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CN101193837A - 涂敷有金属的石墨膜 - Google Patents

涂敷有金属的石墨膜 Download PDF

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CN101193837A
CN101193837A CNA2006800207871A CN200680020787A CN101193837A CN 101193837 A CN101193837 A CN 101193837A CN A2006800207871 A CNA2006800207871 A CN A2006800207871A CN 200680020787 A CN200680020787 A CN 200680020787A CN 101193837 A CN101193837 A CN 101193837A
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graphite film
metal
coated
graphite
film
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O·奥廷格尔
M·克里斯特
L·菲舍尔
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SGL Carbon SE
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Abstract

本发明涉及具有至多100nm厚的金属涂层的石墨膜及其制备，例如通过连续蒸镀石墨膜，和其用途。尽管金属层的厚度很小，但石墨膜通过焊接可以相互连接或与其它的金属制或涂敷有金属的材料制的构件连接。此外，薄的金属涂层保护石墨膜的表面，防止颗粒漏出、脱落或剥落。

Description

涂敷有金属的石墨膜
本发明涉及具有至多100nm厚的金属涂层的石墨膜及其制备和用途。
石墨膜通过压缩和压紧石墨膨胀体而制得。当急剧加热石墨嵌入化合物或者石墨盐例如石墨硫酸氢盐或石墨硝酸盐时，形成石墨膨胀体。此时石墨颗粒体积增大200到400倍，并且堆积密度下降到2到20g/l。所得到的石墨膨胀体由蜗杆状或手风琴状庞大的团聚物构成。如果该颗粒在压力下被压缩，则它们彼此勾挂和衔接。由于该效应，可以在没有添加粘合剂情况下制备自支撑的平面结构，例如膜或板。石墨膜在平面上，即垂直于压制方向上表现出高的导电和导热性，并易于适应邻近的表面。
对于某些应用而言，需要石墨膜在至少一个表面上全面或部分地设置金属涂层。该涂层可以满足不同的功能，如机械强化，提高导热和导电性以及腐蚀防护性。此外，尤其是当石墨膜制的构件要通过焊接点或焊接接头与其它的、尤其是金属构件或者与膨胀的石墨制的其它构件连接时，需要金属表面。
专利US 5 100 737公开了由至少一层石墨膜和在它们的至少一个表面上具有金属层，例如铜或镍制的金属层制成的柔韧的层状复合物。石墨膜的厚度为0.1到10mm，金属层的厚度为1到200μm，优选在3和50μm之间。该层状复合物应用于电屏蔽，密封或作为冷却器(降热)。任选在石墨层或/和金属层上设置额外的连接层，以便相互连接多层这样的层状复合物。所述连接层可以设计为薄的金属层(厚度1到5μm)或者设计为粘合层。
金属层的制备优选通过化学(即通过还原剂无电流进行)或电镀沉积进行。虽然原则上不排除涂敷有金属的其它方法，例如喷熔融的金属，热喷，真空沉积技术或CVD，但不太优选这些方法，因为它们连续运行的能力较差。此外，用这些技术实现薄层的困难也很突出。
由专利DE 28 17 371 C2同样公开了涂敷有金属的石墨膜。这种涂敷有金属的石墨膜的堆叠排列作为磨具在接触刷电机中使用。所述层的涂布可以按照已知的薄层法进行，例如电镀，化学无电流镀，等离子体或离子镀，溅射或蒸镀。蒸镀技术是优选的，因为在此实现了金属特别良好地粘合在石墨膜上。在每种情况下，在涂敷时，避免将石墨膜加热到100℃以上，因为否则石墨膜强烈气化，因而减小了金属的粘合性。所涂布的层的厚度为0.1和500μm之间，优选为1和50μm之间。
本发明涉及具有至少一侧金属涂层的石墨膜，其中所述金属层的厚度为至多100nm。
本发明尤其还涉及片状、带状等石墨膜制的半成品，其中，该半成品的至少一个平面和至少一个棱具有厚度至多为100nm的金属涂层。
根据本发明涂敷的石墨膜具有多种有利的性质。比如令人惊讶地发现，尽管金属层的厚度很小，但根据本发明的石墨膜通过焊接可以毫无困难地与金属或涂敷有金属的石墨制的其它构件连接。
此外，薄的金属涂层对石墨膜的表面以及任选还对石墨膜制的半成品的棱起到突出的保护作用，防止石墨颗粒漏出、脱落或剥落。
本发明另一目的在于，提供一种方法，从而在石墨膜上制备其厚度不超过100nm的金属涂层。
本发明还涉及这样涂敷的石墨膜的组合以及其应用。
本发明的其它细节和优点来自于以下详细的描述和实施例和附图。
图1示例性表示一种构件，其中，由根据本发明涂敷的石墨膜制的半成品彼此焊接在一起。
图2表示一种冷却器，其锤头(Finnen)由在固定区域中根据本发明涂敷的石墨膜制成。
用于涂敷石墨膜的一种金属或多种金属相应于预期的应用而进行选择。例如提到由铝或铜制的涂层，其能够形成与金属或涂敷有金属的材料制的其它构件的焊接连接，以及由镍、银、金或铂金属制的涂层。所述涂层可以含有多种金属。
如果要涂敷膨胀的石墨膜制的面，例如幅面(Bahnen)，则例如通过连续蒸镀上所希望的金属而进行。取决于所使用的设备，在此有利的是，石墨膜通过一侧遮盖塑料膜，例如PET制的膜而得以强化，从而提高了抗断强度。在未遮盖的表面上，石墨膜现在一侧用金属蒸镀。在蒸镀完成后，再机械地从石墨膜未涂敷的表面上除去塑料膜。
不过本发明不局限于这些方法，还有″PVD″-方法(物理气相沉积)组的其它方法适于制备本发明涂敷的石墨膜，例如通过喷洒(溅射)和通过离子喷射法进行涂敷。
除了这些制备方法外，还有电镀或无电流沉积金属层。
代替石墨膜制的连续幅面，还可以为已经具有预期的应用所需的尺寸和形状，例如正方形或矩形的膜块或膜条的单个的石墨膜制半成品，设置厚度至多100nm的金属层。半成品在此一般是指石墨膜制的结构，不同于连续的膜幅面而具有有限的平面尺寸，其中，这些平面的形状是任意的，基本上视预期的应用而定。
该做法的优点在于，除了平面外，膜块的棱也可以被涂敷。在操作、加工、安装等时，同样尤其是片状、带状的等半成品的棱由于撞击等而遭受机械负荷。因此特别希望，除了平面外，棱也因合适的涂层而受到保护，以免石墨颗粒漏出、脱落或剥落。这点能够通过根据本发明的涂层而实现。
在蒸镀方法情况下，任选为了避免在膜块的棱上的遮暗效果，必须相应改变蒸镀源的位置或朝向。
如果需要，可以掩盖石墨膜表面的一定区域，从而使其不被涂敷。因此可以通过涂敷石墨膜表面上选定的区域而形成一定的结构(图案)。
首先从一侧涂敷有金属的石墨膜，通过层压两个一侧涂敷的膜，其中所涂敷的表面分别朝外，可以两侧地，即在两个外侧上制备涂敷有金属的石墨膜制层压件。
可选地，在使用蒸镀设备情况下，对要涂敷的膜的抗拉强度提出较低的要求，因此不必遮盖，也可以在一个工序中进行两侧涂敷。
要涂敷的石墨膜的密度最大为1.9g/cm3，优选0.3到1.9g/cm3，特别优选为0.3到1.3g/cm3。
如果需要，石墨膜在涂布金属层前用树脂等浸渍，以便填充和封闭膜中的孔。从而防止在膜上沉积的金属进入膜内部。
特别有利的是，膜在电镀或无电流沉积金属之前从电解液浴中进行浸渍，因为通过浸渍，减少了液态电解液渗入孔中，因此降低了接下来干燥所涂敷的膜的成本。
根据本发明涂敷有金属的石墨膜例如可以用于传送、传导和分散热量，例如在电气设备中。
石墨膜用于电气设备中热量管理的用途例如由专利文本US 6 482520所公开。该文献公开了一种热量管理装置，包括热源，其在它们的外表面之一上与用于热量传导的石墨膜(所谓的热界面)接触。可选择地，远离热源的石墨膜表面与冷却器接触。在专利申请US2002/0163076所述的对该热界面改进之一中建议，为了避免石墨膜脱落，远离热源的表面以及任选还有膜的棱被设置有保护涂层。建议由不同塑料制的涂层。不过，该涂层几乎不导热，因此热界面传导热量的真正功能因而受到影响。
与之相反，根据本发明所建议的金属涂层具有保护表面以防具有导热性优点的石墨颗粒脱落的优点。
在石墨膜中，导热性被设计成各向异性的，优选在膜平面中导热，反之，在金属中是各向同性的。在石墨膜内部，由于优选的侧向热量扩散，也可以实现热量宽的面分散，而通过金属层，可以影响热导入石墨膜中或者热从中传导出来，由于金属层的各向同性，即使与膜平面横向上，也能大规模导热。
由于能够形成焊接连接，由适当成型的根据本发明涂敷的石墨膜制的片状半成品，任选连接由别的涂敷有金属的材料制的或由金属制的构件，可以形成三维结构。以此方式，根据本发明涂敷的石墨膜例如可以用于制备换热器、散热器(heat spreader)、冷却器或双极冷却板，用于燃料电池组。在这些应用以及其它可想到的应用中，除了本发明能够形成焊接连接的优点外，本发明的组合也可以用于从侧向传导电流或热量到石墨膜中，以及各向同性传导电流或热量到金属层中。
所需的半成品，例如正方形或矩形的膜块或膜条，从根据本发明涂敷的石墨膜切成或冲裁成。或者，也可以由未涂敷的膜幅面切成或冲裁成所希望的半成品，然后对其进行涂敷。该做法的优点是，除了平面外，还可以为半成品的棱设置金属涂层，因此所述半成品的棱区域也受到保护，以防石墨颗粒漏出、脱落或剥落。
还可以使用由涂敷有金属的石墨膜制的层压件作为形成三维结构的半成品。
对于不能或不适合通过焊接来固定涂敷有金属的石墨膜的应用情形而言，可以在金属涂层上涂布薄的粘合剂层。不过，该粘合剂层应该尽可能薄，以便热量传导到金属层不受影响。用10μm厚的粘合剂层达到良好效果。
如果打算用没有金属涂敷的石墨膜侧同样固定在别的构件上时，可以以同样的方式提供薄的粘合剂层。
粘合剂的涂布可以直接在使用前进行。或者可以用粘合剂层将涂敷有金属的石墨膜预制在金属层上或/和在没有金属涂敷的表面上，其用可剥去的塑料膜覆盖，而且在使用前直接剥去。
实施例1：
用薄的金属层涂敷石墨膜的方法
一厚度为0.4mm并且密度为1.2g/cm3的石墨膜幅面的一侧用厚度为12μm的PET-膜所遮盖，以便提高石墨膜的抗拉强度。该膜的长度约为50m，宽度约为1m。由石墨膜和PET-膜制的该膜复合件在连续工作的高真空-涂敷设备中，在未被PET-膜覆盖的石墨膜的表面上一侧用铝蒸镀。膜在涂敷设备中的运行速度约为5m/s。
为了确定铝层的厚度，从该涂敷的膜复合件冲裁出30×70mm2大小的样品。将PET-膜机械地从样品上除去。通过原子发射光谱(ICP-AES)确定剩下的石墨-铝层状复合件的铝含量(260μg)。由样品的面积和铝层的质量求出铝层的基于面积计的质量(0.12g/m2)。借助铝的密度(2.7g/cm3)，从而计算出蒸镀的铝层的厚度约为45nm。
实施例2：
根据本发明涂敷有铝的石墨膜之间焊接连接的形成
在相应于实施例1的一侧设置有薄铝涂层2的石墨膜1上焊接由另一种一侧涂敷有铝2′的石墨膜制的条3(参见图1)
为此首先用水揉和购得的硬焊粉末，其以名称″Amasan″(生产商：Fa.Armack GmbH-Lttechnik)出售并适合焊接铝和轻金属ALU22。用毛刷将该物料涂布在要焊接的膜条涂敷有铝的面上，并撒布粒径＜100μm的铝粉末(生产商：Fa.Schlenk Metallpulver GmbH&Co.KG)。然后将要焊接的膜条置于根据实施例1中所述的方法涂敷的石墨膜涂敷有铝的面上，并装入冷的炉中用于固定的两个板之间。将该炉在约2小时内加热到650℃。保持该温度达20分钟，然后使炉中的样品冷却。
焊接的膜条很好地粘合在石墨膜上。在石墨膜真空涂敷期间，为强化而层压上铝的PET-膜，在炉运行期间被无残留地灼烧掉。通过比较缓慢的加热，因膜放气而导致的形成气泡受到压制。
所焊接的板的厚度在重叠的位置增加约0.4mm(焊接层)。在该位置视觉上不再能发现铝层。
由这样制得的相应于图1的结构，通过将另一个根据本发明涂敷的石墨膜焊接在于早先石墨膜1上焊接的条3上，可以形成沟道(Kanal)结构，其尤其可用于换热器中。
实施例2的比较实施例
在比较实验中，根据上述方法，没有被涂敷的石墨膜的条被焊接在没有涂敷的石墨膜上。在该实验中，焊接的部分之间的粘合性明显低于在涂敷有铝的石墨膜之间焊接连接情况下的粘合性。这些条中的一些完全溶解，另外的至少部分地从基础上溶下来。
实施例3
具有焊接的石墨膜制的锤头的冷却器
根据图2的冷却器含有石墨膜制的冷却锤头4，其从基板5伸出并由此引走热量。在通常由金属形成的基板5的表面上，设置凹槽来容纳冷却锤头4。该冷却锤头4焊接在基板的该凹槽中。为此，石墨膜制的冷却锤头4至少在它们的表面区域(其伸入凹槽中(固定区域))设置根据本发明的金属涂层。
或者可以使用石墨制的基板，其中凹槽的壁面涂敷有金属，因此，在固定区域设置有根据本发明的金属涂层的石墨膜制的锤头，通过焊接可以固定在该基板的凹槽中。

Claims (15)

1.在至少一个表面上具有金属涂层的石墨膜，其特征在于，所述涂层的厚度为至多100nm。
2.根据权利要求1的涂敷有金属的石墨膜，其特征在于，所述涂层含有金属铝、铜、镍、银、金或铂金属的至少一种。
3.根据权利要求1的涂敷有金属的石墨膜，其特征在于，所述石墨膜用树脂进行浸渍。
4.根据权利要求1到3之一的涂敷有金属的石墨膜，其特征在于，石墨膜表面仅有选定的区域涂敷有金属。
5.根据权利要求1到4之一的涂敷有金属的石墨膜，其特征在于，在金属层上或/和在未涂敷有金属的表面上有厚度至多10μm的粘合剂层，其被可剥去的膜覆盖。
6.由两个一侧涂敷有金属的根据权利要求1的石墨膜制的层压件，其中所述石墨膜这样排列，使得它们的涂敷有金属的表面朝外，从而该层压件的两个外侧具有金属层。
7.石墨膜制的片状或带状半成品，其特征在于，该半成品的至少一个平面和至少一个棱具有厚度至多为100nm的金属涂层。
8.根据权利要求1到5之一的涂敷有金属的石墨膜、根据权利要求6的由涂敷有金属的石墨膜制的层压件或根据权利要求7的半成品用于传送、传导或分散热量的用途，尤其是用在电气设备中。
9.根据权利要求1到4之一的涂敷有金属的石墨膜、根据权利要求6的由涂敷有金属的石墨膜制的层压件或根据权利要求7的半成品用于制备换热器、冷却器、散热器或燃料电池组用的双极冷却板的用途。
10.由根据权利要求1到4之一的涂敷有金属的石墨膜制的半成品或构件、根据权利要求6的层压件或根据权利要求7的半成品相互连接，或者与由其它的涂敷有金属的材料或由金属制的半成品或构件连接的方法，其特征在于，相互焊接所述构件。
11.冷却器，包含石墨膜制的冷却锤头和具有凹槽的金属制基板或具有凹槽的石墨制基板，其壁涂敷有金属，其中锤头焊接在凹槽中，其特征在于，石墨膜制的冷却锤头至少在伸入凹槽的的表面区域中用根据权利要求1的金属层进行涂敷。
12.在石墨膜上制备一侧金属涂层的方法，包括以下步骤
-一侧用塑料膜遮盖石墨膜制的幅面，
-用所希望的金属以所希望的层厚度进行连续蒸镀，
-机械式除去遮盖。
13.根据权利要求12的方法，其特征在于，所述石墨膜用PET膜遮盖。
14.根据权利要求12的方法，其特征在于，所述石墨膜用树脂进行浸渍。
15.根据权利要求12的方法，其特征在于，所选定的应保持未涂敷的表面区域用掩盖物进行覆盖。
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CN101710493B (zh) * 2009-05-12 2012-03-21 大连丽昌新材料有限公司 一种石墨散热模组
US8955580B2 (en) 2009-08-14 2015-02-17 Wah Hong Industrial Corp. Use of a graphite heat-dissipation device including a plating metal layer
CN102555325A (zh) * 2010-12-31 2012-07-11 常州碳元科技发展有限公司 一种复合固定型高散热膜结构
CN109874345A (zh) * 2015-04-15 2019-06-11 株式会社钟化 离子束电荷转换装置的电荷转换膜
CN109874345B (zh) * 2015-04-15 2023-10-31 株式会社钟化 离子束电荷转换装置的电荷转换膜
CN110744875A (zh) * 2019-10-25 2020-02-04 北京中石伟业科技无锡有限公司 一种高导热复合石墨散热片及其制备方法

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