ja) * | 1993-06-04 | 1998-08-13 | 片山特殊工業株式会社 | 電池用缶材料の製造方法及び該電池用缶材料 |
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- 1996-05-23 US US08/973,002 patent/US6022631A/en not_active Expired - Lifetime
- 1996-05-23 KR KR1019970708603A patent/KR100274686B1/ko not_active IP Right Cessation
- 1996-05-23 AT AT96914411T patent/ATE480647T1/de not_active IP Right Cessation
- 1996-05-23 CN CNB961943408A patent/CN1152982C/zh not_active Expired - Lifetime
- 1996-05-23 CA CA002222759A patent/CA2222759C/en not_active Expired - Fee Related
- 1996-05-23 WO PCT/JP1996/001368 patent/WO1996038600A1/ja active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
JP2971366B2 (ja) | 1999-11-02 |
CA2222759A1 (en) | 1996-12-05 |
CN1186527A (zh) | 1998-07-01 |
KR19990022124A (ko) | 1999-03-25 |
ATE480647T1 (de) | 2010-09-15 |
DE69638255D1 (de) | 2010-10-21 |
WO1996038600A1 (fr) | 1996-12-05 |
EP0829555A4 (en) | 2000-07-26 |
JPH08333689A (ja) | 1996-12-17 |
EP0829555B1 (en) | 2010-09-08 |
US6022631A (en) | 2000-02-08 |
KR100274686B1 (ko) | 2000-12-15 |
EP0829555A1 (en) | 1998-03-18 |
AU5778796A (en) | 1996-12-18 |
CA2222759C (en) | 2004-05-04 |
AU701969B2 (en) | 1999-02-11 |
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