CN1976807B - 树脂浸渍的柔性石墨制品 - Google Patents

树脂浸渍的柔性石墨制品 Download PDF

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Publication number
CN1976807B
CN1976807B CN2004800433619A CN200480043361A CN1976807B CN 1976807 B CN1976807 B CN 1976807B CN 2004800433619 A CN2004800433619 A CN 2004800433619A CN 200480043361 A CN200480043361 A CN 200480043361A CN 1976807 B CN1976807 B CN 1976807B
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China
Prior art keywords
graphite
resin
laminated material
acid
pressure
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Expired - Fee Related
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CN2004800433619A
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English (en)
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CN1976807A (zh
Inventor
J·诺尔利
J·J·布拉迪
G·格茨
J·克卢格
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Graftech Inc
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Graftech Inc
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B1/00—Methods for turning or working essentially requiring the use of turning-machines; Use of auxiliary equipment in connection with such methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F28F21/02—Constructions of heat-exchange apparatus characterised by the selection of particular materials of carbon, e.g. graphite
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Abstract

由树脂浸渍的柔性石墨材料制备复合材料。在高温和高压下压缩和固化浸渍的材料，形成适用于例如电子热处理(ETM)装置、超级电容器和二次电池应用的结构。

Description

树脂浸渍的柔性石墨制品
技术领域
本发明涉及由树脂浸渍的、膨胀(exfoliated)石墨(通常称为柔性石墨)的压缩颗粒形成的制品，该制品在热和压力下固化，并用于应用例如电子热处理(ETM)中使用的传热器，或者超级电容器和二次电池的集电器。
技术背景
作为包含树脂浸渍的石墨片的复合材料，压缩的膨胀石墨制品为本领域所熟知。这些结构在例如制备垫圈中发现了用途。
除它们在垫圈材料中的用途外，石墨复合材料还发现作为传热器或制冷设备的用途。各种固体结构作为传热器的用途为本领域所熟知。例如，Banks，美国专利5,316,080和5,224,030公开：钻石和气体衍生的石墨纤维与适当粘合剂结合作为传热装置的用途。使用这样的装置将热量从热源例如半导体，被动地传导到散热器。
石墨-基热处理元件在电子应用方面提供几个优势，可有助于消除计算机、通讯设备和其它电子装置中产热元件的潜在负面影响。石墨-基热处理元件包括散热器、热管和热扩散器。所有石墨-基热处理元件提供相等于或优于铜或铝的导热性，但其重量仅为那些材料的一部分，并且提供了显著更大的设计弹性。石墨-基热处理产品利用石墨的高度定向从敏感元件除去热量。与用于热处理的典型铝合金相比，本发明石墨元件可以具有最高达300％的热导率，与铜的值(每米开氏温度～400瓦特，即W/mK)相当或比其更高。此外，铝和铜是各向同性的，使其难于在优选方向上引导热量。
用于本发明的石墨材料是由膨胀石墨的压缩颗粒形成的石墨材料。
下面简要描述石墨以及一般将其加工成柔性材料的方法。用显微镜可见，石墨由碳原子的六角形排列层状平面或网络所构成。这些六角形排列的碳原子层状平面基本上是平的，其取向或顺序使彼此之间基本平行并距离相等。基本平、平行、等距的碳原子片或层，通常称为石墨平面(graphene)层或基面，互相连结或结合，其中的基团排列成微晶。高度有序的石墨材料由相当大的微晶组成，该微晶相互之间高度排列或取向，并具有非常有序的碳层。换句话说，高度有序的石墨具有高的优选微晶取向度。应理解根据定义，石墨具有各向异性结构，因此显示或具有许多高度定向的特性，例如导热性和导电性以及流动扩散。
简而言之，石墨的特征在于碳的层状结构，即由通过弱范德华力结合在一起的碳原子迭生层或层组成的结构。鉴于石墨的结构，通常记录两个轴或方向，就是“c”轴或方向和“a”轴或方向。简单地说，这个“c”轴或方向可以认为是垂直于碳层的方向。这个“a”轴或方向可以认为是平行于碳层的方向或垂直于“c”向的方向。石墨适用于制备具有非常高取向度的柔性石墨制品。
如上所述，将碳原子平行层保持在一起的结合力仅仅是弱范德华力。因为天然石墨可以进行化学处理，所以迭生碳层或片之间的空间可以适当打开，以便在层的垂直方向，就是“c”向提供显著膨胀，因而形成膨胀的石墨结构，其中碳层的层状特性基本得到保持。
鳞片石墨经过化学膨胀或热膨胀，更特别是膨胀使其最终厚度或“c”向尺寸为原始“c”向尺寸的多达约80倍或更多倍，不使用粘合剂就可形成粘着或完整的膨胀石墨片，例如网、纸、条、带等(典型地称为“柔性石墨”)。石墨颗粒膨胀至最终厚度或“c”尺寸为原始“c”向尺寸的多达约80倍或更多倍，不使用任何粘合材料就可以将石墨颗粒压缩形成完整的柔性制品，认为这可能是由于极度膨胀的石墨颗粒之间获得的机械连结或内聚力。
除柔性之外，如上所述，石墨材料也发现在导热性和导电性及流动扩散方面均有高的各向异性度，但是和天然石墨原料相比稍微小点，这是由于膨胀的石墨颗粒取向基本平行于非常高压，例如辊轧处理形成材料的反面。这样制备的材料具有优良的柔性、良好的强度和非常高的取向度。在加工处理中需要更充分地利用这些特性。
简而言之，制备无粘结剂型各向异性石墨材料例如片、制品、网、纸、条、带、箔、垫等的方法，包括在预定负荷和不使用粘合剂的情况下进行压缩或压实，从而将“c”向尺寸为原颗粒多达约80倍或更多倍的膨胀石墨颗粒，形成基本平、完整的石墨制品。典型地，形成的制品是柔软、相对薄(即5mm或更薄)的片，虽然采用这种方法也能制备更厚的制品。在外观上通常像蠕虫状的膨胀石墨颗粒，一旦被压缩就维持压缩的状态，背向片的主要表面排列。通过在压缩步骤前，涂和/或加粘合剂或添加剂可以改变制品的性质。见Shane等的美国专利3,404,061。通过控制压缩的程度可以改变材料的密度和厚度。
当表面元件需要压纹或模塑时，较低密度是有利的，较低密度有助于获得良好的元件。然而，较高密度片一般对较高的面内强度、导热性和导电性是有利的。典型地，材料密度大约在0.04g/cm3至约1.4g/cm3范围内。
由于石墨颗粒的排列平行于材料的主要反向平行表面，如上所述制备的石墨材料典型地显示可测的各向异性度，随着各向异性度的增加，辊压时增加密度。在辊压各向异性材料中，厚度，即垂直于反向平行表面的方向包含“c”向，而沿着长度和宽度的方向，即沿着或平行于反向主要表面的方向包含“a”向，材料在“c”和“a”向的热、电和流动扩散特性有很大的不同，典型地达到数量级的差异。
发明公开
本发明的目的是提供适用于电子热处理(ETM)、超级电容器或二次电池的树脂浸渍的石墨制品。
本发明的再一个目的是提供具有增强的面内特性的石墨结构。
本发明的再一个目的是提供可加工的石墨结构，该石墨结构在“a”向具有相对高的导热性，而在“c”向具有相对低的传导性。
本发明提供了包含树脂浸渍的石墨制品的结构，完成了这些和其它目的，所述制品由膨胀石墨的压缩颗粒形成。
实施本发明的最佳方式
本发明基于以下发现：当压缩(例如通过压延)环氧树脂浸渍的石墨制品，然后高温、高压下固化时，所得材料显示出乎意料的良好机械和热特性，还具有良好的机械加工性。
在描述本发明改进现有材料的方法以前，先简要描述石墨及其成型为完整制品，该制品将成为形成本发明产品的主要基材。
石墨制品的制备
石墨是碳的结晶态，其中在层状平面内包含共价结合的原子，而平面之间结合较弱。通过用插入剂例如硫酸和硝酸溶液，对石墨例如天然片状石墨颗粒处理，石墨的晶体结构反应形成石墨和插入剂的复合物。其后，已处理过的石墨颗粒称为“插入石墨的颗粒”。当暴露于高温下，石墨内的插入物分解和挥发，导致插入石墨的颗粒按照类似折叠的方式，在“c”向即垂直于石墨晶体平面的方向，其尺寸膨胀至原体积的多达约80倍或更多倍。膨胀石墨颗粒的外观呈蠕虫状，因此通常称为蠕虫石墨，在本文有时称为“膨胀石墨颗粒”。可将蠕虫石墨压缩成为制品，与原来的片状石墨不同，该制品可以通过机械撞击变形，形成和切割成各种形状，并提供小的横向孔。
用于本发明材料的石墨原料包括高碳含量的石墨材料，该材料能插入有机和无机酸以及卤素，并且当暴露于热时膨胀。这些高碳含量的石墨材料最优选石墨化度为约1.0。用于本公开的术语“石墨化度”指按照以下公式的g值：
g = 3.45 - d ( 002 ) 0.095
其中d(002)是以埃为单位测量的晶体结构中石墨碳层之间的间距。采用标准X射线衍射技术测量石墨层间的间距d。测量了对应于(002)、(004)和(006)米勒指数的衍射峰位置，采用标准最小二乘方技术推算出将所有这些峰的总误差减到最小的间距。高碳含量的石墨材料实例包括各种来源的天然石墨，以及其它含碳材料例如通过化学蒸发沉淀制备的碳等。天然石墨最优选。
本发明所用材料的石墨原料可含非碳成分，只要原料的晶体结构保持必需的石墨化度，并且它们能够膨胀。通常，其晶体结构具有必需的石墨化度并且它能够膨胀的任何含碳材料，均适用于本发明。这样的石墨优选灰分含量低于20％重量。更优选，用于本发明的石墨纯度至少约94％。在最优选的实施方案中，使用的石墨纯度至少约98％。
Shane等在美国专利第3,404,061号描述了制备石墨片材的通用方法，该专利内容通过引用结合到本文中。在实施Shane等方法的一个实施方案中，通过将天然片状石墨分散于例如含硝酸和硫酸混合物的溶液中，天然片状石墨被插入，最好每100重量份片状石墨(pph)插入剂溶液的水平为约20至约300重量份。插入溶液含氧化剂和本领域熟知的其它插入剂。实例包括含氧化剂和氧化混合物的那些，例如含以下物质的溶液：硝酸、氯酸钾、铬酸、高锰酸钾、铬酸钾、重铬酸钾、过氯酸等；或混合物，例如浓硝酸和氯酸盐、铬酸和磷酸、硫酸和硝酸，或强有机酸例如三氟乙酸与溶于有机酸中强氧化剂的混合物。或者可使用电势引起石墨氧化。可使用电解氧化引入石墨晶体的化学物质包括硫酸和其它酸。
在优选的实施方案中，插入剂为硫酸、或硫酸和磷酸与氧化剂混合物的溶液，该氧化剂即硝酸、高氯酸、铬酸、高锰酸钾、过氧化氢、碘酸或高碘酸等。虽然很少优选，但是插入溶液可以含金属卤化物例如氯化铁以及与硫酸混合的氯化铁；或卤化物，例如溴和硫酸溶液的溴或在有机溶剂中的溴。
插入溶液的量可以为约20至约150pph，更典型地为约50至约120pph。片被插入之后，从一个或多个片中排出任何过量溶液，并用水洗。或者，插入溶液的量可以限定在约10至约50pph，这样允许省略洗涤步骤，如美国专利第4,895,713号所教导和描述的那样，该专利内容也通过引用结合到本文中。
经插入溶液处理的片状石墨颗粒可以任选例如通过掺混和有机还原剂接触，该有机还原剂选自醇、糖、醛和酯，其可以在25℃至125℃，与氧化性插入溶液的表面膜反应。合适的具体有机还原剂包括十六醇、十八醇、1-辛醇、2-辛醇、癸醇、1，10-癸二醇、癸醛、1-丙醇、1，3-丙二醇、乙二醇、聚丙二醇、葡萄糖、果糖、乳糖、蔗糖、马铃薯淀粉、乙二醇单硬脂酸酯、二甘醇二苯甲酸酯、丙二醇单硬脂酸酯、甘油单硬脂酸酯、肉铁质酸(oxylate)二甲酯、肉铁质酸二乙酯、甲酸甲酯、甲酸乙酯、抗坏血酸和木质素衍生化合物，例如木质素磺酸钠。以片状石墨颗粒计，有机还原剂的合适量为约0.5-4％重量。
在插入之前、期间或其后立即，使用膨胀助剂也可提供改善。其中，这些改善可以降低膨胀温度和增加膨胀体积(也称为“蠕虫体积”)。上下文中的膨胀助剂最好是可充分溶解于插入溶液的有机物质，以实现膨胀改善。更准确地说，可使用这类优选仅含碳、氢和氧的有机物质。已发现羧酸特别有效。用作膨胀助剂的合适羧酸可以选自芳族、脂族或环状脂族直链或支链、饱和及不饱和的一元羧酸、二元羧酸和多元羧酸，具有至少1个碳原子，优选最多达约15个碳原子，其以有效提供一个或多个膨胀方面的可测量改善的量，溶于插入溶液中。可用合适的有机溶剂改善有机膨胀助剂在插入溶液中的溶解性。
饱和脂族羧酸的代表性实例是酸例如式为H(CH2)nCOOH的那些酸，其中n为0至约5，包括甲酸、乙酸、丙酸、丁酸、戊酸、己酸等。也可以使用酐或活性羧酸衍生物例如烷基酯来替代羧酸。代表性烷基酯是甲酸甲酯和甲酸乙酯。硫酸、硝酸和其它熟知的水性插入剂有分解甲酸的能力，最终分解成水和二氧化碳。因此，最好在片浸入水性插入剂之前，将甲酸和其它敏感膨胀助剂与该片状石墨接触。代表性二元羧酸是具有2至12个碳原子的脂族二羧酸，特别是草酸、延胡索酸、丙二酸、马来酸、琥珀酸、戊二酸、己二酸、1，5-戊烷二甲酸、1，6-己烷二甲酸、1，10-癸烷二甲酸、环己烷-1，4-二甲酸和芳族二羧酸，例如邻苯二甲酸或对苯二甲酸。代表性烷基酯是肉铁质酸二甲酯和肉铁质酸二乙酯。代表性环状脂族酸是环己烷羧酸，代表性芳族羧酸是苯甲酸、萘甲酸、邻氨基苯甲酸、对氨基苯甲酸、水杨酸，邻-、间-和对-甲基苯甲酸、甲氧基和乙氧基苯甲酸、乙酰基乙酰氨基苯甲酸、乙酰氨基苯甲酸、苯乙酸和萘甲酸。代表性羟基芳酸是羟基苯甲酸、3-羟基-1-萘甲酸、3-羟基-2-萘甲酸、4-羟基-2-萘甲酸、5-羟基-1-萘甲酸、5-羟基-2-萘甲酸、6-羟基-2-萘甲酸和7-羟基-2-萘甲酸。在多元羧酸中突出的是柠檬酸。
插入溶液为水溶液，优选含约1-10％的膨胀助剂，该量对促进膨胀有效。在实施方案中，在浸入插入水溶液之前或之后，将膨胀助剂与片状石墨接触，可以通过合适的方法，例如V型搅拌机，将膨胀助剂与石墨混合，以片状石墨计，膨胀助剂的量一般为约0.2％至约10％重量。
插入片状石墨之后，接着将插入剂涂覆的已插入片状石墨与有机还原剂掺混，将该掺混物暴露于25℃至125℃，以促进还原剂与插入剂涂层之间的反应。加热时间最长达约2小时，以及在上述温度范围内的较高温度下加热更短的时间，例如至少约10分钟。可采用在较高温度下加热半小时或更短时间，例如10至25分钟的数量级。
通过在石墨化温度，即约3000℃及以上温度下，预处理片状石墨和通过将润滑添加剂加入到插入剂中，上述片状石墨的插入和膨胀方法可得到有利的增强。
当随后进行片的插入和膨胀时，片状石墨的预处理或退火导致膨胀度的显著增加(即膨胀体积增加最多达300％或更大)。确实，期望与没有退火步骤的相似加工相比，膨胀度增加至少约50％。因为温度甚至降低100℃就会导致膨胀度显著地降低，所以退火步骤采用的温度不应显著低于3000℃。
本发明进行退火的时间，足以导致片在插入和随后的膨胀时提高膨胀度。一般需要时间1小时或更长，优选1至3小时，且最好在惰性环境中进行。为了获得最大效益，已退火的片状石墨也可进行其它本领域熟知的方法，以提高膨胀度-即在有机还原剂、插入助剂例如有机酸以及表面活性剂的存在下插入，插入后洗涤。而且，为了获得最大效益，可以重复插入步骤。
可在感应炉或其它在石墨化领域熟知和认可的这种设备中进行本发明的退火步骤；此处采用的温度在3000℃范围内，在石墨化处理中采用该范围的高端。
因为观察到，在使用经历插入前退火的石墨制备的蠕虫有时可以聚集成“簇”，其可负面影响单位面积重量的均匀性，所以非常需要有助于形成“自由流动”蠕虫的添加剂。将润滑添加剂加入插入溶液中，促进石墨蠕虫更均匀地分布于压缩设备床(例如压延机站的床，该压延机站常用于将石墨蠕虫压缩或“压延”形成完整的石墨制品)。因此得到的石墨制品具有更高的单位面积重量均匀性和更大的抗张强度。润滑添加剂优选是长链烃，更优选具有至少约10个碳的烃。也可采用具有长链烃基的其它有机化合物，即使存在其它官能团。
更优选润滑添加剂是油，特别是考虑到矿物油不易腐败和发出气味，所以最优选是矿物油，这对于长期贮藏非常重要。注意上面详述的某些膨胀助剂也符合润滑添加剂的定义。当这些物质用作膨胀助剂时，不必在插入剂中加入另外的润滑添加剂。
润滑添加剂在插入剂中的含量至少约1.4pph，更优选至少约1.8pph。虽然润滑添加剂含量的上限不像下限那样重要，但是润滑添加剂的含量大于约4pph水平并没有出现任何显著的额外优势。
这样处理的石墨颗粒有时称为“插入石墨的颗粒”。当暴露于高温，例如至少约160℃，特别约700℃至1200℃以及更高温度下，插入石墨的颗粒按类似折叠的方法，在c向，即垂直于构成石墨颗粒的晶体平面的方向，其原体积膨胀多达约80至1000倍或更多倍。膨胀的石墨颗粒在外观上呈蠕虫状，因此通常称为石墨蠕虫。石墨蠕虫可压缩在一起形成制品，与原来的片状石墨不同，该制品可以形成和切割成各种形状，通过在下文描述的机械撞击变形提供小的横向孔。
按所述制备的石墨材料粘在一起，具有好的处理强度，例如通过模塑或辊-压，被适当地压缩至约0.075-30mm的厚度和约0.1-1.5g/cm3(g/cc)的典型密度。如美国专利第5,902,762号(它通过引用结合于本文中)所描述的那样，可以将大约1.5-30％重量陶瓷添加剂和插入的片状石墨掺混，在最终石墨产品中提供提高的树脂浸渍。该添加剂包括长度为约0.15-1.5mm的陶瓷纤维颗粒。适宜的颗粒宽度为约0.04-0.004mm。该陶瓷纤维颗粒不和石墨反应，不粘附于石墨，在温度达约1100℃，优选约1400℃或更高温度时稳定。适宜的陶瓷纤维颗粒由浸软的石英玻璃纤维、碳和石墨纤维、氧化锆、氮化硼、碳化硅和氧化镁纤维、天然存在的矿物纤维例如硅酸钙纤维、硅酸钙铝纤维、氧化铝纤维等形成。
如上所述，也用树脂处理石墨材料，固化后，吸收的树脂提高该材料的抗湿性和处理强度即劲度，并“固定”片的形态。环氧树脂浸渍的石墨制品内，树脂的量应该足以保证最终固化结构强化和粘着，并且保持或改善强化石墨结构的各向异性导热性。适宜的树脂含量优选为至少约3％重量，更优选约5-35％重量，合适地最高至约60％重量。在本发明的实施中，发现特别有用的树脂包括丙烯酸-、环氧-和酚-基树脂系统、氟-基聚合物或其混合物。适宜的环氧树脂系统包括那些基于双酚A二缩水甘油醚(DGEBA)的树脂系统和其它多官能的树脂系统；可以使用的酚醛树脂包括甲阶酚醛树脂和线型酚醛树脂(novolac)。除树脂外或代替树脂，还可以任选使用纤维和/或盐浸渍柔性石墨。另外，树脂系统可以使用活性或非活性添加剂，以使特性(例如粘性、材料的流动性、疏水性等)改性。
在典型的树脂浸渍步骤中，将柔性石墨材料通过管，并用来自例如喷嘴的树脂系统浸渍，该树脂系统最好经真空室“通过垫吸出”。一般但不是必需，将树脂系统溶剂化，以便施用至柔性石墨中。此后优选干燥该树脂，以降低树脂和树脂浸渍制品的粘性。
或者，本发明的柔性石墨可以利用重新研磨的柔性石墨材料颗粒，而不是刚刚膨胀的石墨蠕虫。该重新研磨材料可以是新形成的材料、回收利用的材料、废材料或任何其它合适的来源。
本发明的方法也可以使用初始材料和回收利用材料的掺混物。
回收利用材料的源材料可以是按上述方法压缩模塑的制品或制品的修剪部分，或者是用例如压延前的辊压缩但还没有用树脂浸渍的片。此外，源材料可以用树脂浸渍但还没有固化，或者用树脂浸渍并固化。源材料也可以是回收利用的柔性石墨燃料电池组件，例如流场板或电极。每种不同来源的石墨可以单独使用，或与天然片状石墨掺混使用。
一旦得到柔性石墨的源材料，就可以通过熟知的方法或装置，例如射流磨、空气碾磨机、掺混机等粉碎源材料，制备颗粒。优选，大多数颗粒具有可通过20目(美国)的直径；更优选主要部分(大于约20％，最优选大于约50％)不能通过80目(美国)。最优选颗粒的粒度不大于约20目。当它为树脂浸渍的时，柔性石墨可能需要冷却，因为它在粉碎时，要避免在粉碎过程中对树脂系统的热损伤。
可以选择粉碎颗粒的尺寸，以便使石墨制品的机械加工性和可成形性与期望的热特性平衡。这样，较小的颗粒将导致产生易于机械加工和/或成形的石墨制品，然而较大的颗粒将导致产生具有较高各向异性，并因此具有更大面内电导率和热导率的石墨制品。
一旦源材料被粉碎(假如已经用树脂浸渍源材料，那么优选将树脂从颗粒中除去)，然后将其再次膨胀。可以利用上述插入和膨胀方法，以及Shane等的美国专利第3,404,061号和Greinke等的美国专利第4,895,713号所述方法进行再膨胀。
一般地，插入后，通过在熔炉中加热插入的颗粒，使颗粒膨胀。在该膨胀步骤期间，可以将插入的天然片状石墨加至回收利用的插入颗粒中。优选在再膨胀步骤期间，将颗粒膨胀到比容为至少约100cc/g至高达约350cc/g或更大。最后，在再膨胀步骤之后，如所述，再膨胀颗粒可以压缩成粘着材料和用树脂浸渍。
按前述方法制备的石墨材料通常也可以称为膨胀石墨的压缩颗粒。因为材料是树脂浸渍的，所以在片用于其预定用途例如电子热处理之前，需要固化片中的树脂。
按照本发明，将按照上述方法制备的树脂浸渍的石墨材料压缩成期望的厚度和形状，通常厚度为约0.35mm至0.5mm，此时浸渍垫的密度为约1.4g/cm3至约1.9g/cm3。
一类连续形成树脂浸渍和压缩的柔性石墨材料的设备，见国际公布第WO00/64808号，其内容通过引用结合到本文中。
在压缩步骤(例如通过压延)之后，将浸渍材料切割成合适大小的片，置于压机内，其中树脂在高温下固化。温度应足以保证在固化压力下强化层状结构，而不会对该结构的热特性产生不利的影响。通常，这需要至少约90℃，一般最高达约200℃。最优选，固化温度为约150℃至200℃。用于固化的压力多少是所用温度的函数，但足以保证强化层状结构，而没有不利地影响该结构的热特性。通常，为了便于制备，利用最小必需压力来强化结构至必需程度。这样的压力通常为至少约7Mpa(相当于约1000磅/英寸2)，不需要超过约35Mpa(相当于约5000psi)，更通常约7至约21Mpa(1000至3000psi)。固化时间可根据所采用的树脂系统、温度和压力而变化，但范围通常为约0.5至2小时。固化完成后，发现复合材料的密度为至少约1.8g/cm3，通常为约1.8g/cm3至2.0g/cm3。
虽然通过压延或模塑形成片，是形成用于实施本发明的石墨材料的最常用方法，但是也可以应用其它形成方法。例如，膨胀石墨颗粒可以压缩模塑成网状或近似网状。因而，如果终端用途要求制品，例如散热器或热扩散器呈现某种形状或轮廓，在树脂浸渍之前或之后，可以将那种形状或轮廓模塑成石墨制品。然后在呈现同样形状的模具中进行固化；的确，在优选的实施方案中，压缩和固化将在同一个模具中进行。然后可以完成最终形状的加工。
本发明的温度和压力固化石墨/树脂复合材料，首次提供具有与铜相当或优于铜的面内导热性的石墨基复合材料，而其重量仅为铜重量的一部分。更具体地讲，本发明的复合材料显示至少约300W/mK的面内热导率和低于约15W/mK的穿透平面(through plane)热导率，更优选低于约10W/mK。这些材料在散热应用方面非常有用，例如在散热器、热扩散器、热管等中，尤其在铜的重量引起不便之处。
上述说明书将使本领域技术人员能够实施本发明。对于技术人员来讲，通过阅读该说明书即显而易见的所有可能变化和修改，本文不再详述。然而，包括在本发明范围内的所有这些修改和变化，将在权利要求书中定义。权利要求书将涵盖任何排列或顺序的指定元素和步骤，所述元素和步骤可有效地符合本发明所预定的目的，除非上下文明确指出相反情况。

Claims (23)

1.一种树脂/石墨层压材料，所述层压材料包含多个树脂浸渍的柔性石墨片，所述柔性石墨在90℃-200℃的温度和1000psi-5000psi的压力下固化。
2.权利要求1的层压材料，其中所述树脂为环氧树脂。
3.权利要求1的层压材料，其中所述多个片在90℃-200℃的温度下压力固化。
4.权利要求1的层压材料，其中所述固化层压材料的密度大于1.85g/cm3。
5.权利要求1的树脂/石墨层压材料，其中所述树脂含量为至少3％重量。
6.权利要求5的树脂/石墨层压材料，其中所述树脂含量不大于60％重量。
7.权利要求1的树脂/石墨层压材料，其中所述柔性石墨片的树脂含量为5％至35％重量。
8.一种树脂/石墨层压材料，所述层压材料包含树脂浸渍的柔性石墨片层，其中所述层压材料在90℃-200℃的温度和1000psi-5000psi的压力下固化，其中所述树脂为环氧树脂。
9.权利要求8的层压材料，所述层压材料在低于200℃的温度和低于35Mpa压力下压力固化。
10.一种电子热处理装置，所述装置包含层状结构，该结构包含树脂浸渍的柔性石墨片，所述柔性石墨在90℃-200℃的温度和1000psi-5000psi的压力下固化。
11.权利要求10的装置，其中所述层状结构在90℃-200℃的温度下固化。
12.权利要求10的装置，所述装置具有性质上各向异性的热导率，且显示至少300W/mK的面内热导率。
13.权利要求12的装置，其中当在具有较高热导率的平面和具有较低热导率的平面之间时，所述各向异性的热导率按至少15的系数变化。
14.权利要求10的装置，其中所述压力固化的层状结构的密度大于1.85g/cm3。
15.权利要求10的电子热处理装置，其中所述柔性石墨片的树脂含量至少为3％重量。
16.一种各向异性电子热处理装置，所述装置在面内方向的热导率大于300W/mC，穿透平面热导率小于10W/mK，并包含在1000psi-5000psi的压力下固化的树脂浸渍的柔性石墨片。
17.权利要求16的电子热处理装置，其中所述树脂是环氧树脂。
18.权利要求16的电子热处理装置，其中所述树脂浸渍柔性石墨片形成密度至少为1.85g/cm3的层状结构。
19.权利要求16的电子热处理装置，其中所述树脂浸渍的柔性石墨片已在90℃-200℃的温度和压力下固化形成层状结构。
20.一种树脂/石墨层压材料，所述层压材料包含多个树脂浸渍的柔性石墨片，所述柔性石墨在至少90℃和至少1000psi的压力下固化。
21.权利要求20的层压材料，其中所述树脂为环氧树脂。
22.权利要求20的层压材料，其中所述多个片在至少90℃的温度下压力固化。
23.权利要求20的层压材料，其中所述固化层压材料的密度大于1.85g/cm3。
CN2004800433619A 2004-04-23 2004-05-26 树脂浸渍的柔性石墨制品 Expired - Fee Related CN1976807B (zh)

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