TWI564432B - 鋁製品及其製備方法 - Google Patents

鋁製品及其製備方法 Download PDF

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TWI564432B
TWI564432B TW100146072A TW100146072A TWI564432B TW I564432 B TWI564432 B TW I564432B TW 100146072 A TW100146072 A TW 100146072A TW 100146072 A TW100146072 A TW 100146072A TW I564432 B TWI564432 B TW I564432B
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alloy layer
aluminum
plating
layer
electroless
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曹達華
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富智康(香港)有限公司
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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
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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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    • 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
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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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
    • 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
    • C23C18/18Pretreatment 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
    • 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
    • C23C18/36Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23C18/48Coating 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
    • 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.]
    • Y10T428/12771Transition 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • 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
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less

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Description

鋁製品及其製備方法
本發明涉及一種鋁製品及其處理方法,尤其涉及一種具有較好電磁屏蔽功能及防腐功能的鋁製品及其製備方法。
鋁合金具有品質輕、散熱性能好、導電性好等優點,因此廣泛應用在電子、通訊產品的內外構件上。在空氣中鋁合金表面會形成氧化鋁保護膜,在一般的大氣環境下,鋁合金表面的氧化鋁膜能夠有效地對鋁合金基體進行保護,但在含有電解質的濕氣中,例如海洋表面大氣環境,鋁合金表面容易出現點蝕,這樣會降低產品的電磁屏蔽性能並影響產品的通信性能,同時導致產品使用壽命縮短。
有鑒於此,本發明提供一種具有較好的電磁屏蔽功能及防腐功能的鋁製品。
另外,本發明還提供一種上述鋁製品的製備方法。
一種鋁製品,包括鋁基體及形成於該鋁基體上的複合鍍層,該複合鍍層包括一Ni-Cu-P合金層及一Ni-P合金層,該Ni-Cu-P合金層位於Ni-P合金層與基體之間,該Ni-Cu-P合金層具有納米晶態結構,該Ni-P合金層具有非晶態結構,該Ni-Cu-P合金層與該Ni-P合金層藉由化學鍍方法形成。
一種鋁製品的製備方法,包括以下步驟:在鋁基材上化學鍍一Ni-Cu-P合金層,化學鍍該Ni-Cu-P合金層的鍍液為含以下組分的水溶液:20-25g/L NiSO4.6H2O,2.0-2.5g/L CuSO4.5H2O,20-25g/L NaH2PO2.H2O,20-30g/L乳酸,20-25g/L檸檬酸鈉,30-40g/L焦磷酸鈉,0.1g/L十二烷基硫酸鈉,該鍍液的pH值範圍為8.5-10.5,溫度為83℃-87℃;在Ni-Cu-P合金層上化學鍍一Ni-P合金層,化學鍍該Ni-P合金層的鍍液為含以下組分的水溶液:20-25g/L NiSO4.6H2O,25-30g/L NaH2PO2.H2O,25-35g/L乳酸,15-20g/L檸檬酸鈉,0.1g/L十二烷基硫酸鈉,該鍍液的pH值範圍為4.5-5.5,溫度為81℃-85℃。
上述鋁製品10表面採用Ni-Cu-P合金層131與Ni-P合金層133形成的複合鍍層13具有如下優越性:
1、利用Ni-Cu-P合金層131中的高含量Cu的特性,具有良好的導電性,同時,Ni具有良好的磁性,使得Ni-Cu-P合金層131既具有良好的導電性有具有良好的導磁性,因此具有良好的電磁屏蔽效能。
2、電磁屏蔽效能SE=A+R+B,其中A為:在屏蔽體內部傳輸時,電磁能量被吸收引起的吸收損耗A,這種吸收要求膜層具有導電性及導磁性;R為:電磁波通過屏蔽體表面時,由於阻抗突變引起的反射損耗; B為:兩個介面間多次反射而需要考慮的修正係數。
該複合鍍層為Ni-Cu-P層/Ni-P層這種雙層結構,因為Ni-Cu-P合金層中包括高含量的導電性優良的Cu及導磁性良好的Ni,因此能使電磁波產生較大吸收損耗A。另外,由於Ni-Cu-P合金層與Ni-P合金層係兩種阻抗不一樣的膜層,電磁波在Ni-Cu-P合金層與Ni-P合金層之間就會因為阻抗突變而引起反射損耗(R+B)。故,該複合鍍層的Ni-Cu-P層/Ni-P層的雙層結構使得該複合鍍層具有吸收電磁波A的同時,還具有阻抗突變引起的反射損耗(R+B),因此可以進一步提高電磁屏蔽的效果。
3、利用非晶結構的Ni-P合金層的優異的耐腐蝕性能及耐磨性能,使該鋁製品具有優異的表面耐腐蝕性能及耐磨性能。
上述鋁製品的製備方法中,化學鍍該Ni-Cu-P合金層採用鹼性化學鍍液(pH值範圍為8.5-10.5),在鹼性鍍液環境中有利於獲得納米晶的Ni-Cu-P合金層。一般來說,鹼性化學鍍液不穩定,容易分解,故上述化學鍍該Ni-Cu-P合金層採用多種絡合劑,尤其係為了防止鍍液分解,使用了強絡合劑焦磷酸鈉,可以保證在鹼性化學鍍的過程中鍍液的穩定性。另外,化學鍍該Ni-Cu-P合金層的鍍液中CuSO4.5H2O的使用量達到2.0-2.5g/L,使鍍層中銅含量達到60-75%,具有良好的導電性。
10‧‧‧鋁製品
11‧‧‧鋁基體
12‧‧‧化學鍍鎳層
13‧‧‧複合鍍層
131‧‧‧Ni-Cu-P合金層
133‧‧‧Ni-P合金層
圖1係本發明一較佳實施例鋁製品的剖視圖。
圖2係本發明另一較佳實施例鋁製品的剖視圖。
圖3係本發明一較佳實施例鋁製品的Ni-Cu-P合金層的X射線衍射 圖。
圖4係本發明一較佳實施例鋁製品的Ni-Cu-P合金層放大500倍的掃描電鏡圖。
圖5係本發明一較佳實施例鋁製品的Ni-Cu-P合金層放大5000倍的掃描電鏡圖。
圖6係本發明一較佳實施例鋁製品的Ni-P合金層的X射線衍射圖。
圖7係本發明一較佳實施例鋁製品的Ni-P合金層放大500倍的掃描電鏡圖。
圖8係本發明一較佳實施例鋁製品的Ni-P合金層放大5000倍的掃描電鏡圖。
請參閱圖1,本發明較佳實施例的鋁製品10包括鋁鋁基體11、形成於鋁基體11上的複合鍍層13。
鋁基體11可以為鋁或鋁合金。
該複合鍍層13包括一Ni-Cu-P合金層131及一Ni-P合金層133。該Ni-Cu-P合金層131位於Ni-P合金層133與鋁基體11之間。該Ni-Cu-P合金層131具有納米晶態結構。該Ni-Cu-P合金層131中銅的質量百分含量為60%-75%,Ni的質量百分含量為23%-37%,P的質量百分含量為1%-3%。Ni-Cu-P合金層131的厚度可為7.5μm-8.5μm。該Ni-P合金層133具有非晶態結構。Ni-P合金層133中Ni的質量百分含量為88%-93%,P的質量百分含量為7%-12%。Ni-P合金層133的厚度可以為9μm-11μm。
該Ni-Cu-P合金層131與該Ni-P合金層133藉由化學鍍膜方法形成。
請參閱圖2,在其他實施例中,為了使該複合鍍層13能夠更好的附著於鋁基體11上,該鋁製品10還可以在複合鍍層13與鋁基體11之間形成一化學鍍鎳層12。
上述鋁製品10表面採用Ni-Cu-P合金層131與Ni-P合金層133形成的複合鍍層13具有如下優越性:
1、利用納米Ni-Cu-P合金層131中的高含量Cu的特性,具有良好的導電性,同時,Ni具有良好的磁性,使得Ni-Cu-P合金層131既具有良好的導電性有具有良好的導磁性,因此具有良好的電磁屏蔽效能。
2、電磁屏蔽效能SE=A+R+B,其中A為:在屏蔽體內部傳輸時,電磁能量被吸收引起的吸收損耗A,這種吸收要求膜層具有導電性及導磁性;R為:電磁波通過屏蔽體表面時,由於阻抗突變引起的反射損耗;B為:兩個介面間多次反射而需要考慮的修正係數。
該複合鍍層13為Ni-Cu-P層/Ni-P層這種雙層結構,因為Ni-Cu-P合金層131中包括高含量的導電性優良的Cu及導磁性良好的Ni,因此能使電磁波產生較大吸收損耗A。另外,由於Ni-Cu-P合金層131與Ni-P合金層133係兩種阻抗不一樣的膜層,電磁波在Ni-Cu-P合金層131與Ni-P合金層133之間就會因為阻抗突變而引 起反射損耗(R+B)。故,該複合鍍層13的Ni-Cu-P層/Ni-P層的雙層結構使得該複合鍍層13具有吸收電磁波A的同時,還具有阻抗突變引起的反射損耗(R+B),因此可以進一步提高電磁屏蔽的效果。
3、利用非晶結構的Ni-P合金層133的優異的耐腐蝕性能及耐磨性能,使該鋁製品10具有優異的表面耐腐蝕性能及耐磨性能。
該鋁製品10的製備方法,主要包括採用化學鍍方法在鋁基體11上依次沉積該Ni-Cu-P合金層131及Ni-P合金層133。
化學鍍該Ni-Cu-P合金層131採用的鍍液為含以下組分的水溶液:NiSO4.6H2O,20-25g/L;CuSO4.5H2O,2.0-2.5g/L;NaH2PO2.H2O,20-25g/L;乳酸,20-30g/L;檸檬酸鈉,20-25g/L;焦磷酸鈉(Na4P2O7),30-40g/L;十二烷基硫酸鈉,0.1g/L。其中,該乳酸、檸檬酸鈉、焦磷酸鈉、十二烷基硫酸鈉均用作絡合劑。該鍍液的pH值範圍為8.5-10.5,優選為8.8-9.0可以,可採用氨水調節。該鍍液的溫度為83℃-87℃。上述條件下製備的Ni-Cu-P合金層131具有納米晶結構。當該鍍液的pH值小於8.5時,難以獲得納米晶結構的Ni-Cu-P合金層131。
化學鍍該Ni-P合金層133採用的鍍液為含以下組分的水溶液:NiSO4.6H2O,20-25g/L;NaH2PO2.H2O,25-30g/L;乳酸,25-35g/L;檸檬酸鈉,15-20g/L;十二烷基硫酸鈉,0.1g/L。該鍍液的pH值範圍為4.5-5.5,可採用NaOH溶液調節。該鍍液的溫度為81℃-85℃。
為了使該Ni-Cu-P合金層131及Ni-P合金層133能夠更好的附著於 鋁基體11上,該鋁製品的製備方法還可包括在化學鍍該Ni-Cu-P合金層131之前對鋁基體11進行預鍍鎳的步驟,以在鋁基體11上形成一化學鍍鎳層12。該預鍍鎳採用的鍍液為含以下組分的水溶液:NiSO4.6H2O,0.020-0.038mol/L;檸檬酸鈉(C6H5Na3O7),0.20-0.38mol/L;酒石酸鉀鈉(NaKC4H4O6),0.02-0.038mol/L。該鍍液的pH值範圍為10-12,可採用NaOH溶液調節。該鍍液的溫度為室溫。
優選情況下,該鋁製品的製備方法還可包括化學鍍前按如下方法及順序對鋁基體11進行前處理:
(a)除油清洗:可採用常規市售鋁合金除油液。
(b)水洗:去離子水漂洗。
(c)第一次活化:將鋁基體11於室溫下的鹽酸與水按體積比為1:4配製的溶液中浸置6s-30s。
(d)水洗:去離子水漂洗。
(e)酸性浸蝕:將將鋁基體11於室溫下的硝酸與水按體積比為1:1配製的溶液中浸置3s-5s。
(f)水洗:去離子水漂洗。
(g)第二次活化:將鋁基體11於室溫下的10%的硫酸溶液中浸置50s-60s。
(h)水洗:去離子水漂洗。
上述化學鍍該Ni-Cu-P合金層131採用鹼性化學鍍液(pH值範圍為8.5-10.5),在鹼性鍍液環境中有利於獲得納米晶的Ni-Cu-P合 金層131。一般來說,鹼性化學鍍液不穩定,容易分解,故上述化學鍍該Ni-Cu-P合金層131採用多種絡合劑,尤其係為了防止鍍液分解,使用了強絡合劑焦磷酸鈉,可以保證在鹼性化學鍍的過程中鍍液的穩定性。另外,化學鍍該Ni-Cu-P合金層131的鍍液中CuSO4.5H2O的使用量達到2.0-2.5g/L,使鍍層中銅含量達到60-75%,得到的鍍層係銅基的納米Ni-Cu-P層。
請參閱圖3,從上述Ni-Cu-P合金層131的X射線衍射圖可以看出,Ni-Cu-P合金層131在Cu(111)、Cu(200)及Cu(220)面出現了三強峰,但衍射峰較晶態的衍射峰要寬(晶態的衍射峰幾乎為一條直線)有一定寬化,為典型的納米晶結構。請參閱圖4及圖5,從上述Ni-Cu-P合金層131的SEM表面形貌圖也可看出,在放大500X時,其表面形貌由許多顆粒組成,將其放大到5000X時,可以看出由許多大的胞狀單元組成,但每個大的胞狀單元又包含了許多納米級的細小胞狀單元,符合納米晶的形貌特徵。這種納米晶態結構的鍍層導電性及磁性都較好,因此,電磁屏蔽性能優越。
請參閱圖6,從上述化學鍍該Ni-P合金層133的X射線衍射圖可以看出,Ni-P合金層133在Ni(11i)面呈現一拓寬的饅頭峰,係非晶態的典型特徵。請參閱圖7及圖8,從Ni-P合金層133的SEM表面形貌圖也可看出,其表面形貌由許多細小顆粒組成,將其放大到5000X時,可看到其由清晰的單元式的胞狀結構組成,而且非常緻密,符合非晶結構的形貌特徵。該種非晶態結構的鍍層由於沒有晶界,故,耐腐蝕性能優越。
下面藉由具體實施例對本發明進行進一步詳細說明。
實施例1
1.按如下方法及順序對鋁合金材質的鋁基體11進行前處理:
(a)除油清洗:將鋁基體11於70℃-75℃下的含30g/L Na3PO4、25g/L Na2CO3及8g/LNa2SiO3的溶液中清洗2min。
(b)水洗:去離子水漂洗。
(c)第一次活化:將鋁基體11於室溫下的鹽酸與水按體積比為1:4配製的溶液中浸置10s。
(d)水洗:去離子水漂洗。
(e)酸性浸蝕:將將鋁基體11於室溫下的硝酸與水按體積比為1:1配製的溶液中浸置3s。
(f)水洗:去離子水漂洗。
(g)第二次活化:將鋁基體11於室溫下的10%的硫酸溶液中浸置50s。
(h)水洗:去離子水漂洗。
2.預鍍鎳:在鋁基體11鍍上化學鍍鎳層12;化學鍍鎳層12的鍍液配方為:NiSO4.6H2O,0.025mol/L;檸檬酸鈉,0.25mol/L;酒石酸鉀鈉,0.03mol/L;鍍液pH值為10,溫度為室溫。
3.化學鍍Ni-Cu-P合金層131:化學鍍Ni-Cu-P合金層131的鍍液配方為:NiSO4.6H2O,21g/L,CuSO4.5H2O,2.2g/L;NaH2PO2.H2O,20g/L;乳酸,25g/L;檸檬酸鈉,24g/L;焦磷酸鈉(Na4P2O7),35g/L;十二烷基硫酸鈉,0.1g/L;鍍液的pH值為8.9-9.0, 採用氨水調節,溫度為83℃-87℃,沉積時間為50min。鍍得Ni-Cu-P合金層131的厚度為8μm。
4.化學鍍Ni-P合金層133:化學鍍Ni-P合金層133的鍍液配方為:NiSO4.6H2O,20g/L;NaH2PO2.H2O,25g/L;乳酸,30g/L;檸檬酸鈉,15g/L;十二烷基硫酸鈉,0.1g/L。該鍍液的pH值範圍為4.5-5.5,採用2mol/L的NaOH溶液調節。該鍍液的溫度為81℃-85℃,沉積時間為60min。鍍得Ni-P合金層133的厚度為10μm。實施例1的樣品記做S1。
實施例2
1.按如下方法及順序對鋁合金材質的鋁基體11進行前處理:
(a)除油清洗:將鋁基體11於70℃-75℃下的含30g/L Na3PO4、25g/L Na2CO3及8g/LNa2SiO3的溶液中清洗4min。
(b)水洗:去離子水漂洗。
(c)第一次活化:將鋁基體11於室溫下的鹽酸與水按體積比為1:4配製的溶液中浸置10s。
(d)水洗:去離子水漂洗。
(e)酸性浸蝕:將將鋁基體11於室溫下的硝酸與水按體積比為1:1配製的溶液中浸置5s。
(f)水洗:去離子水漂洗。
(g)第二次活化:將鋁基體11於室溫下的10%的硫酸溶液中浸置60s。
(h)水洗:去離子水漂洗。
2.預鍍鎳:在鋁基體11鍍上化學鍍鎳層12;化學鍍鎳層12的鍍液配方為:NuSO4.6H2O,0.03mol/L;檸檬酸鈉,0.3mol/L;酒石酸鉀鈉,0.035mol/L;鍍液pH值為11,溫度為室溫。
3.化學鍍Ni-Cu-P合金層131:化學鍍Ni-Cu-P合金層131的鍍液配方為:NiSO4.6H2O,25g/L;CuSO4.5H2O,2.4g/L;NaH2PO2.H2O,23g/L;乳酸,30g/L;檸檬酸鈉,20g/L;焦磷酸鈉(Na4P2O7),40g/L;十二烷基硫酸鈉,0.1g/L;鍍液的pH值為8.9-9.0,採用氨水調節,溫度為83℃-87℃,沉積時間為50min。鍍得Ni-Cu-P合金層131的厚度為8.2μm。
4.化學鍍Ni-P合金層133:化學鍍Ni-P合金層133的鍍液配方為:NiSO4.6H2O,20g/L;NaH2PO2.H2O,28g/L;乳酸,30g/L;檸檬酸鈉,20g/L;十二烷基硫酸鈉,0.1g/L。該鍍液的pH值範圍為4.5-5.5,採用2mol/L的NaOH溶液調節。該鍍液的溫度為81℃-85℃,沉積時間為60min。鍍得Ni-P合金層133的厚度為9.5μm。實施例2的樣品記做S2。
實施例3
1.按如下方法及順序對鋁合金材質的鋁基體11進行前處理:
(a)除油清洗:將鋁基體11於70℃-75℃下的含30g/L Na3PO4、25g/L Na2CO3及8g/LNa2SiO3的溶液中清洗5min。
(b)水洗:去離子水漂洗。
(c)第一次活化:將鋁基體11於室溫下的鹽酸與水按體積比為1 :4配製的溶液中浸置15s。
(d)水洗:去離子水漂洗。
(e)酸性浸蝕:將將鋁基體11於室溫下的硝酸與水按體積比為1:1配製的溶液中浸置4s。
(f)水洗:去離子水漂洗。
(g)第二次活化:將鋁基體11於室溫下的10%的硫酸溶液中浸置55s。
(h)水洗:去離子水漂洗。
2.預鍍鎳:在鋁基體11鍍上化學鍍鎳層12;化學鍍鎳層12的鍍液配方為:NiSO4.6H2O,0.035mol/L;檸檬酸鈉,0.35mol/L;酒石酸鉀鈉,0.033mol/L;鍍液pH值為12,溫度為室溫。
3.化學鍍Ni-Cu-P合金層131:化學鍍Ni-Cu-P合金層131的鍍液配方為:NiSO4.6H2O,23g/L;CuSO45H2O,2.3g/L;NaH2PO2.H2O,25g/L;乳酸,20g/L;檸檬酸鈉,25g/L;焦磷酸鈉(Na4P2O7),30g/L;十二烷基硫酸鈉,0.1g/L;鍍液的pH值為8.9-9.0,採用氨水調節,溫度為83℃-87℃,沉積時間為50min。鍍得Ni-Cu-P合金層131的厚度為7.8μm。
4.化學鍍Ni-P合金層133:化學鍍Ni-P合金層133的鍍液配方為:NiSO4.6H2O,25g/L;NaH2PO2.H2O,30g/L;乳酸,35g/L;檸檬酸鈉,20g/L;十二烷基硫酸鈉,0.1g/L。該鍍液的pH值範圍為4.5-5.5,採用2mol/L的NaOH溶液調節。該鍍液的溫度為81℃-85℃,沉積時間為60min。鍍得Ni-P合金層133的厚度為10.2μm 。實施例3的樣品記做S3。
電磁屏蔽效能測試
對樣品S1-S3進行電磁屏蔽效能測試,該測試採用的網路頻譜儀為Agilent公司生產,其型號為E5071C。測試表明,在100KHz~4.5GHz的頻率範圍,樣品S1-S3的電磁屏蔽效能分別為100dB、105dB、110dB。在10Hz-10KHZ的頻率範圍,樣品S1-S3的電磁屏蔽效能分別為60dB、63dB、65dB。而金屬鋁的電磁屏蔽效能在低頻時很低,尤其係工頻50HZ以下,電磁屏蔽效能幾乎為零。
耐腐蝕性測試
對樣品S1-S3進行耐腐蝕性測試。將樣品S1-S3放入5%的Nacl溶液中浸泡12天,每過4天檢查鍍層表面的腐蝕性能。
浸泡4天,樣品S1-S3表面無點蝕;浸泡8天,樣品S1-S3表面無點蝕;浸泡12天,樣品S1出現1個點蝕;樣品S2無點蝕,樣品S3無點蝕。
以上說明,樣品S1-S3表面的膜層具有良好的耐腐蝕性能。
上述鋁製品10表面由Ni-Cu-P合金層131及Ni-P合金層133組成的複合鍍層13結合了非晶優越的耐腐蝕性能和納米晶優異的導電性及磁性,同時,Ni-Cu-P合金層131中銅元素的加入,也提高了其導電性,從而同時具有優異的電磁屏蔽效能和耐腐蝕雙重性能。
10‧‧‧鋁製品
11‧‧‧鋁基體
13‧‧‧複合鍍層
131‧‧‧Ni-Cu-P合金層
133‧‧‧Ni-P合金層

Claims (10)

  1. 一種鋁製品,包括鋁基體及形成於該鋁基體上的複合鍍層,其改良在於:該複合鍍層包括一Ni-Cu-P合金層及一Ni-P合金層,該Ni-Cu-P合金層位於Ni-P合金層與基體之間,該Ni-Cu-P合金層具有納米晶態結構,所述Ni-Cu-P合金層中銅的質量百分含量為60%-75%,Ni的質量百分含量為23%-37%,P的質量百分含量為1%-3%,該Ni-P合金層具有非晶態結構,該Ni-Cu-P合金層與該Ni-P合金層藉由化學鍍方法形成。
  2. 如申請專利範圍第1項所述之鋁製品,其中所述Ni-Cu-P合金層的厚度為7.5μm-8.5μm。
  3. 如申請專利範圍第1項所述之鋁製品,其中所述Ni-P合金層中Ni的質量百分含量為88%-93%,P的質量百分含量為7%-12%。
  4. 如申請專利範圍第1項所述之鋁製品,其中所述Ni-P合金層的厚度為9μm-11μm。
  5. 如申請專利範圍第1項所述之鋁製品,其中所述鋁基體為鋁或鋁合金。
  6. 如申請專利範圍第1項所述之鋁製品,其中所述鋁製品還包括一位於該鋁基體與該Ni-Cu-P合金層之間的化學鍍鎳層。
  7. 一種鋁製品的製備方法,包括以下步驟:在鋁基材上化學鍍一Ni-Cu-P合金層,所述Ni-Cu-P合金層中銅的質量百分含量為60%-75%,Ni的質量百分含量為23%-37%,P的質量百分含量為1%-3%,化學鍍該Ni-Cu-P合金層的鍍液為含以下組分的水溶液:20-25g/L NiSO4.6H2O,2.0-2.5g/L CuSO4.5H2O,20-25g/L NaH2PO2.H2O,20-30g/L乳酸,20-25g/L檸檬酸鈉,30-40g/L焦磷酸鈉,0.1g/L十二烷基硫酸鈉,該鍍液的pH值範圍為8.5-10.5,溫度為 83℃-87℃;在Ni-Cu-P合金層上化學鍍一Ni-P合金層,化學鍍該Ni-P合金層的鍍液為含以下組分的水溶液:20-25g/LNiSO4.6H2O,25-30g/L NaH2PO2.H2O,25-35g/L乳酸,15-20g/L檸檬酸鈉,0.1g/L十二烷基硫酸鈉,該鍍液的pH值範圍為4.5-5.5,溫度為81℃-85℃。
  8. 如申請專利範圍第7項所述之鋁製品的製備方法,其中化學鍍該Ni-Cu-P合金層的鍍液的pH值範圍為8.8-9.0。
  9. 如申請專利範圍第7項所述之鋁製品的製備方法,其中該鋁製品的製備方法還包括在化學鍍該Ni-Cu-P合金層之前對鋁基體進行預鍍鎳的步驟,以在鋁基體上形成一化學鍍鎳層。
  10. 如申請專利範圍第9項所述之鋁製品的製備方法,其中所述預鍍鎳採用的鍍液為含以下組分的水溶液:0.020-0.038mOl/LNiSO4.6H2O,0.20-0.38mol/L檸檬酸鈉,0.02-0.038mol/L酒石酸鉀鈉,該鍍液的pH值範圍為10-12,溫度為室溫。
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