CN1318634C - 通过浸入金属熔体浴液制备锌-铝合金镀层的改进方法 - Google Patents
通过浸入金属熔体浴液制备锌-铝合金镀层的改进方法 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title 1
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- 244000137852 Petrea volubilis Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
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- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/12—Aluminium or alloys based thereon
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Abstract
一种采用Zn-Al合金对金属件进行不连续镀覆的方法,其包括如下步骤:采用金属层对金属件进行预镀覆,该金属层足够厚,从而能够保护金属件不发生氧化,并且,该预镀层还足够薄,结果预镀层能够与Zn-Al合金熔体浴液基本完全反应或者基本完全溶解进入其中;对所述预镀覆件进行表面活化处理,包括:将其浸泡在盐酸中,之后,使具有氯化盐保护镀层的表面干燥,并且,之后,将所述金属件浸入Zn-Al镀液中。
Description
这是系列号为09/138,049的美国专利申请的部分继续申请,该申请的提交日期是1998年8月21日,题目是“在金属制品上制备锌-铝合金不连续镀层的方法”。该申请此后称作“049申请”,在此全部引入作为参考。
发明领域
本发明涉及通过浸入金属熔体浴液制备锌-铝合金镀层的改进方法,更确切地,本发明涉及一种改进的通过浸入锌-铝合金熔体浴液中,用所述合金对金属件进行不连续镀覆的方法。
发明背景
技术背景
049申请中提出采用锌-铝合金对金属件进行不连续镀覆。而且还指出,其存在的缺点是获得的镀层不均匀或存在裸露区。在该公开的方法之前,要获得的可接受的镀层比较困难,且所用方法复杂、费时。
049申请中公开了一种克服这种缺点的极好办法,其主要包括在浸入锌-铝熔体浴液之前,优选采用金属预镀层对将要不连续镀覆的金属件进行非电解预镀覆的方法。该预镀层优选金属铜或镍。也可以采用钴,但从包括成本和毒性等若干方面考虑,不优选钴。预镀层很薄,其作用是促进锌-铝合金的良好结合。
然而,即使采用预镀层,最终的锌-铝合金层可能还会存在一些结合性、致密性以及外观方面的缺陷,这与在预镀覆之后和将已预镀覆的金属件浸入Zn-Al镀液之前进行空气干燥期间金属氧化物的形成有关。
这种氧化物阻碍最终镀层的适当形成。尤其对于含有0.1-25%wt.%Al的镀液而言,这一外部氧化层是预镀覆金属与镀液中的Al相互作用或反应的物理障碍。
曾试图通过机械抛光来消除这种表面氧化层,所述机械抛光先采用砂纸进行,然后再借助浸渍氧化铝的砂布进行最终处理。所采用的另一种处理方法是通过在稀释的盐酸中酸洗,之后再水洗并干燥来进行表面活化。但是,没有一种所述方法能够始终获得令人满意的结果。
本发明的目的是避免上述缺点,通过表面转化处理,获得一种致密、连续且有光泽的镀层。
发明描述
根据本发明,在采用保护性金属薄层对金属件进行预镀覆之后,但是在锌-铝合金熔体浴液中浸渍之前,通过浸泡在含盐酸的稀释溶液中来对金属件进行表面活化处理。活化处理的目的是在预镀覆表面上形成一个盐层,以保护表面在浸入Zn-Al镀液之前不发生进一步氧化。通过将预镀覆的金属件浸泡在盐酸中,则预镀覆金属与盐酸发生反应,从而形成氯化物盐。之后,当将金属件从盐酸溶液中取出时,使所述酸溶剂蒸发,结果在表面上留下干燥的保护性盐层。当采用盐酸对预镀覆表面处理之后进行水洗时,由于金属件表面上的盐溶液被洗掉,因此效果较差。当随后对表面进行干燥时,表面上会形成氧化物。该氧化物会干扰随后在Zn-Al镀液中进行的镀覆步骤。
另外,如049申请中所述,金属预镀层或者基本与Zn-Al镀液中的Al完全反应(例如与Ni预镀层形成界面Ni-Al化合物)或者在镀液中溶解(例如Cu预镀层),由此使金属件表面与Zn-Al合金直接接触。因此,必须使通过活化步骤产生的氯化物盐层的熔点低于Zn-Al镀液的温度,以便当金属件浸泡在Zn-Al镀液时,该氯化物盐能在较短时间内熔化。当铜为预镀覆金属时,优选形成的氯化物盐是CuCl。化学物理手册(CRC出版社,第77版,1996-1997,第4-54页和4-55页)指出,CuCl的熔点为430℃,该温度足够低,当盐表面浸入温度高于430℃,例如450-600℃的Zn-Al镀液时能够发生熔化。而另一方面,CuCl2的熔点是630℃,该温度太高,不能始终获得良好结果。在上述两种情形下,氯化物均是与Cu预镀层反应。因此,优选对Cu和Cl反应进行控制,以使过多的Cl不会与CuCl反应产物进一步反应并形成大量的CuCl2。这一点通过控制盐酸溶液中的Cl浓度和/或通过限制反应时间,例如将在盐酸中的浸泡时间限制为几秒钟来实现。
一般地,氯化物盐或者氯化物盐的混合物的熔点依据Zn-Al组成应该在300-600℃之间。
活化溶液也可以含有一种酸性离子表面活性剂或者非离子型表面活性剂,以及一种或多种附加的IA,IIA,IB和IIB族元素的氯化物。
用于盐酸的稀释剂是水或者选自甲醇、乙醇、丙醇等,优选乙醇和丙三醇的醇类物质。
在待镀覆的金属件表面上的薄预镀覆层通过电解或化学沉积或者渗镀(cementation)形成。优选渗镀法,因其能够获得极薄的单原子涂层。
优选处理溶液中的盐酸浓度为5-20%(体积),优选10-15%(体积),同时,添加的氯化物浓度为10-100g/l,优选10-24g/l。
由于溶剂完全蒸发,所述溶液中含有的盐沉淀在预镀覆的表面上。在采用铜预镀覆时,能够获得一种氯化亚铜与上述盐的混合物,从而保护铜表面不被氧化,并且起熔剂作用,因为在其浸泡在锌-铝合金镀液期间会发生熔化,其中镀液的温度依据合金中的铝含量处于430-600℃之间。这样能够确保待镀覆表面干干净净,从而能够获得高质量镀层。
下面的实施例展示的是本发明的一些优选实施方案,它们不会对本发明的范围和目的构成任何限制。
实施例1
通过用铁离子渗镀,并且在含10g/l的CuSO4和98%H2SO4的水溶液中室温浸泡20秒来将铜镀覆在钢试样上。
为了改善铜镀层的均匀性,通过用砂纸抛光钢试样表面并且用浸渍氧化铝的砂布最终处理来降低钢试样的表面粗糙度并且将表面氧化物去除。脱脂处理之后,试样通过渗镀形成铜镀层,并进行水洗和空气干燥,然后,在450℃,含有5%(重量)的铝(Zn-Al 5%)的锌合金熔体浴液中分别浸泡30,60,120,240,480,960秒。
上述浸泡时间均未得到良好镀层。尽管由于铜在锌熔体中的溶解度极高,预计铜层的溶解极快,但是,甚至经过长时间浸泡,铜仍存在于试样表面。如上所述,这归因于在浸入熔体浴液之前,或在浸泡期间,在空气与镀液界面处的铜表面被氧化成了CuO2。
实施例2
对钢试样进行脱脂、冲洗、酸洗、漂洗处理,并且进行电镀铜(镀层厚约1微米),其中电镀液温度为40℃,电镀液含有402g/l的焦磷酸铜,98g/l的焦磷酸钾,并且添加有磷酸,以使PH值达8.5。采用铜作为阳极,电流密度为3-8A/dm2。对镀铜试样再次漂洗并随后进行空气干燥。在室温下,对所述试样在10%(重量)的盐酸中进行表面活化处理,时间为几秒钟。随后,用水漂洗并进行空气干燥。然后,在450℃下,将所述试样浸泡在Zn-Al 5%的熔体浴液中,时间为4分钟。所获结果不可重复,因为它们强烈依赖于干燥处理与浸入熔体浴液之间的时间。
EXAMPLE 3
采用与实施例2相同的镀液,将铜电镀在钢试样上。
对试样进行脱脂、冲洗、酸洗、漂洗、镀铜,并再次漂洗和空气干燥。然后,在室温下,对所述试样在10%(重量)的HCl溶液中进行表面活化处理,时间为几秒钟。随后,在50℃下进行空气干燥。
至于HCl的溶剂,可分别采用水、甲醇、乙醇、丙醇和丙三醇。也可以使用这些溶剂的混合物。
然后,在450℃下,将所述试样浸泡在Zn-Al5%的熔体浴液中,时间为4分钟。之后,以约15mm/s的速度将试样取出。
不论在表面活化中使用何种溶剂,所有试样均被完全镀覆,并具有平滑、光亮的表面。
在放大倍数为1000X的SEM下观察试样的金相剖面,在界面处未发现任何脆性相,镀层总厚度约为30μm。
采用90°弯曲测试镀层的结合性。证实该镀层结合性能优异,在压缩和延伸区均不存在裂纹。
实施例4
电镀试样已获得极佳结果,现在采用渗镀试样进行其他一些试验。采用实施例1的溶液制备出铜镀层。
对试样进行脱脂、冲洗、酸洗、漂洗、镀铜,并再次漂洗和空气干燥。然后进行表面活化处理,包括将所述试样浸渍在溶剂为丙三醇、浓度10%b/w的HCl溶液中,时间为几秒钟。随后,在50℃下进行空气干燥。
然后,在440℃下,将所述试样浸泡在Zn-Al 5%的熔体浴液中,时间为4分钟。之后,以约15mm/s的速度将试样取出。浴液温度也可以降低,因为对于非电解镀覆,只有更少量待溶解进入镀液中的铜存在试样表面上。
镀覆试样表面具有极佳的外观,且在界面处没有脆性相生成,镀层厚度约30微米。
实施例5
下面的实施例也使用渗镀作为铜镀覆技术。
所测试的表面转化处理很可靠,并且能够获得质量良好的镀层。
试样的制备包括:在50-60℃下,浓度为80g/l的碱性皂溶液中脱脂处理10分钟;在室温下,用软化水冲洗;在室温下,采用1∶1的HCl酸洗,时间为3分钟;以及,在室温下,用软化水冲洗。随后,在室温下,在10g/l的98%硫酸和10g/l的硫酸铜溶液中渗镀铜,时间约20秒。然后,在室温下,用软化水漂洗所获试样,之后,在50-60℃的空气中干燥处理。然后,通过在室温下,在1∶10的HCl溶液(溶剂为甲醇)浸泡几秒钟来进行表面转化处理,随后,喷吹50-60℃的空气进行干燥。然后,在440℃下,将所述试样浸泡在Zn-Al 5%的熔体浴液中,时间为3-4分钟。之后,以10-15mm/s的速度将试样从浴液中取出,并且在静止空气中冷却。结果能够始终获得良好涂层。
实施例6
测试了具有不同Al浓度的各种Zn-Al镀液。
也测试了低于0.0005%的Al浓度范围,尽管该浓度太低,不能获得Al浓度较高(例如:>0.1%,优选约5%,直至25%或者甚至更高)的Zn-Al镀层的耐腐蚀性。
另外,Al含量较高的Zn-Al镀层迄今遇到的问题在Al含量极低的镀层(即,传统的Zn镀层)中未出现。在下面的试验中,非电解Cu迅速达0.3μm,随后,热浸到450℃的Zn-Al中,浸渍时间为6分钟。
%(重量) | 活化 | 未活化 | |
Zn 99.999 | X | 镀层质量良好,完全覆盖工件 | |
Zn+0.0005 Al | X | 镀层质量良好,完全覆盖工件 | |
Zn+0.005 Al | X | 工件未被完全覆盖 | |
Zn+0.005 Al | X | 镀层质量良好,完全覆盖工件 | |
Zn+0.1 Al | X | 存在10%未覆盖区 | |
Zn+0.1 Al | X | 镀层质量良好,完全覆盖工件 | |
Zn+0.5 Al | X | 存在50%未覆盖区 | |
Zn+0.5 Al | X | 镀层质量良好,完全覆盖工件 | |
Zn+5 Al | X | 存在80%未覆盖区 | |
Zn+5 Al | X | 镀层质量良好,完全覆盖工件 |
虽然结合在Zn-Al 5%b/w的熔体浴液中进行的处理对本发明进行了介绍,但是,只要是不对所述方法进行实质修改,铝含量可以在很大范围,一般为1-60%b/w的范围内进行变化。
Claims (15)
1.一种在Zn-Al合金熔体浴液中采用Zn-Al合金对金属件进行不连续镀覆的方法,其包括:采用金属预镀覆层对金属件表面进行预镀覆,以获得均匀、连续的金属薄层,从而能够在浸入浴液之前充分保护金属件表面不发生氧化,并且,该预镀层还足够薄,结果预镀层能够与Zn-Al合金熔体浴液中的Al基本完全反应或者基本完全溶解进入熔体浴液中;对所述预镀覆的表面进行表面活化处理,包括:将所述预镀覆件浸泡在稀盐酸溶液中,结果在预镀覆件的表面上形成包含熔点低于Zn-Al合金熔体浴液的氯化物盐覆层的保护层,并且,将具有氯化盐保护覆层的预镀覆金属浸入Zn-Al合金熔体浴液中,并且控制温度和浸渍时间,以使氯化物盐熔化,并且预镀层与浴液中的Al基本完全反应形成界面化合物层或者基本完全溶解进入浴液中,由此引起Zn-Al合金浴液与金属件表面反应形成结合层并且产生连续镀层。
2.根据权利要求1的方法,其中,所述金属预镀层包含铜和镍的至少一种。
3.根据权利要求2的方法,其中,所述金属预镀层包含铜。
4.根据权利要求2的方法,其中,所述金属预镀层包含镍。
5.根据权利要求1的方法,其中,所述金属预镀层包含钴。
6.根据权利要求2的方法,其中,在表面活化处理之后,将所述金属件从处理溶液中取出并且不经漂洗直接进行干燥。
7.根据权利要求2的方法,其中,用于盐酸的稀释剂选自水和醇。
8.根据权利要求7的方法,其中,所述醇是选自甲醇、乙醇、丙醇和丙三醇中的至少一种。
9.根据权利要求2的方法,其中,所述预镀层采用一种选自电解沉积、非电解沉积和渗镀的方法获得。
10.根据权利要求2的方法,其中,在所述稀释溶液中的盐酸浓度为5-20体积%。
11.根据权利要求10的方法,其中,所述盐酸浓度为10-15体积%。
12.根据权利要求2的方法,其中,将氯化物添加至盐酸溶液中,并且,添加至盐酸溶液中的所述氯化物的浓度为10-100g/l。
13.根据权利要求12的方法,其中,添加至盐酸溶液中的所述氯化物的浓度为10-25g/l。
14.根据权利要求3的方法,其中,氯化物盐保护覆层含有足够的CuCl,以保持该覆层熔点低于Zn-Al合金熔体浴液的熔点。
15.根据权利要求14的方法,其中,氯化物盐保护覆层的熔点低于600℃。
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US09/615,515 US6284122B1 (en) | 1998-06-09 | 2000-07-12 | Production of a zinc-aluminum alloy coating by immersion into molten metal baths |
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US6372296B2 (en) * | 1999-05-21 | 2002-04-16 | University Of Cincinnati | High aluminum galvanized steel |
US20060228482A1 (en) * | 2005-04-07 | 2006-10-12 | International Lead Zinc Research Organization, Inc. | Zinc-aluminum alloy coating of metal objects |
ES2425172T3 (es) * | 2005-12-20 | 2013-10-11 | Teck Metals Ltd. | Fundente y procedimiento de galvanizado por inmersión en caliente |
CN102044427B (zh) * | 2009-10-09 | 2012-06-06 | 中芯国际集成电路制造(上海)有限公司 | 铜互连线的形成方法及电镀装置 |
CN101760717B (zh) * | 2009-12-28 | 2011-09-21 | 江苏麟龙新材料股份有限公司 | 一种对耐海洋气候工程零件涂层进行扩散处理的方法 |
JP5419226B2 (ja) * | 2010-07-29 | 2014-02-19 | 日東電工株式会社 | フリップチップ型半導体裏面用フィルム及びその用途 |
US8853072B2 (en) * | 2011-06-06 | 2014-10-07 | Micron Technology, Inc. | Methods of forming through-substrate interconnects |
JP6352631B2 (ja) * | 2013-12-25 | 2018-07-04 | イビデン株式会社 | 積層セラミックコンデンサの製造方法 |
CN106158727A (zh) * | 2015-03-30 | 2016-11-23 | 中芯国际集成电路制造(上海)有限公司 | 铜金属化工艺 |
CN105506591B (zh) * | 2015-11-11 | 2019-04-23 | 华南理工大学 | 一种基于还原性水基溶液浴预热的化学镀方法 |
JP7247946B2 (ja) * | 2020-04-24 | 2023-03-29 | Jfeスチール株式会社 | 溶融亜鉛めっき鋼板及びその製造方法 |
CN113732294A (zh) * | 2021-09-26 | 2021-12-03 | 中国科学院上海应用物理研究所 | 一种通过熔盐廉价大规模合成金属团簇的方法 |
CN114657544B (zh) * | 2022-03-24 | 2023-10-27 | 彭州航大新材料有限公司 | 一种镍基高温合金内腔表面的渗铝钴工艺及钴铝渗层 |
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JPS5534642A (en) * | 1978-09-01 | 1980-03-11 | Nisshin Steel Co Ltd | Manufacture of alloyed type zinc plated steel sheet according to dry flux method |
EP0763608A1 (en) * | 1995-03-28 | 1997-03-19 | Nippon Steel Corporation | Rust-preventive steel sheet for fuel tank and process for producing the sheet |
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