CN103144370B - 铝制品及其制备方法 - Google Patents

铝制品及其制备方法 Download PDF

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CN103144370B
CN103144370B CN201110403314.2A CN201110403314A CN103144370B CN 103144370 B CN103144370 B CN 103144370B CN 201110403314 A CN201110403314 A CN 201110403314A CN 103144370 B CN103144370 B CN 103144370B
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layer
alloy
aluminum
plating
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CN103144370A (zh
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曹达华
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RUGAO LANTU KNITTING CLOTHING Co.,Ltd.
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Shenzhen Futaihong Precision Industry Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/017Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C19/03Alloys based on nickel or cobalt based on nickel
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
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    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1646Characteristics of the product obtained
    • C23C18/165Multilayered product
    • C23C18/1651Two or more layers only obtained by electroless plating
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    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/1803Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837Multistep pretreatment
    • C23C18/1844Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48Coating with alloys
    • C23C18/50Coating with alloys with alloys based on iron, cobalt or nickel
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736Al-base component
    • Y10T428/1275Next to Group VIII or IB metal-base component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12944Ni-base component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495Thickness [relative or absolute]
    • Y10T428/24967Absolute thicknesses specified
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
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    • Y10T428/2651 mil or less

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Abstract

本发明提供一种铝制品,包括铝基体及形成于该铝基体上的复合镀层,该复合镀层包括一Ni-Cu-P合金层及一Ni-P合金层,该Ni-Cu-P合金层位于Ni-P合金层与基体之间,该Ni-Cu-P合金层具有纳米晶态结构,该Ni-P合金层具有非晶态结构,该Ni-Cu-P合金层与该Ni-P合金层通过化学镀方法形成。该铝制品同时具有优异的电磁屏蔽效能和耐腐蚀双重性能。本发明还提供一种上述铝制品的制备方法。

Description

铝制品及其制备方法
技术领域
本发明涉及一种铝制品及其处理方法,尤其涉及一种具有较好电磁屏蔽功能及防腐功能的铝制品及其制备方法。
背景技术
铝合金具有质量轻、散热性能好、导电性好等优点,因此广泛应用在电子、通讯产品的内外构件上。在空气中铝合金表面会形成氧化铝保护膜,在一般的大气环境下,铝合金表面的氧化铝膜能够有效地对铝合金基体进行保护,但在含有电解质的湿气中,例如海洋表面大气环境,铝合金表面容易出现点蚀,这样会降低产品的电磁屏蔽性能并影响产品的通信性能,同时导致产品使用寿命缩短。
发明内容
有鉴于此,本发明提供一种具有较好的电磁屏蔽功能及防腐功能的铝制品。
另外,本发明还提供一种上述铝制品的制备方法。
一种铝制品,包括铝基体及形成于该铝基体上的复合镀层,该复合镀层包括一Ni-Cu-P合金层及一Ni-P合金层,该Ni-Cu-P合金层位于Ni-P合金层与基体之间,该Ni-Cu-P合金层具有纳米晶态结构,该Ni-P合金层具有非晶态结构,该Ni-Cu-P合金层与该Ni-P合金层通过化学镀方法形成。
一种铝制品的制备方法,包括以下步骤:
在铝基材上化学镀一Ni-Cu-P合金层,化学镀该Ni-Cu-P合金层的镀液为含以下组分的水溶液:20-25g/LNiSO4·6H2O,2.0-2.5g/LCuSO4·5H2O,20-25g/LNaH2PO2·H2O,20-30g/L乳酸,20-25g/L柠檬酸钠,30-40g/L焦磷酸钠,0.1g/L十二烷基硫酸钠,该镀液的pH值范围为8.5-10.5,温度为83℃-87℃;
在Ni-Cu-P合金层上化学镀一Ni-P合金层,化学镀该Ni-P合金层的镀液为含以下组分的水溶液:20-25g/LNiSO4·6H2O,25-30g/LNaH2PO2·H2O,25-35g/L乳酸,15-20g/L柠檬酸钠,0.1g/L十二烷基硫酸钠,该镀液的pH值范围为4.5-5.5,温度为81℃-85℃。
上述铝制品10表面采用Ni-Cu-P合金层131与Ni-P合金层133形成的复合镀层13具有如下优越性:
1、利用Ni-Cu-P合金层131中的高含量Cu的特性,具有良好的导电性,同时,Ni具有良好的磁性,使得Ni-Cu-P合金层131既具有良好的导电性有具有良好的导磁性,因此具有良好的电磁屏蔽效能。
2、电磁屏蔽效能SE=A+R+B,其中
A为:在屏蔽体内部传输时,电磁能量被吸收引起的吸收损耗A,这种吸收要求膜层具有导电性及导磁性;
R为:电磁波通过屏蔽体表面时,由于阻抗突变引起的反射损耗;
B为:两个界面间多次反射而需要考虑的修正系数。
该复合镀层为Ni-Cu-P层/Ni-P层这种双层结构,因为Ni-Cu-P合金层中包括高含量的导电性优良的Cu及导磁性良好的Ni,因此能使电磁波产生较大吸收损耗A。另外,由于Ni-Cu-P合金层与Ni-P合金层是两种阻抗不一样的膜层,电磁波在Ni-Cu-P合金层与Ni-P合金层之间就会因为阻抗突变而引起反射损耗(R+B)。所以,该复合镀层的Ni-Cu-P层/Ni-P层的双层结构使得该复合镀层具有吸收电磁波A的同时,还具有阻抗突变引起的反射损耗(R+B),因此可以进一步提高电磁屏蔽的效果。
3、利用非晶结构的Ni-P合金层的优异的耐腐蚀性能及耐磨性能,使该铝制品具有优异的表面耐腐蚀性能及耐磨性能。
上述铝制品的制备方法中,化学镀该Ni-Cu-P合金层采用碱性化学镀液(pH值范围为8.5-10.5),在碱性镀液环境中有利于获得纳米晶的Ni-Cu-P合金层。一般来说,碱性化学镀液不稳定,容易分解,所以上述化学镀该Ni-Cu-P合金层采用多种络合剂,尤其是为了防止镀液分解,使用了强络合剂焦磷酸钠,可以保证在碱性化学镀的过程中镀液的稳定性。另外,化学镀该Ni-Cu-P合金层的镀液中CuSO4·5H2O的使用量达到2.0-2.5g/L,使镀层中铜含量达到60-75%,具有良好的导电性。
附图说明
图1是本发明一较佳实施例铝制品的剖视图。
图2是本发明另一较佳实施例铝制品的剖视图。
图3是本发明一较佳实施例铝制品的Ni-Cu-P合金层的X射线衍射图。
图4是本发明一较佳实施例铝制品的Ni-Cu-P合金层放大500倍的扫描电镜图。
图5是本发明一较佳实施例铝制品的Ni-Cu-P合金层放大5000倍的扫描电镜图。
图6是本发明一较佳实施例铝制品的Ni-P合金层的X射线衍射图。
图7是本发明一较佳实施例铝制品的Ni-P合金层放大500倍的扫描电镜图。
图8是本发明一较佳实施例铝制品的Ni-P合金层放大5000倍的扫描电镜图。
主要元件符号说明
铝制品 10
铝基体 11
化学镀镍层 12
复合镀层 13
Ni-Cu-P合金层 131
Ni-P合金层 133
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
请参阅图1,本发明较佳实施例的铝制品10包括铝铝基体11、形成于铝基体11上的复合镀层13。
铝基体11可以为铝或铝合金。
该复合镀层13包括一Ni-Cu-P合金层131及一Ni-P合金层133。该Ni-Cu-P合金层131位于Ni-P合金层133与铝基体11之间。该Ni-Cu-P合金层131具有纳米晶态结构。该Ni-Cu-P合金层131中铜的质量百分含量为60%-75%,Ni的质量百分含量为23%-37%,P的质量百分含量为1%-3%。Ni-Cu-P合金层131的厚度可为7.5μm-8.5μm。该Ni-P合金层133具有非晶态结构。Ni-P合金层133中Ni的质量百分含量为88%-93%,P的质量百分含量为7%-12%。Ni-P合金层133的厚度可以为9μm-11μm。
该Ni-Cu-P合金层131与该Ni-P合金层133通过化学镀膜方法形成。
请参阅图2,在其它实施例中,为了使该复合镀层13能够更好的附着于铝基体11上,该铝制品10还可以在复合镀层13与铝基体11之间形成一化学镀镍层12。
上述铝制品10表面采用Ni-Cu-P合金层131与Ni-P合金层133形成的复合镀层13具有如下优越性:
1、利用纳米Ni-Cu-P合金层131中的高含量Cu的特性,具有良好的导电性,同时,Ni具有良好的磁性,使得Ni-Cu-P合金层131既具有良好的导电性有具有良好的导磁性,因此具有良好的电磁屏蔽效能。
2、电磁屏蔽效能SE=A+R+B,其中
A为:在屏蔽体内部传输时,电磁能量被吸收引起的吸收损耗A,这种吸收要求膜层具有导电性及导磁性;
R为:电磁波通过屏蔽体表面时,由于阻抗突变引起的反射损耗;
B为:两个界面间多次反射而需要考虑的修正系数。
该复合镀层13为Ni-Cu-P层/Ni-P层这种双层结构,因为Ni-Cu-P合金层131中包括高含量的导电性优良的Cu及导磁性良好的Ni,因此能使电磁波产生较大吸收损耗A。另外,由于Ni-Cu-P合金层131与Ni-P合金层133是两种阻抗不一样的膜层,电磁波在Ni-Cu-P合金层131与Ni-P合金层133之间就会因为阻抗突变而引起反射损耗(R+B)。所以,该复合镀层13的Ni-Cu-P层/Ni-P层的双层结构使得该复合镀层13具有吸收电磁波A的同时,还具有阻抗突变引起的反射损耗(R+B),因此可以进一步提高电磁屏蔽的效果。
3、利用非晶结构的Ni-P合金层133的优异的耐腐蚀性能及耐磨性能,使该铝制品10具有优异的表面耐腐蚀性能及耐磨性能。
该铝制品10的制备方法,主要包括采用化学镀方法在铝基体11上依次沉积该Ni-Cu-P合金层131及Ni-P合金层133。
化学镀该Ni-Cu-P合金层131采用的镀液为含以下组分的水溶液:NiSO4·6H2O,20-25g/L;CuSO4·5H2O,2.0-2.5g/L;NaH2PO2·H2O,20-25g/L;乳酸,20-30g/L;柠檬酸钠,20-25g/L;焦磷酸钠(Na4P2O7),30-40g/L;十二烷基硫酸钠,0.1g/L。其中,该乳酸、柠檬酸钠、焦磷酸钠、十二烷基硫酸钠均用作络合剂。该镀液的pH值范围为8.5-10.5,优选为8.8-9.0可以,可采用氨水调节。该镀液的温度为83℃-87℃。上述条件下制备的Ni-Cu-P合金层131具有纳米晶结构。当该镀液的pH值小于8.5时,难以获得纳米晶结构的Ni-Cu-P合金层131。
化学镀该Ni-P合金层133采用的镀液为含以下组分的水溶液:NiSO4·6H2O,20-25g/L;NaH2PO2·H2O,25-30g/L;乳酸,25-35g/L;柠檬酸钠,15-20g/L;十二烷基硫酸钠,0.1g/L。该镀液的pH值范围为4.5-5.5,可采用NaOH溶液调节。该镀液的温度为81℃-85℃。
为了使该Ni-Cu-P合金层131及Ni-P合金层133能够更好的附着于铝基体11上,该铝制品的制备方法还可包括在化学镀该Ni-Cu-P合金层131之前对铝基体11进行预镀镍的步骤,以在铝基体11上形成一化学镀镍层12。该预镀镍采用的镀液为含以下组分的水溶液:NiSO4·6H2O,0.020-0.038mol/L;柠檬酸钠(C6H5Na3O7),0.20-0.38mol/L;酒石酸钾钠(NaKC4H4O6),0.02-0.038mol/L。该镀液的pH值范围为10-12,可采用NaOH溶液调节。该镀液的温度为室温。
优选情况下,该铝制品的制备方法还可包括化学镀前按如下方法及顺序对铝基体11进行前处理:
(a)除油清洗:可采用常规市售铝合金除油液。
(b)水洗:去离子水漂洗。
(c)第一次活化:将铝基体11于室温下的盐酸与水按体积比为1:4配制的溶液中浸置6s-30s。
(d)水洗:去离子水漂洗。
(e)酸性浸蚀:将将铝基体11于室温下的硝酸与水按体积比为1:1配制的溶液中浸置3s-5s。
(f)水洗:去离子水漂洗。
(g)第二次活化:将铝基体11于室温下的10%的硫酸溶液中浸置50s-60s。
(h)水洗:去离子水漂洗。
上述化学镀该Ni-Cu-P合金层131采用碱性化学镀液(pH值范围为8.5-10.5),在碱性镀液环境中有利于获得纳米晶的Ni-Cu-P合金层131。一般来说,碱性化学镀液不稳定,容易分解,所以上述化学镀该Ni-Cu-P合金层131采用多种络合剂,尤其是为了防止镀液分解,使用了强络合剂焦磷酸钠,可以保证在碱性化学镀的过程中镀液的稳定性。另外,化学镀该Ni-Cu-P合金层131的镀液中CuSO4·5H2O的使用量达到2.0-2.5g/L,使镀层中铜含量达到60-75%,得到的镀层是铜基的纳米Ni-Cu-P层。
请参阅图3,从上述Ni-Cu-P合金层131的X射线衍射图可以看出,Ni-Cu-P合金层131在Cu(111)、Cu(200)及Cu(220)面出现了三强峰,但衍射峰较晶态的衍射峰要宽(晶态的衍射峰几乎为一条直线)有一定宽化,为典型的纳米晶结构。请参阅图4及图5,从上述Ni-Cu-P合金层131的SEM表面形貌图也可以看出,在放大500X时,其表面形貌由许多颗粒组成,将其放大到5000X时,可以看出由许多大的胞状单元组成,但每个大的胞状单元又包含了许多纳米级的细小胞状单元,符合纳米晶的形貌特征。这种纳米晶态结构的镀层导电性及磁性都较好,因此,电磁屏蔽性能优越。
请参阅图6,从上述化学镀该Ni-P合金层133的X射线衍射图可以看出,Ni-P合金层133在Ni(111)面呈现一拓宽的馒头峰,这是非晶态的典型特征。请参阅图7及图8,从Ni-P合金层133的SEM表面形貌图也可以看出,其表面形貌由许多细小颗粒组成,将其放大到5000X时,可以看到它由清晰的单元式的胞状结构组成,而且非常致密,符合非晶结构的形貌特征。这种非晶态结构的镀层由于没有晶界,因此,耐腐蚀性能优越。
下面通过具体实施例对本发明进行进一步详细说明。
实施例1
1.按如下方法及顺序对铝合金材质的铝基体11进行前处理:
(a)除油清洗:将铝基体11于70℃-75℃下的含30g/LNa3PO4、25g/LNa2CO3及8g/LNa2SiO3的溶液中清洗2min。
(b)水洗:去离子水漂洗。
(c)第一次活化:将铝基体11于室温下的盐酸与水按体积比为1:4配制的溶液中浸置10s。
(d)水洗:去离子水漂洗。
(e)酸性浸蚀:将将铝基体11于室温下的硝酸与水按体积比为1:1配制的溶液中浸置3s。
(f)水洗:去离子水漂洗。
(g)第二次活化:将铝基体11于室温下的10%的硫酸溶液中浸置50s。
(h)水洗:去离子水漂洗。
2.预镀镍:在铝基体11镀上化学镀镍层12;化学镀镍层12的镀液配方为:NiSO4·6H2O,0.025mol/L;柠檬酸钠,0.25mol/L;酒石酸钾钠,0.03mol/L;镀液pH值为10,温度为室温。
3.化学镀Ni-Cu-P合金层131:化学镀Ni-Cu-P合金层131的镀液配方为:NiSO4·6H2O,21g/L;CuSO4·5H2O,2.2g/L;NaH2PO2·H2O,20g/L;乳酸,25g/L;柠檬酸钠,24g/L;焦磷酸钠(Na4P2O7),35g/L;十二烷基硫酸钠,0.1g/L;镀液的pH值为8.9-9.0,采用氨水调节,温度为83℃-87℃,沉积时间为50min。镀得Ni-Cu-P合金层131的厚度为8μm。
4.化学镀Ni-P合金层133:化学镀Ni-P合金层133的镀液配方为:NiSO4·6H2O,20g/L;NaH2PO2·H2O,25g/L;乳酸,30g/L;柠檬酸钠,15g/L;十二烷基硫酸钠,0.1g/L。该镀液的pH值范围为4.5-5.5,采用2mol/L的NaOH溶液调节。该镀液的温度为81℃-85℃,沉积时间为60min。镀得Ni-P合金层133的厚度为10μm。实施例1的样品记做S1。
实施例2
1.按如下方法及顺序对铝合金材质的铝基体11进行前处理:
(a)除油清洗:将铝基体11于70℃-75℃下的含30g/LNa3PO4、25g/LNa2CO3及8g/LNa2SiO3的溶液中清洗4min。
(b)水洗:去离子水漂洗。
(c)第一次活化:将铝基体11于室温下的盐酸与水按体积比为1:4配制的溶液中浸置10s。
(d)水洗:去离子水漂洗。
(e)酸性浸蚀:将将铝基体11于室温下的硝酸与水按体积比为1:1配制的溶液中浸置5s。
(f)水洗:去离子水漂洗。
(g)第二次活化:将铝基体11于室温下的10%的硫酸溶液中浸置60s。
(h)水洗:去离子水漂洗。
2.预镀镍:在铝基体11镀上化学镀镍层12;化学镀镍层12的镀液配方为:NiSO4·6H2O,0.03mol/L;柠檬酸钠,0.3mol/L;酒石酸钾钠,0.035mol/L;镀液pH值为11,温度为室温。
3.化学镀Ni-Cu-P合金层131:化学镀Ni-Cu-P合金层131的镀液配方为:NiSO4·6H2O,25g/L;CuSO4·5H2O,2.4g/L;NaH2PO2·H2O,23g/L;乳酸,30g/L;柠檬酸钠,20g/L;焦磷酸钠(Na4P2O7),40g/L;十二烷基硫酸钠,0.1g/L;镀液的pH值为8.9-9.0,采用氨水调节,温度为83℃-87℃,沉积时间为50min。镀得Ni-Cu-P合金层131的厚度为8.2μm。
4.化学镀Ni-P合金层133:化学镀Ni-P合金层133的镀液配方为:NiSO4·6H2O,20g/L;NaH2PO2·H2O,28g/L;乳酸,30g/L;柠檬酸钠,20g/L;十二烷基硫酸钠,0.1g/L。该镀液的pH值范围为4.5-5.5,采用2mol/L的NaOH溶液调节。该镀液的温度为81℃-85℃,沉积时间为60min。镀得Ni-P合金层133的厚度为9.5μm。实施例2的样品记做S2。
实施例3
1.按如下方法及顺序对铝合金材质的铝基体11进行前处理:
(a)除油清洗:将铝基体11于70℃-75℃下的含30g/LNa3PO4、25g/LNa2CO3及8g/LNa2SiO3的溶液中清洗5min。
(b)水洗:去离子水漂洗。
(c)第一次活化:将铝基体11于室温下的盐酸与水按体积比为1:4配制的溶液中浸置15s。
(d)水洗:去离子水漂洗。
(e)酸性浸蚀:将将铝基体11于室温下的硝酸与水按体积比为1:1配制的溶液中浸置4s。
(f)水洗:去离子水漂洗。
(g)第二次活化:将铝基体11于室温下的10%的硫酸溶液中浸置55s。
(h)水洗:去离子水漂洗。
2.预镀镍:在铝基体11镀上化学镀镍层12;化学镀镍层12的镀液配方为:NiSO4·6H2O,0.035mol/L;柠檬酸钠,0.35mol/L;酒石酸钾钠,0.033mol/L;镀液pH值为12,温度为室温。
3.化学镀Ni-Cu-P合金层131:化学镀Ni-Cu-P合金层131的镀液配方为:NiSO4·6H2O,23g/L;CuSO4·5H2O,2.3g/L;NaH2PO2·H2O,25g/L;乳酸,20g/L;柠檬酸钠,25g/L;焦磷酸钠(Na4P2O7),30g/L;十二烷基硫酸钠,0.1g/L;镀液的pH值为8.9-9.0,采用氨水调节,温度为83℃-87℃,沉积时间为50min。镀得Ni-Cu-P合金层131的厚度为7.8μm。
4.化学镀Ni-P合金层133:化学镀Ni-P合金层133的镀液配方为:NiSO4·6H2O,25g/L;NaH2PO2·H2O,30g/L;乳酸,35g/L;柠檬酸钠,20g/L;十二烷基硫酸钠,0.1g/L。该镀液的pH值范围为4.5-5.5,采用2mol/L的NaOH溶液调节。该镀液的温度为81℃-85℃,沉积时间为60min。镀得Ni-P合金层133的厚度为10.2μm。实施例3的样品记做S3。
电磁屏蔽效能测试
对样品S1-S3进行电磁屏蔽效能测试,该测试采用的网络频谱仪为Agilent公司生产,其型号为E5071C。测试表明,在100KHz~4.5GHz的频率范围,样品S1-S3的电磁屏蔽效能分别为100dB、105dB、110dB。在10Hz-10KHZ的频率范围,样品S1-S3的电磁屏蔽效能分别为60dB、63dB、65dB。而金属铝的电磁屏蔽效能在低频时很低,尤其是工频50HZ以下,电磁屏蔽效能几乎为零。
耐腐蚀性测试
对样品S1-S3进行耐腐蚀性测试。将样品S1-S3放入5%的Nacl溶液中浸泡12天,每过4天检查镀层表面的腐蚀性能。
浸泡4天,样品S1-S3表面无点蚀;
浸泡8天,样品S1-S3表面无点蚀;
浸泡12天,样品S1出现1个点蚀;样品S2无点蚀,样品S3无点蚀。
以上说明,样品S1-S3表面的膜层具有良好的耐腐蚀性能。
上述铝制品10表面由Ni-Cu-P合金层131及Ni-P合金层133组成的复合镀层13结合了非晶优越的耐腐蚀性能和纳米晶优异的导电性及磁性,同时,Ni-Cu-P合金层131中铜元素的加入,也提高了其导电性,从而同时具有优异的电磁屏蔽效能和耐腐蚀双重性能。

Claims (9)

1.一种铝制品,包括铝基体及形成于该铝基体上的复合镀层,其特征在于:该复合镀层包括一Ni-Cu-P合金层及一Ni-P合金层,该Ni-Cu-P合金层位于Ni-P合金层与基体之间,该Ni-Cu-P合金层具有纳米晶态结构,该Ni-P合金层具有非晶态结构,该Ni-Cu-P合金层与该Ni-P合金层通过化学镀方法形成,该Ni-Cu-P合金层中铜的质量百分含量为60%-75%,Ni的质量百分含量为23%-37%,P的质量百分含量为1%-3%,该Ni-P合金层中Ni的质量百分含量为88%-93%,P的质量百分含量为7%-12%。
2.如权利要求1所述的铝制品,其特征在于:该Ni-Cu-P合金层的厚度为7.5μm-8.5μm。
3.如权利要求1所述的铝制品,其特征在于:该Ni-P合金层的厚度为9μm-11μm。
4.如权利要求1所述的铝制品,其特征在于:该铝基体为铝或铝合金。
5.如权利要求1所述的铝制品,其特征在于:该铝制品还包括一位于该铝基体与该Ni-Cu-P合金层之间的化学镀镍层。
6.一种铝制品的制备方法,包括以下步骤:
在铝基材上化学镀一Ni-Cu-P合金层,化学镀该Ni-Cu-P合金层的镀液为含以下组分的水溶液:20-25g/LNiSO4·6H2O,2.0-2.5g/LCuSO4·5H2O,20-25g/LNaH2PO2·H2O,20-30g/L乳酸,20-25g/L柠檬酸钠,30-40g/L焦磷酸钠,0.1g/L十二烷基硫酸钠,该镀液的pH值范围为8.5-10.5,温度为83℃-87℃;
在Ni-Cu-P合金层上化学镀一Ni-P合金层,化学镀该Ni-P合金层的镀液为含以下组分的水溶液:20-25g/LNiSO4·6H2O,25-30g/LNaH2PO2·H2O,25-35g/L乳酸,15-20g/L柠檬酸钠,0.1g/L十二烷基硫酸钠,该镀液的pH值范围为4.5-5.5,温度为81℃-85℃。
7.如权利要求6所述的铝制品的制备方法,其特征在于:化学镀该Ni-Cu-P合金层的镀液的pH值范围为8.8-9.0。
8.如权利要求6所述的铝制品的制备方法,其特征在于:铝制品的制备方法还包括在化学镀该Ni-Cu-P合金层之前对铝基体进行预镀镍的步骤,以在铝基体上形成一化学镀镍层。
9.如权利要求8所述的铝制品的制备方法,其特征在于:该预镀镍采用的镀液为含以下组分的水溶液:0.020-0.038mol/LNiSO4·6H2O,0.20-0.38mol/L柠檬酸钠,0.02-0.038mol/L酒石酸钾钠,该镀液的pH值范围为10-12,温度为室温。
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