CN102099506B - 带材上的金属/cnt-和/或富勒烯-复合材料-涂层 - Google Patents

带材上的金属/cnt-和/或富勒烯-复合材料-涂层 Download PDF

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CN102099506B
CN102099506B CN200980127356.9A CN200980127356A CN102099506B CN 102099506 B CN102099506 B CN 102099506B CN 200980127356 A CN200980127356 A CN 200980127356A CN 102099506 B CN102099506 B CN 102099506B
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sheet metal
metal strip
carbon nanotube
soccerballene
graphene
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H·施密特
I·伯斯克
U·阿德勒
D·罗德
S·普里格梅尔
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Wieland Werke AG
TE Connectivity Germany GmbH
KME Special Products GmbH and Co KG
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Abstract

本发明涉及金属带材或经预冲压的金属带材上的金属/碳纳米管(CNT)-和/或富勒烯-复合物涂层，所述金属带材或经预冲压的金属带材具有改善的摩擦系数和/或良好的接点过渡电阻和/或良好的耐摩擦腐蚀性和/或良好的耐磨损性和/或良好的成形性。本发明还涉及根据本发明的涂布的金属带材的制备方法。

Description

带材上的金属/CNT-和/或富勒烯-复合材料-涂层
技术领域
本发明涉及金属带材上的金属/碳纳米管(CNT)-和/或富勒烯-复合材料-涂层，所述金属带材具有改善的摩擦系数(Reibwert)、良好的接点过渡电阻(Kontaktübergangswiderstand)、良好的耐摩擦腐蚀性、良好的耐磨损性和良好的成形性。本发明还涉及根据本发明的经涂布的金属带材的制备方法。
背景技术
Sumiolijama于1991年发现了碳纳米管(CNT)(参见S.lijama，Nature，1991，354，56)。lijama在一定反应条件下的富勒烯生成器的煤烟中发现了直径仅为数十纳米而长度直至数微米的管状结构。由他发现的化合物由多个聚集的被称作多壁碳纳米管(MWCNT)的石墨管组成。不久之后，lijama和Ichihashi发现了直径仅约1纳米的单壁CNT，其被相应地称作单壁碳纳米管(SWCNT)(参见S.lijama，T.Ichihashi，Nature，1993，363，6430)。
CNT的突出特征包括，例如其约40GPa或1TPa的机械抗拉伸强度和刚度(比钢的抗拉伸强度和刚度高20或5倍)。
CNT中存在导体材料和半导体材料。碳纳米管属于富勒烯家族且具有1纳米至数百纳米的直径。碳纳米管是由碳形成的精微的很小的管状结构(分子纳米管)。其壁如同富勒烯的壁或者如同石墨平面仅由碳组成，其中碳原子采取具有六个角和各三个键合对象(Bindungspartnern)的蜂窝状结构(通过sp2杂化确定)。管的直径通常为1至50纳米，但是也制备了具有仅0.4纳米直径的管。对于单管已经达到了数微米的长度以及对于管束已经达到了直至20厘米的长度。
通常通过从气相或等离子体中沉积碳来合成碳纳米管。对于电子工业来说，载流量(Strombelastbarkeit)和导热性是特别令人感兴趣的。载流量比铜线的载流量约高1000倍，室温下6000W/m*K的导热性几乎是金刚石(最好的天然来源热导体)的导热性的两倍。
如上所述，碳纳米管属于富勒烯类。富勒烯是由碳原子形成的具有高对称性的球形分子，其是除金刚石和石墨之外的碳的第三种同素异形体。通常通过在减压下和在保护气体气氛(例如氩气)下用电阻加热或在电弧中蒸发石墨而制备富勒烯。作为副产物，通常产生上述碳纳米管。富勒烯具有半导至超导性能。
现有技术中已知将碳纳米管与传统塑料混合。由此大大改善塑料的机械性能。此外，有可能制备导电塑料，例如已经使用纳米管来赋予抗静电膜传导性。
在当今的具有锡或银或镍涂层的实施方案(Ausführung)中，电子机械元件(例如连接器、转换器、继电器弹簧、可直插式冲压栅条(Stanzgitter)等)通常具有摩擦系数和/或接点过渡电阻差、耐磨损性低和/或成形性差的问题。在现有技术中，迄今为止还未公开使用碳纳米管和/或富勒烯来改善这些性能。
发明内容
因此，本发明的任务是提供克服了上述缺点，即具有改善的摩擦系数和/或良好的接点过渡电阻和/或良好的耐磨损性和/或良好的成形性的电子机械元件。
通过包含由碳纳米管和/或富勒烯和金属组成的涂层的金属带材解决该任务。
在本发明范畴中，金属带材被优选理解为优选由铜和/或铜合金、铝和/或铝合金或铁和/或铁合金组成的金属带材或电子机械元件。
金属带材优选包含扩散阻挡层，该扩散阻挡层优选被施加在金属带材的两侧。金属带材应该是非绝缘体。因此，扩散阻挡层优选包含过渡金属或由过渡金属组成。
优选的过渡金属为例如Mo、B、Co、Fe/Ni、Cr、Ti、W或Ce。
碳纳米管以柱状排布在金属带材上，这可通过下述根据本发明的方法来实现。碳纳米管可以是单壁或多壁的碳纳米管，这也同样可通过根据本发明的方法来控制。富勒烯优选以球体形式排布在金属带材上。
涂层也可优选包含石墨烯。
石墨烯被人们称作是sp2杂化的碳原子的单原子层。石墨烯沿其平面显示出非常良好的导电性和导热性。通过在石墨的基准面(Basalebenen)内裂解石墨而制造石墨烯。在此过程中首先插入(interkaliert)氧气。氧气部分地与碳反应并导致层的相互排斥。随后使石墨烯悬浮，并根据使用目的例如将其插入聚合物中或如本发明中所述作为金属带材的涂层组分。
制造单个石墨烯层的另一可能性是将六边形碳化硅表面加热至高于1400℃的温度。由于硅的较高蒸气压，硅原子比碳原子更快蒸发。之后在表面上形成由少量石墨烯单层组成的薄层单晶石墨。
在一个优选的实施方案中，石墨烯和/或碳纳米管和/或富勒烯形成复合材料。这意味着，石墨烯与碳纳米管、石墨烯与富勒烯、富勒烯与碳纳米管或所有组分一起可以形成复合材料。特别优选地，石墨烯正交排布在碳纳米管和/或富勒烯上，其中它们例如在轴向上构成管的末端，或者石墨烯和富勒烯正交排布在碳纳米管上。石墨烯在富勒烯上的正交排布近似意味着石墨烯在富勒烯上的正切排布。富勒烯在碳纳米管上的正交排布可被设想为如同“权杖(Zepter)”，其中富勒烯位于碳纳米管的末端。
金属带材优选具有0.06至3毫米，特别优选0.08至2.7毫米的厚度。
本发明的主题还在于一种用碳纳米管和/或富勒烯和金属涂布的金属带材的制备方法，该方法包括如下步骤：
a)用扩散阻挡层涂布金属带材，
b)在扩散阻挡层上施加成核层，
c)将根据步骤a)和b)处理的金属带材置于包含有机气态化合物的气氛中，
d)在200℃至1500℃的温度下在金属带材上形成碳纳米管和/或富勒烯，
e)用金属渗透(Durchdringen)碳纳米管和/或富勒烯。
在根据本发明的方法中，优选用扩散阻挡层来涂布金属带材的两侧。在扩散阻挡层上优选施加成核层，该成核层支持碳纳米管的柱状生长或富勒烯的沉积。在该方法中使用的成核层优选包含选自元素周期表的Fe族、第8、9和10副族的金属的金属盐。
随后将如此处理的金属带材暴露于优选为烃气氛的气氛中。烃气氛特别优选为甲烷气氛，其中另外地向所述气氛或烃气氛中加入载气。作为载气可以例如为氩气。
通常在200℃至1500℃的温度下在金属带材上形成碳纳米管和/或富勒烯。在200℃至900℃的温度下主要形成多壁碳纳米管(MWCNT)。在大于900℃至约1500℃的温度下优选形成单壁碳纳米管(SWCNT)。当在潮湿环境中进行生长时，可改善碳纳米管的质量。碳纳米管于金属带材上的形成以柱状形式进行，这通过成核层来支持促进。富勒烯优选以球状沉积在金属带材上。
然后再用金属渗透碳纳米管和/或富勒烯。作为金属的是上述金属Sn、Ni、Ag、Au、Pd、Cu或W以及它们的合金。
优选通过真空法，例如CVD(化学气相沉积)或PVD(物理气相沉积)，电解，无电还原或通过熔入/渗进从而用金属渗透碳纳米管和/或富勒烯。
优选还在涂层中引入石墨烯。石墨烯和/或碳纳米管和/或富勒烯优选形成复合材料。这意味着，石墨烯与碳纳米管、石墨烯与富勒烯、富勒烯与碳纳米管或所有三种组分一起可以形成复合材料。特别优选地，石墨烯正交地排布在碳纳米管和/或富勒烯上，其中它们例如在轴向上构成管的末端，或者石墨烯和富勒烯正交排布在碳纳米管上。石墨烯在富勒烯上的正交排布近似意味着石墨烯在富勒烯上的正切排布。富勒烯在碳纳米管上的正交排布可被设想为如同“权杖(Zepter)”，其中富勒烯位于碳纳米管的末端。
如此制备的用金属和碳纳米管和/或富勒烯(和石墨烯)涂布的金属带材的特征在于改善的摩擦系数、良好的接点过渡电阻、良好的耐磨损性和良好的成形性，并因此特别适合作为电子机械元件，例如用于连接器、转换器、继电器弹簧等。特别地，当以上述复合材料形式与石墨烯结合时，可在水平和垂直方向上提供导电性和导热性，这是特别有利的。

Claims (28)

1.包含由碳纳米管和/或富勒烯和金属组成的涂层的金属带材，其特征在于，所述涂层包含石墨烯，并且所述金属是Sn、Ni、Ag、Au、Pd、Cu或W以及它们的合金。
2.根据权利要求1所述的金属带材，其在金属带材的两侧还包含扩散阻挡层。
3.根据权利要求2所述的金属带材，其特征在于，扩散阻挡层是非绝缘体。
4.根据权利要求2或3所述的金属带材，其特征在于，扩散阻挡层包含过渡金属。
5.根据权利要求1至3任一项所述的金属带材，其特征在于，涂层的金属选自Sn、Ni、Ag、Au、Pd、Cu、W或它们的合金。
6.根据权利要求1至3任一项所述的金属带材，其特征在于，碳纳米管以柱状排布在金属带材上。
7.根据权利要求1至3任一项所述的金属带材，其特征在于，所述碳纳米管是单壁或多壁的碳纳米管。
8.根据权利要求1至3任一项所述的金属带材，其特征在于，所述金属带材具有0.06至3mm的厚度。
9.根据权利要求8所述的金属带材，其特征在于，所述石墨烯和/或碳纳米管和/或富勒烯形成复合材料。
10.根据权利要求1所述的金属带材，其特征在于，所述石墨烯和/或富勒烯正交排布在碳纳米管上，或者石墨烯正交排布在碳纳米管和/或富勒烯上。
11.根据权利要求1至3任一项所述的金属带材，其特征在于，所述金属带材被预冲压。
12.用碳纳米管和/或富勒烯和金属涂布的金属带材的制备方法，该方法包括如下步骤：
a)用扩散阻挡层涂布金属带材，
b)在扩散阻挡层上施加成核层，
c)将根据步骤a)和b)处理的金属带材置于包含有机气态化合物的气氛中，
d)在200℃至1500℃的温度下在金属带材上形成碳纳米管和/或富勒烯，
e)用金属渗透碳纳米管和/或富勒烯，
其中在涂层中引入石墨烯，并且所述金属是Sn、Ni、Ag、Au、Pd、Cu或W以及它们的合金。
13.根据权利要求12所述的方法，其特征在于，用扩散阻挡层双面涂布金属带材。
14.根据权利要求12或13所述的方法，其特征在于，使用选自元素周期表的Fe族、第8、9或10副族的金属的金属盐作为成核层。
15.根据权利要求14所述的方法，其特征在于，部分地施加成核层。
16.根据权利要求12至13任一项所述的方法，其特征在于，金属带材暴露于烃气氛。
17.根据权利要求16所述的方法，其特征在于，除了烃气氛之外使用载气。
18.根据权利要求12至13任一项所述的方法，其特征在于，将金属带材置于具有有机气态化合物的水分含量为50至90％的气氛中。
19.根据权利要求12至13任一项所述的方法，其特征在于，形成碳纳米管和/或富勒烯的温度为200℃至900℃。
20.根据权利要求19所述的方法，其特征在于，形成多壁碳纳米管。
21.根据权利要求12至13任一项所述的方法，其特征在于，形成碳纳米管和/或富勒烯的温度为＞900℃至1500℃。
22.根据权利要求21所述的方法，其特征在于，形成单壁碳纳米管。
23.根据权利要求12至13任一项所述的方法，其特征在于，碳纳米管以柱状形成于金属带材上。
24.根据权利要求12至13任一项所述的方法，其特征在于，通过真空法，电解、无电还原或通过熔入/渗入而用金属渗透碳纳米管和/或富勒烯。
25.根据权利要求12所述的方法，其特征在于，石墨烯正交排布在碳纳米管和/或富勒烯上，或者石墨烯和/或富勒烯正交排布在碳纳米管上。
26.根据权利要求12或25所述的方法，其特征在于，石墨烯和/或碳纳米管和/或富勒烯形成复合材料。
27.根据权利要求1至11任一项所述的金属带材或者由根据权利要求12至26任一项所述的方法制备的金属带材作为电子机械元件的用途。
28.根据权利要求27所述的用途，其特征在于，所述电子机械元件是冲压栅条。
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