CN1168844C - 带状复合材料及其制备方法 - Google Patents

带状复合材料及其制备方法 Download PDF

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CN1168844C
CN1168844C CNB971143609A CN97114360A CN1168844C CN 1168844 C CN1168844 C CN 1168844C CN B971143609 A CNB971143609 A CN B971143609A CN 97114360 A CN97114360 A CN 97114360A CN 1168844 C CN1168844 C CN 1168844C
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oil
matrix material
zinc
tin
metal
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CN1195034A (zh
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I・布雷斯赫
I·布雷斯赫
露姆
H·斯吐尔姆
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Wieland Werke AG
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • C25D5/50After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/08Tin or alloys based thereon
    • 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
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/939Molten or fused coating
    • 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.]
    • Y10T428/12708Sn-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.]
    • Y10T428/12708Sn-base component
    • Y10T428/12715Next to Group IB metal-base component

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating With Molten Metal (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Gasket Seals (AREA)
  • Chemically Coating (AREA)
  • Lubricants (AREA)

Abstract

本发明涉及一种带状复合材料,其中其基体材料为金属或金属合金,表面为镀锡层,两层间形成一金属间位相(1MP)。为使复合材料达到良好的抗磨损和抗腐蚀性,同时防止表面氧化,在锡层外边缘部分渗有厚度D低于2微米的1-50%(原子量计)的碳(C)。本文还描述据本发明的复合材料的制备方法(浸油处理)与装置。

Description

带状复合材料及其制备方法
技术领域
本发明涉及一种带状复合材料及其制备方法。
背景技术
为准确控制金属间的相(1MP)的厚度,将经过热法镀锡处理的带状复合材料送入温度为150-180℃的罩式炉,传送带式炉或悬式带状炉中进行热处理。如果用罩式炉时,其处理时间为16个小时以上。对于电镀锡的复合材料还需通过红外辐射线或热空气流处理,以便通过锡的再熔融,使锡能更好地焊接或粘贴在基体材料上,但是,上述两种情况,其表面都易氧化或者无法防止继续氧化。这样,在受到机械负荷的情况下,就不能确保持续的较小的接触阻力。
发明内容
本发明的任务是,制备出具有抗氧化表面的带状复合材料,该材料具有良好的抗腐蚀性和耐磨性。
上述任务的技术方案在于带状的复合材料,其中其基体材料为金属或金属合金,其表层是经电镀或熔镀法而成的镀锡表层或锡合金表层,在所述基体材料和表层材料之间形成一金属中间相,其特征是,在锡层的外边缘部分渗入厚度D低于2微米的1-50%按原子量计的碳(C)。
在锡层中渗碳会改善摩擦性能。即当用该材料作为插塞连接体时,可以减少其插入或拨出力。同时,改善了抗腐蚀性,特别是抗摩擦磨蚀性,并且在用该材料制成的插塞连接体的使用寿命期内,还可确保持续的接触阻力。然而,在丙酮中进行超声波处理时,不可能除去油。连接方式可有多种多样,但关键是主要部件的连接结构不被氧化。
据本发明的复合材料中的基体材料最好是铜或铜合金,铁或铁合金,镍或镍合金,或者锌或锌合金。
一个据本发明的复合材料的制备方法,其特征是,将镀锡后的基体材料浸入一个热油浴中处理1-130分钟,该油浴中的热油含有天然或合成的,作为基物的石蜡和/或酯和/或脂肪酸,以及普通的添加剂,其中油温高于镀锡时的熔点温度。该油浴中的热油最好含有石蜡油或石蜡基的溶剂精制液,但不含有氯或PCB(多氯联苯)。该油温应高于镀锡时的熔点温度,其中纯锡的熔点为240℃,SnPb(锡铅)的熔点为200℃SnAg0.5sb1的熔点为250℃,浸油处理时间为2-4分钟。
金属间的位相(1MP)厚度可根据锡层的厚度和处理时的温度及时间控制在整个锡层厚度的10-100%,锡表面呈现高光泽度,并且具有耐腐蚀性,特别是抗磨蚀性。经浸油处理后的静态接触阻力不变,但摩擦力降低20-75%。
最好将经浸油热处理后的复合材料立即浸入一个冷油浴中进行淬火处理。冷油中含有天然的或合成的,作为基物的石蜡和/或酯和/或脂肪酸,以及普通的添加剂,其中油温为5-50℃,最好是10-30℃。经淬火处理后,锡层中的碳的含量进一步提高。复合材料浸于冷油浴中的时间为2-10分钟。
根据本发明的原理,也可以在基体材料刚镀完锡后,直接地把油喷洒在依然很热的锡表层上,该油含有天然或合成的,作为基物的石蜡和/或酯和/或脂肪酸,以及普通的添加剂。在此,该油不会很牢固的“结合”在镀锡层上,与不经此处理的材料相比,经此处理的材料在抗摩擦腐蚀性方面具有明显的优点。
附图说明
图1表示带状的镀锡复合材料在热油中的热处理示意图。
具体实施方式
如图所示,将带状的镀锡复合材料1送入热油管道3内浸入热油2中,进行热处理,接着将其送入冷油管道5内浸入冷油4中进行冷处理。其中,将冷的带状复合材料1经未在图中详述的一个开卷机6,通过导向滑轮7与闸门8浸入一个其温度为190-270℃的热油浴2中。热油的温度须高于镀锡时的熔点温度。如果带状复合材料1经温度升高后才浸入热油浴2中,那么就有可能出现脱网和“狗骨效应”的危险。
在热油管道3的最高点装有一个抽烟机9。
经热闸门10,通过导向滑轮11,使上述带状的复合材料1浸入一个其温度为5-50℃,或10-30℃的冷油浴4中,其中不与空气接触。多余的油经过排出喷嘴12或挤压式筒管,从冷油浴4中向外排出。带状的复合材料1经过导向滑轮13,被一个未在图中详述的卷料机14所绞卷。热油2在与之相连的加热装置中循环加热。冷油4在与之相连的冷却装置中循环冷却。出口装置15只在维修保养时才使用。
数据举例
将一个其规格为0.63毫米×80毫米的带状的CuSn 6-Bronze青铜复合材料,通过热镀法镀上纯锡(锡层厚度约为1.8毫米)。然后,将其浸入于一个装有商业上惯用的石蜡基的溶剂精制液的油浴中进行处理。(下表的第一栏I中,显示了各种处理数据)。
        I                   II         III         IV
      处理(或淬火处理)                  厚度RFA(微米)coul(正面/背面)(正面/背面)   碳含量(原子量-%)深度0→2微米      磨损侵蚀(毫Ω/周期)
  处理完毕时状态            1.5/1.7 1.1/1.5   0.7%→0%     1000/1250
  195℃/1分钟195℃/4分钟淬火处理            1.5/1.7 0.8/1.31.5/1.8 0.8/0.7   6%→0.8%1%→0.6%     1000/20801000/1850
  250℃/4分钟250℃/4分钟淬火处理            1.4/1.8 n.n.2.)/0.21.4/1.8 n.n.2..)/n.n.2.)   10%→0.1%25.8%→0.1%     3.8/50002.6/5000
           n.n.2.)为无据可查
在表格的第二栏II中,显示了带状的复合材料的正面(VS)与背面(RS)的表层厚度。用X射线荧光分析仪(RFA)测得的层厚度是表面锡层与金属间位相(IMP)的总厚度,用库仑分析仪只测得单一的表面锡层的厚度,而未测得IMP的厚度。
表格第三栏III中显示了,经俄歇电子能谱仪(AES)和二次离子质谱仪(Sims)测得的碳含量。
表格第四栏IV中显示了,经所谓的“在平面上的游码”法(rider-on-flat)测得的受磨损侵蚀的程度(在IN接触力和25微米振幅情况下,据周期n所测得的以毫Ω计的接触阻力)。假如接触阻力达到1000毫Ω时,表格中记录的是该阻力的相对应的周期数;假如接触阻力未达到1000毫Ω时,记录的是周期数为5000时的相对应的接触阻力,从表格中可以看出,若浸油热处理的温度为195℃时,那么经处理后的材料在1MP的形成和抗磨损侵蚀方面仅略有改善;只有据本发明将浸油热处理的温度控制在250℃时,才有可能显著缩短调整1MP时所需的时间(在表格中第二栏II中再也测不出单一的表面锡层的厚度)。
碳含量愈高,抗磨损侵蚀性愈强。

Claims (8)

1、带状的复合材料,其中其基体材料为金属或金属合金,其表层是经电镀或熔镀法而成的镀锡表层或锡合金表层,在所述基体材料和表层材料之间形成一金属中间相,其特征是,在锡层的外边缘部分渗入厚度低于2微米的1-50%按原子量计的碳。
2、根据权利要求1的复合材料,其特征是,上述渗入的碳量按原子量计为6-30%。
3、根据权利要求1或2的复合材料,其特征是,上述基体材料是由铜或铜合金,铁或铁合金,镍或镍合金,或者锌或锌合金组成的。
4、如权利要求1或2所述复合材料的制备方法,其特征是,将镀锡后的基体材料浸入一个热油浴中处理1-130分钟,该油浴中的热油含有天然或合成的,作为基物的石蜡和/或酯和/或脂肪酸,以及添加剂,其中,油温高于镀锡时的熔点温度。
5、根据权利要求4的方法,其特征是,上述的浸油热处理时间为2-4分钟。
6、根据权利要求4或5的方法,其特征是,将上述经浸油热处理后的复合材料直接浸入冷油浴中,在淬火处理温度为5-50℃进行淬火处理,该冷油中含有天然或合成的、作为基物的石蜡和/或酯和/或脂防酸,以及添加剂。
7、根据权利要求6的方法,其特征是,淬火处理温度为10-30℃。
8、据权利要求6的方法,其特征是,上述复合材料浸于冷油中的时间为2-10分钟。
CNB971143609A 1996-12-19 1997-12-05 带状复合材料及其制备方法 Expired - Fee Related CN1168844C (zh)

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DE19652987A DE19652987C2 (de) 1996-12-19 1996-12-19 Bandförmiges Verbundmaterial sowie Verfahren und Vorrichtung zu dessen Herstellung
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DE (2) DE19652987C2 (zh)
ES (1) ES2156330T3 (zh)
MY (1) MY125545A (zh)

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EP0849373A1 (de) 1998-06-24
EP0849373B1 (de) 2001-03-21
US6099977A (en) 2000-08-08
MY125545A (en) 2006-08-30
DE19652987A1 (de) 1998-06-25
ES2156330T3 (es) 2001-06-16
DE59703183D1 (de) 2001-04-26
DE19652987C2 (de) 2000-10-05
JPH10195692A (ja) 1998-07-28

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