CN106715329B - 碳复合材料和制造方法 - Google Patents

碳复合材料和制造方法 Download PDF

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CN106715329B
CN106715329B CN201580050462.7A CN201580050462A CN106715329B CN 106715329 B CN106715329 B CN 106715329B CN 201580050462 A CN201580050462 A CN 201580050462A CN 106715329 B CN106715329 B CN 106715329B
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binder
carbon
carbon composite
composition
temperature
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CN106715329A (zh
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徐志跃
赵磊
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Baker Hughes Holdings LLC
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Baker Hughes Inc
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Abstract

一种用于制造碳复合材料的方法包括：在约350℃至约1200℃的温度和约500psi至约30,000psi的压力下，压缩包括碳和粘结剂的复合材料以形成碳复合材料；其中粘结剂包括非金属、金属、金属的合金、或其组合；其中非金属选自由以下组成的组：SiO2、Si、B、B2O3、及其组合；以及金属选自由以下组成的组：铝、铜、钛、镍、钨、铬、铁、锰、锆、铪、钒、铌、钼、锡、铋、锑、铅、镉、硒、及其组合。

Description

碳复合材料和制造方法
相关申请的交叉引用
本申请要求2014年9月29日提交的美国申请No.14/499397的权益，其以引用的方式全部并入本文。
背景技术
石墨为碳的同素异形体并且具有层状平面结构。在每层中，碳原子通过共价键布置成六边形排列或者网状。然而，不同碳层仅仅通过弱的范德华力保持在一起。
由于石墨导热和导电优异、质轻、摩擦系数低并且耐热和耐蚀性高，其已经广泛用于各种应用，包括电子设备、核能、热金属加工、涂料、航天等。然而，石墨没有弹性并且具有低强度，这可能限制其进一步应用。因此，本行业一直接受具有改进的弹性和机械强度的新石墨材料。如果这类材料还具有改进的高温耐蚀性，那将是更有利的。
发明内容
在一个实施例中，一种碳复合材料及其制造方法克服了在本领域中的上述缺陷和其它缺陷。在一个实施例中，一种用于制造碳复合材料的方法包括：在约350℃至约1200℃的温度和约500psi至约30,000psi的压力下，压缩包括碳和粘结剂的复合材料以形成碳复合材料；其中粘结剂包括非金属、金属、金属的合金、或其组合；其中非金属选自由以下组成的组：SiO2、Si、B、B2O3、及其组合；以及金属选自由以下组成的组：铝、铜、钛、镍、钨、铬、铁、锰、锆、铪、钒、铌、钼、锡、铋、锑、铅、镉、硒、及其组合。
在另一实施例中，一种用于制造碳复合材料的方法包括：通过对包括碳和粘结剂的复合材料进行加压形成坯块；以及对坯块进行加热以形成碳复合材料；其中粘结剂包括非金属、金属、金属的合金、或其组合；其中非金属选自由以下组成的组：SiO2、Si、B、B2O3、及其组合；以及金属选自由以下组成的组：铝、铜、钛、镍、钨、铬、铁、锰、锆、铪、钒、铌、钼、锡、铋、锑、铅、镉、硒、及其组合。
还公开了一种用于制造包括碳复合材料的片材的方法。该方法包括热轧包括粘结剂和碳的复合材料；其中粘结剂包括非金属、金属、金属的合金、或其组合；其中非金属选自由以下组成的组：SiO2、Si、B、B2O3、及其组合；金属选自由以下组成的组：铝、铜、钛、镍、钨、铬、铁、锰、锆、铪、钒、铌、钼、锡、铋、锑、铅、镉、硒、及其组合；以及碳选自由以下组成的组：膨胀石墨、可膨胀石墨、天然石墨、合成石墨、及其组合。
一种用于包括制造碳复合材料的粒料的方法包括：挤出包括粘结剂和碳的复合材料；其中粘结剂包括非金属、金属、金属的合金、或其组合；其中非金属选自由以下组成的组：SiO2、Si、B、B2O3、及其组合；金属选自由以下组成的组：铝、铜、钛、镍、钨、铬、铁、锰、锆、铪、钒、铌、钼、锡、铋、锑、铅、镉、硒、及其组合；以及碳选自由以下组成的组：膨胀石墨、可膨胀石墨、天然石墨、合成石墨、及其组合。
碳复合材料包括：具有在碳微结构中的间隙空间的碳微结构；以及粘结剂，该粘结剂设置在间隙空间中的至少某些间隙空间中；其中碳微结构包括在碳微结构内的未填充空隙。
在另一实施例中，碳复合材料包括：至少两种碳微结构；以及设置在至少两种碳微结构之间的粘结相；其中粘结相包括粘结剂，该粘结剂包括非金属、金属、金属的合金、或其组合；其中非金属选自由以下组成的组：SiO2、Si、B、B2O3、及其组合；以及金属选自由以下组成的组：铝、铜、钛、镍、钨、铬、铁、锰、锆、铪、钒、铌、钼、锡、铋、锑、铅、镉、硒、及其组合。
复合材料可以是条、块、片、管形、圆柱形坯料、环形体、粉末或者粒料的形式。
附图说明
以下说明不应以任何方式视为限制性的。参照所附附图，相同的元件以相同的方式编号。
图1是在室温和大气压下共混的包含膨胀石墨和微米大小或者纳米大小的粘结剂的复合材料的扫描电子显微镜(“SEM”)图像；
图2是根据本公开的一个实施例的在高压和高温条件下由膨胀石墨和微米大小或者纳米大小的粘结剂形成的碳复合材料的SEM图像；
图3是根据本公开的另一实施例的碳微结构的SEM图像；
图4是根据本公开的一个实施例的碳复合材料的示意性图示；
图5示出了以下的应力-应变曲线：(A)天然石墨；(B)膨胀石墨；(C)膨胀石墨和微米大小或者纳米大小的粘结剂的混合物，其中在室温和高压下压制样品；(D)根据本公开的一个实施例的在高温和低压下由膨胀石墨和微米大小或者纳米大小的粘结剂压制的碳复合材料(还称为“软复合材料”)；以及(E)根据本公开的另一实施例的在高压和高温条件下由膨胀石墨和微米大小和纳米大小的粘结剂形成的碳复合材料(还称为“硬复合材料”)；
图6示出了碳复合材料在不同负载情况下的环路试验结果；
图7示出了碳复合材料的分别在室温和500°F下试验的滞后结果；
图8是碳复合材料在500℃下暴露于空气25小时之前和在500℃下暴露于空气25小时之后的比较；
图9A是碳复合材料在热冲击之后的照片；图9B图示了关于热冲击的情况；
图10是碳复合材料样品(A)在200°F下暴露于自来水20小时之前和(B)在200°F下暴露于自来水20小时之后，或者(C)在200°F下暴露于自来水3天之后的比较；
图11是碳复合材料样品(A)在200°F下暴露于带有抑制剂的15％HCl溶液20小时之前和(B)在200°F下暴露于带有抑制剂的15％HCl溶液20小时之后，或者(C)在200°F下暴露于15％HCl溶液3天之后的比较；以及
图12示出了碳复合材料在600°F下的密封力松弛试验结果。
具体实施方式
本发明人已发现，与单独的石墨、由相同石墨但是不同粘结剂所形成的复合材料、或者在大气压或者高压下在室温下共混的相同石墨和相同粘结剂的混合物相比，在高温下由石墨和微米大小或者纳米大小的粘结剂形成的碳复合材料具有改进的均衡性能。新的碳复合材料具有优异的弹性。另外，碳复合材料在高温下具有优异的机械性能、耐热性和耐化学性。在另一个有利特征中，复合材料保持石墨的多个出色性能，诸如导热、导电、润滑性等。
不希望受限于理论，据信在机械强度方面的改进通过设置在碳微结构之间的粘结相来实现。在碳微结构之间没有力或者仅仅弱范德华力存在，因此石墨块材料具有弱机械强度。在高温下，微米大小和纳米大小的粘结剂液化以及/或者软化，从而使得在碳微结构中均匀分散。当冷却时，粘结剂固化并且形成粘结相通过机械互锁使碳纳米结构粘结在一起。
进一步不希望受限于理论，对于具有改进的机械强度和改进的弹性两者的复合材料，据信碳微结构自身是在堆叠层之间具有空间的层状结构。粘结剂仅仅将微结构选择性地锁在它们的边界处而不穿透微结构。因此，在微结构内的无界层提供弹性，并且设置在碳微结构之间的粘结相提供机械强度。
碳微结构是在将石墨压缩为高凝状态之后所形成的石墨的在显微镜下的结构。它们包括沿压缩方向堆叠在一起的石墨基面。如此处所使用的，碳基面指基本上平坦、平行的碳原子片或者层，其中每片或者每层具有单一原子厚度。石墨基面还称为碳层。碳微结构通常是平坦并且薄的。它们可以具有不同的形状，并且还可以称为微薄片、微盘等。在一个实施例中，碳微结构基本上彼此平行。
在碳复合材料中存在两类空隙-在碳微结构中的空隙或者间隙空间和在每个单独的碳微结构内的空隙。在碳微结构中的间隙空间具有约0.1微米至约100微米的大小，特别是约1微米至20微米，然而在碳微结构内的空隙更小得多并且通常在约20纳米至约1微米之间，特别是约200纳米至约1微米。空隙或者间隙空间的形状不特别限制。如此处所使用的，空隙或者间隙空间的大小指空隙或者间隙空间的最大尺寸，并且可以通过高分辨率电子或者原子力显微镜技术来确定。
用微米或者纳米大小的粘结剂填充在碳微结构中的间隙空间。例如，粘结剂可以占据在碳微结构中的间隙空间的约10％至约90％。然而，粘结剂不穿透单独的碳微结构，从而在碳微结构内的空隙未被填充，即，没有被任何粘结剂填充。因此，在碳微结构内的碳层通过粘结剂没有锁在一起。通过该机制，碳复合材料，具体地，膨胀碳复合材料的柔性可以被保留。
碳微结构具有约1微米至约200微米，约1微米至约150微米，约1微米至约100微米，约1微米至约50微米，或者约10微米至约20微米的厚度。碳微结构的直径或者最大尺寸为约5微米至约500微米或者约10微米至约500微米。碳微结构的纵摆比可以为约10至约500，约20至约400，或者约25至约350。在一个实施例中，在碳微结构中的碳层之间的距离为约0.3纳米至约1微米。碳微结构可以具有约0.5g/cm3至约3g/cm3，或者约0.1g/cm3至约2g/cm3的密度。
如此处所使用的，石墨包括天然石墨、合成石墨、可膨胀石墨、膨胀石墨、或者包括前述中至少一种的组合。天然石墨是天然形成的石墨。其可以分类为“鳞片”石墨、“脉”石墨和“无定形”石墨。合成石墨是由碳材料制成的制成品。热解石墨是合成石墨的一种形式。可膨胀石墨指具有插入在天然石墨或者合成石墨的各层之间的插层材料的石墨。已经使用多种化学品以对石墨材料进行插层。这些包括酸、氧化剂、卤化物等。示例性插层材料包括硫酸、硝酸、铬酸、硼酸、SO3或者卤化物诸如FeCl3、ZnCl2和SbCl5。当加热时，插层材料从液态或者固态转化为气相。气体形成生成压力，压力将相邻的碳层推开，生成膨胀石墨。膨胀石墨颗粒在外观上呈蠕虫状，并且因此通常被称为蠕虫。
有利地，碳复合材料包括膨胀石墨微结构。与其它形式的石墨相比，膨胀石墨具有高柔性和压缩回弹，以及更大的各向异性。因此，除了理想的机械强度之外，在高压和高温条件下由膨胀石墨和微米大小或者纳米大小的粘结剂形成的复合材料可以具有优异的弹性。
在碳复合材料中，碳微结构通过粘结相保持在一起。粘结相包括粘结剂，该粘结剂通过机械互锁粘结碳微结构。任选地，在粘结剂与碳微结构之间形成界面层。界面层可以包括化学键、固溶体、或其组合。当存在时，化学键、固溶体、或其组合可以加强碳微结构的互锁。应当理解的是碳微结构可以通过机械互锁和化学结合两者而保持在一起。例如，化学键、固溶体、或其组合可以在某些碳微结构与粘结剂之间形成或者用于仅仅在碳的在碳微结构的表面上的一部分之间的具体碳微结构和粘结剂。对于碳微结构或者碳微结构的不形成化学键、固溶体、或其组合的部分，碳微结构可以通过机械互锁来粘结。粘结相的厚度为约0.1微米至约100微米或者约1微米至约20微米。粘结相可以形成使碳微结构粘结在一起的连续或者不连续网络。
示例性粘结剂包括非金属、金属、合金、或者包括前述中至少一种的组合。非金属选自由以下组成的组：SiO2、Si、B、B2O3、及其组合。金属可以是铝、铜、钛、镍、钨、铬、铁、锰、锆、铪、钒、铌、钼、锡、铋、锑、铅、镉和硒。合金包括铝合金、铜合金、钛合金、镍合金、钨合金、铬合金、铁合金、锰合金、锆合金、铪合金、钒合金、铌合金、钼合金、锡合金、铋合金、锑合金、铅合金、镉合金和硒合金。在一个实施例中，粘结剂包括铜、镍、铬、铁、钛、铜的合金、镍的合金、铬的合金、铁的合金、钛的合金、或者包括前述金属或者金属合金中至少一种的组合。示例性合金包括钢、镍-铬基合金诸如Inconel*、以及镍-铜基合金诸如Monel合金。镍-铬基合金可以包含约40％-75％的Ni，约10％-35％的Cr。镍-铬基合金还可以包含约1％至约15％的铁。在镍-铬基合金中还可以包括少量的Mo、Nb、Co、Mn、Cu、Al、Ti、Si、C、S、P、B、或者包括前述中至少一种的组合。镍-铜基合金主要由镍(高达约67％)和铜组成。镍-铜基合金还可以包含少量的铁、锰、碳和硅。这些材料可以成不同的形状，诸如颗粒、纤维和线材。可以使用材料的组合。
用于制造碳复合材料的粘结剂是微米大小或者纳米大小的。在一个实施例中，粘结剂具有约0.05微米至约10微米，特别地，约0.5微米至约5微米，更特别地约0.1微米至约3微米的平均粒度。不希望受限于理论，据信当粘结剂具有在这些范围内的大小时，其在碳微结构中均匀分散。
当界面层存在时，粘结相包括粘结剂层，该粘结剂层包括粘结剂；以及界面层，该界面层使至少两个碳微结构中的一个结合至粘结剂层。在一个实施例中，粘结相包括粘结剂层、使碳微结构中的一个结合至粘结剂层的第一界面层、以及使碳微结构中的另一个结合至粘结剂层的第二界面层。第一界面层和第二界面层可以具有相同或者不同的复合材料。
界面层包括C-金属键、C-B键、C-Si键、C-O-Si键、C-O-金属键、金属碳固溶体、或者包括前述中至少一种的组合。这些键由在碳微结构的表面上的碳和粘结剂形成。
在一个实施例中，界面层包括粘结剂的碳化物。碳化物包括以下的碳化物：铝、钛、镍、钨、铬、铁、锰、锆、铪、钒、铌、钼、或者包括前述中至少一种的组合。通过使对应金属或者金属合金粘结剂与碳微结构的碳原子反应形成这些碳化物。粘结相还可以包括通过使SiO2或者Si与碳微结构的碳反应所形成的SiC，或者通过使B或者B2O3与碳微结构的碳反应所形成的B4C。当使用粘结剂材料的组合时，界面层可以包括这些碳化物的组合。碳化物可以是盐类碳化物诸如碳化铝、共价型碳化物诸如SiC、B4C、间隙型碳化物诸如第4族、第5族和第5族过渡金属的碳化物、或者中间过渡金属碳化物，例如Cr、Mn、Fe、Co和Ni的碳化物。
在另一实施例中，界面层包括碳的固溶体和粘结剂。碳在特定金属基体中或者在特定温度范围下具有溶解度，这有助于使金属相均浸润和粘结到碳微结构上。通过热处理，在金属中碳的高溶解度可以在低温下被保持。这些金属包括Co、Fe、La、Mn、Ni或者Cu。粘结剂层还可以包括固溶体和碳化物的组合。
基于复合材料的总重量，碳复合材料包括约20wt.％至约95wt.％、约20wt.％至约80wt.％、或者约50wt.％至约80wt.％的碳。基于复合材料的总重量，粘结剂以约5wt.％至约75wt.％或者约20wt.％至约50wt.％的量存在。在碳复合材料中，碳相对于粘结剂的重量比为约1∶4至约20∶1，或者约1∶4至约4∶1，或者约1∶1至约4∶1。
图1是在室温和大气压下共混的包含膨胀石墨和微米大小或者纳米大小的粘结剂的复合材料的SEM图像。如图1所示，粘结剂(白色区域)仅仅沉积在膨胀石墨蠕虫中的某些的表面上。
图2是在高压和高温条件下由膨胀石墨和微米大小或者纳米大小的粘结剂形成的碳复合材料的SEM图像。如图2所示，粘结相(亮区域)在膨胀石墨微结构之间均匀地分布(暗区域)。
碳石墨微结构的SEM图像在图3中示出。碳复合材料的一个实施例在图4中图示。如图4所示，复合材料包括碳微结构1和锁紧碳微结构的粘结相2。粘结相2包括粘结剂层3和设置在粘结剂层与碳微结构之间的任选的界面层4。碳复合材料包含在碳微结构1中的间隙空间5。在碳微结构内，存在未填充空隙6。
碳复合材料可以任选地包括填料。示例性填料包括碳纤维、碳黑、云母、黏土、玻璃纤维、陶瓷纤维和陶瓷中空结构。陶瓷材料包括SiC、Si3N4、SiO2、BN等。填料可以以约0.5wt.％至约10wt.％或者约1wt.％至约8wt.％的量存在。
复合材料可以具有任何理想的形状，包括条、块、片、管形、圆柱形坯料、环形体、粉末、粒料或者其它形式，这样可以加工、形成或者另外用于形成有用的制成品。这些形式的大小或者尺寸不特别限制。示例性地，片材具有约10μm至约10cm的厚度和约10mm至约2m的宽度。粉末包括具有约10μm至约1cm的平均大小的颗粒。粒料包括具有约1cm至约5cm的平均大小的颗粒。
用于形成碳复合材料的一种方法是压缩包括碳和微米大小或者纳米大小的粘结剂的组合以通过冷压提供生坯；以及压缩并且对生坯进行加热从而形成碳复合材料。在另一实施例中，可以在室温下对组合进行加压以形成坯块，并且然后在大气压下对坯块进行加热以形成碳复合材料。这些过程可以称为两步法。可替代地，可以压缩包括碳和微米大小或者纳米大小的粘结剂的组合并且直接加热以形成碳复合材料。该过程可以称为一步法。
在组合中，基于组合的总重量，碳诸如石墨以约20wt.％至约95wt.％、约20wt.％至约80wt.％、或者约50wt.％至约80wt.％的量存在。基于组合的总重量，粘结剂以约5wt.％至约75wt.％或者约20wt.％至约50wt.％的量存在。在组合中的石墨可以呈碎片、粉末、小片、薄片等形式。在一个实施例中，石墨呈薄片的形式，该薄片具有约50微米至约5,000微米的直径，优选地约100微米至约300微米。石墨薄片可以具有约1微米至约5微米的厚度。组合的密度为约0.01g/cm3至约0.05g/cm3，约0.01g/cm3至约0.04g/cm3，约0.01g/cm3至约0.03g/cm3或者约0.026g/cm3。可以经由本领域已知的任何合适方法通过共混石墨和微米大小或者纳米大小的粘结剂形成组合。合适方法的示例包括：球磨混合、声学混合、螺条共混、垂直螺杆混合和V型-共混。
参照两步法，冷压意味着在室温下或者在高温下压缩包括石墨微米大小或者纳米大小的粘结剂的组合，只要粘结剂不与石墨微结构明显结合。在一个实施例中，使大于约80wt.％，大于约85wt.％，大于约90wt.％，大于约95wt.％，或者大于约99wt.％的微结构在生坯中不结合。用于形成生坯的压力可以是约500psi至约10ksi，并且温度可以是约20℃至约200℃。在该阶段的减少比(即，生坯的体积相对于组合的体积)为约40％至约80％。生坯的密度为约0.1g/cm3至约5g/cm3，约0.5g/cm3至约3g/cm3，或者约0.5g/cm3至约2g/cm3。
生坯可以在约350℃至约1200℃，特别是约800℃至约1200℃的温度下加热以形成碳复合材料。在一个实施例中，温度为粘结剂的熔点的约±20℃至约±100℃，或者粘结剂的熔点的约±20℃至约±50℃。在另一实施例中，温度高于粘结剂的熔点，例如，比粘结剂的熔点高约20℃至约100℃，或者高约20℃至约50℃。当温度更高时，粘结剂变得不粘胶并且更好流动，并且可能需要较低压力以便粘结剂在碳微结构之间的空隙中均匀地分布。然而，如果温度太高，可能对仪器产生不良影响。
可以根据预定温度表或者斜率来应用温度。加热的手段不特别限制。示例性加热方法包括直流(DC)加热、感应加热、微波加热和放电等离子体烧结(SPS)。在一个实施例中，经由DC加热进行加热。例如，可以利用电流对包括石墨和微米大小或者纳米大小的粘结剂的组合进行充电，电流流过组合，非常快地生成热。任选地，还可以在惰性气氛下，例如，在氩气或者氮气下进行加热。在一个实施例中，在空气的存在下对生坯进行加热。
可以在约500psi至约30,000psi或者约1000psi至约5000psi的压力下进行加热。压力可以是超压或者负压。不希望受限于理论，据信当超压施加于组合时，微米大小或者纳米大小的粘结剂通过渗透被迫进入在碳微结构之间的空隙。当负压施加于组合时，微米大小或者纳米大小的粘结剂还可以通过毛细力被迫进入在碳微结构之间的空隙。
在一个实施例中，不一次性全部施加用于形成碳复合材料的理想压力。在加载生坯之后，首先在室温下或者在低温下将低压施加于复合材料以封闭在复合材料中的大孔。否则，熔融的粘结剂可以流向模具的表面。当温度达到预定最高温度时，可以施加制造碳复合材料所需的理想压力。可以使温度和压力在预定最大温度和预定最大压力下保持约5分钟至约120分钟。在一个实施例中，预定最大温度为粘结剂的熔点的约±20℃至约±100℃，或者粘结剂的熔点的约±20℃至约±50℃。
在该阶段的减少比(即，碳复合材料的体积相对于生坯的体积)为约10％至约70％或者约20％至约40％。通过控制压缩程度可以改变碳复合材料的密度。碳复合材料具有约0.5g/cm3至约10g/cm3，约1g/cm3至约8g/cm3，约1g/cm3至约6g/cm3，约2g/cm3至约5g/cm3，约3g/cm3至约5g/cm3，或者约2g/cm3至约4g/cm3的密度。
或者，也参考两步法，可以在室温和约500psi至30,000psi的压力下首先对组合进行加压以形成坯块；可以在约350℃至约1200℃，特别是约800℃至约1200℃的温度下对生坯进行进一步加热以制造碳复合材料。在一个实施例中，温度为粘结剂的熔点的约±20℃至约±100℃，或者粘结剂的熔点的约±20℃至约±50℃。在另一实施例中，温度可以比粘结剂的熔点高约20℃至约100℃，或者高约20℃至约50℃。可以在大气压下进行加热。
在另一实施例中，可以由石墨和粘结剂直接制成碳复合材料，无需制造生坯。加压和加热可以同时执行。合适的压力和温度可以与此处关于二步法的第二步骤所讨论的相同。
热压是同时施加温度和压力的方法。其可以在一步法和二步法两者中用于制造碳复合材料。
可以通过一步法或者二步法在模具中制造碳复合材料。可以将所获得的碳复合材料进一步加工或者成形以形成条、块、管状、圆柱形坯料或者环形体。加工包括使用例如铣床、锯条、车床、槽刨机、放电加工机床等进行的切割、锯、烧蚀、铣削、表面加工、车削、镗等。可替代地，可以通过选择具有理想形状的模具将碳复合材料直接模制成有用的形状。
还可以经由热轧制成片状材料诸如网、纸、条、带、箔、垫等。在一个实施例中，可以将通过热轧制成的碳复合材料片材进一步进行加热以允许粘结剂使碳微结构有效地粘结在一起。
可以通过挤出制成碳复合材料粒料。例如，可以首先将石墨和微米大小或者纳米大小的粘结剂的组合装载在容器中。然后，通过活塞将组合推入挤出机。挤出温度可以为约350℃至约1200℃或者约800℃至约1200℃。在一个实施例中，温度为粘结剂的熔点的约±20℃至约±100℃，或者粘结剂的熔点的约±20℃至约±50℃。在另一实施例中，挤出温度高于粘结剂的熔点，例如，比粘结剂的熔点高约20℃至约50℃。在一个实施例中，通过挤出获得线材，其可以切割以形成粒料。在另一实施例中，直接从挤出机获得粒料。任选地，后处理可以应用于粒料。例如，如果在挤出期间碳微结构还未被粘结或者粘结不充分，则可以在高于粘结剂的熔融温度的熔炉中对粒料进行加热从而使得粘结剂可以使碳微结构粘结在一起。
可以通过剪切力(切割力)铣削碳复合材料，例如实心件制成碳复合材料粉末。应该注意的是碳复合材料不应被粉碎。另外，在碳微结构内的空隙可能被破坏，因此碳复合材料失去弹性。
碳复合材料具有多个有利性能适用于广泛应用。在特别有利的特征中，通过形成碳复合材料，碳(诸如石墨)的机械强度和弹性体性能两者均得到改进。
为了说明由碳复合材料实现的弹性能量的改进，关于以下样品的应力-应变曲线在图5中示出：(A)天然石墨，(B)膨胀石墨，(C)在室温和大气压下形成的膨胀石墨和微米大小或者纳米大小的粘结剂的混合物，(D)通过在高温和低压诸如大气压下形成的膨胀石墨和微米大小或者纳米大小的粘结剂的混合物(“软碳复合材料”)；以及(E)在高压和高温条件下由膨胀石墨和微米大小和纳米大小的粘结剂形成的碳复合材料(“硬碳复合材料”)。关于天然石墨，通过在高压下将天然石墨压缩在钢模中制成样品。膨胀石墨样品也按相似方式制成。
如图5所示，天然石墨具有非常低的弹性能量(在应力-应变曲线下的区域)并且非常脆。膨胀石墨的弹性能量和在室温和高压下压制的膨胀石墨和微米大小或者纳米大小的粘结剂的混合物的弹性能量高于天然石墨的弹性能量。相反，与单独的天然石墨、单独的膨胀石墨、以及在室温和高压下压制的膨胀石墨和粘结剂的混合物相比，本公开的硬碳复合材料和软碳复合材料两者均表现出明显改进的弹性，显示出弹性能量显著增加。在一个实施例中，本公开的碳复合材料具有大于约4％，大于约6％或者在约4％与约40％之间的弹性伸长率。
碳复合材料的弹性在图6和图7中进一步图示。图6示出了碳复合材料在不同负载情况下的环路试验结果。图7示出了碳复合材料分别在室温和500°F下试验的滞后结果。如图7所示，碳复合材料的弹性在500°F下被保持。
除了机械强度和弹性之外，碳复合材料还可以在高温下具有优异的热稳定性。图8是碳复合材料在500℃下暴露于空气25小时之前和在500℃下暴露于空气25小时之后的比较。图9A是碳复合材料样品在热冲击8小时之后的照片。关于热冲击的条件在图9B中示出。如图8和图9A所示，碳复合材料样品在500℃下暴露于空气25小时之前或者在热冲击之后不存在变化。碳复合材料可以具有高耐热性，其中操作温度的范围从约-65°F高达约1200°F，特别地高达约1100°F，并且更特别地约1000°F。
碳复合材料还可以在高温下具有优异的耐化学性。在一个实施例中，复合材料化学上耐水、油、卤水和酸，其中耐抗率从良好至优异。在一个实施例中，在高温和高压下，例如，约68°F至约1200°F，或者约68°F至约1000°F，或者约68°F至约750°F在湿条件下，包括碱性和酸性条件下，可以连续使用碳复合材料。因此，当长时间暴露于化学剂(例如，水、盐水、碳氢化合物、酸诸如HCl、溶剂诸如甲苯等)时，甚至在高达200°F的高温下，以及在高压(大于大气压)下，碳复合材料在延长的时间段内抵抗溶胀和性能的降解。碳复合材料的耐化学性在图10和图11中图示。图10是碳复合材料样品在200°F下暴露于自来水20小时之前和在200°F下暴露于自来水20小时之后，或者在200°F下暴露于自来水3天之后的比较。如图10所示，对于样品而言不存在变化。图11是碳复合材料样品在200°F下暴露于带有抑制剂的15％HCl溶液20小时之前和在200°F下暴露于带有抑制剂的15％HCl溶液20小时之后，或者在200°F下暴露于15％HCl溶液3天之后的比较。同样，对于碳复合材料样品而言不存在变化。
碳复合材料是中硬至特硬，其中硬度从以肖氏A计约50至以肖氏D约75。
如进一步有利的特征，碳复合材料在高温下具有稳定的密封力。在恒定压缩应变下部件的应力延迟已知为压缩应力松弛。还已知为密封力松弛试验的压缩应力松弛试验在两块板之间的压缩作用下测量由密封件或者O形环施加的密封力。通过根据时间、温度和环境的函数测量样品的密封力衰减，为预报材料的使用寿命提供决定性信息。图12示出了碳复合材料样品在600°F下的密封力松弛试验结果。如图12所示，碳复合材料的密封力在高温下是稳定的。在一个实施例中，使复合材料的样品的在15％应变和600°F下的密封力在约5800psi下维持至少20分钟，没有松弛。
碳复合材料有助于制备用于很多种应用的制品，包括但不限于，电子设备、核能、热金属加工、涂料、航天、汽车、石油和天然气和航海应用。示例性制品包括密封件、轴承、轴承座、包装件、阀门、发动机、反应器、冷却系统和散热器。因此，在一个实施例中，制品包括碳复合材料。碳复合材料可以用于形成制品的所有或者一部分。
制品可以是井下元件。示例性制品包括密封件、密封孔保护件、刷拭元件保护件、压裂塞的部件、桥塞、压缩包装元件(初级密封件)、膨胀包装元件(ARC密封件)、O形环、结合密封件、子弹密封件、地下安全阀(SSSV)动态密封件、SSSV挡板密封件、V形环、支承环、钻头密封件或者ESP密封件。在一个实施例中，制品为包装件、密封件或者O形环。
本文所公开的所有范围包括端点，并且端点彼此独立组合。本文所使用的后缀“(s)”意在包括其所修饰的术语的单数和复数，因此包括至少一个该术语(例如，着色剂(s)包括至少一种着色剂)。“或者”意味着“以及/或者”。“任选的”或者“任选地”意味着之后所描述的事件或者情况可能发生或者可能不发生，并且该说明包括发生该事件的情形和不发生该事件的情形。如此处所使用的，“组合”包括共混物、混合物、合金、反应产物等。“其组合”意味着“包括所列项目和任选地未列出的类似项目中的一个或者多个项目”。所有参考文献以引用的方式并入本文。
在描述本发明的上下文中(特别是在以下权利要求书的上下文中)，除非本文另有指明或者上下文明显矛盾，术语“一”、“一个”和“该”和相似指示物的使用被解释为覆盖单数和复数两种。进一步地，应该进一步注意的是，术语“第一”、“第二”等在此并不表示任何顺序、数量或者重要性，而是用于区分一个元件与另一个元件。与数量结合使用的修饰语“约”包括所指出的值，并且具有上下文所示的意义(例如，其包括与具体数量的测量相关的误差程度)。
虽然已为说明的目的阐明了典型的实施例，但是前述说明不应被认为是对本文范围的限制。因此，在不背离本文的精神和范围的情况下，本领域技术人员可以做出各种修改、调整以及替换。

Claims (10)

1.一种用于制造碳复合材料的方法，所述方法包括：
在低于500psi至30,000psi的第一压力下并且在低于预定最大温度的第一温度下，对包括膨胀石墨和粘结剂的组合物进行加压；
在所述预定最大温度和500psi至30,000psi的压力下对所述组合物进行加压以形成所述碳复合材料，所述预定最大温度为所述粘结剂的熔点的±20℃至±100℃；
其中所述粘结剂包括以下的一种或者多种：SiO2、Si、B、B2O3、硒，并且
其中所述组合物包括20wt.％至95wt.％的所述膨胀石墨、5wt.％至80wt.％的所述粘结剂，以及任选地以下的一种或者多种：碳纤维、碳黑、云母、黏土、玻璃纤维、陶瓷纤维、或者陶瓷中空结构。
2.一种用于制造碳复合材料的方法，所述方法包括：
通过对包括膨胀石墨和粘结剂的组合物进行加压形成坯块；以及
对所述坯块进行加热以形成所述碳复合材料；
其中所述粘结剂包括以下的一种或者多种：SiO2、Si、B、B2O3、硒；
其中形成所述坯块包括在500psi至10ksi的压力和20℃至200℃的温度下对所述组合物进行加压，从而使得所述坯块的体积相对于所述组合物的体积为40％至80％；以及其中在350℃至1200℃的温度和500psi至30,000psi的压力下进行所述加热，从而使得所述碳复合材料的体积相对于所述坯块的体积为10％至70％，并且
其中所述组合物包括20wt.％至95wt.％的所述膨胀石墨、5wt.％至80wt.％的所述粘结剂，以及任选地以下的一种或者多种：碳纤维、碳黑、云母、黏土、玻璃纤维、陶瓷纤维、或者陶瓷中空结构。
3.根据权利要求2所述的方法，其中所述加热包括：
在低于500psi至30,000psi的第一压力下并且在低于预定最大温度的第一温度下对所述坯块进行加压，所述预定最大温度为所述粘结剂的熔点的±20℃至±100℃；以及
在所述预定最大温度和500psi至30,000psi的压力下对所述坯块进行加压。
4.根据权利要求1所述的方法，其中所述组合物通过以下的一种或者多种进行加热：直流加热、感应加热、微波加热、或者放电等离子体烧结。
5.根据权利要求1至4中任一项所述的方法，其中所述粘结剂具有0.05微米至10微米的大小。
6.根据权利要求1至4中任一项所述的方法，其中所述碳复合材料在模具中制成以形成包括所述碳复合材料的条、块、片、管形、圆柱形坯料或者环形体。
7.根据权利要求1至4中任一项所述的方法，进一步包括加工或者成形所述碳复合材料以形成条、块、片、管形、圆柱形坯料或者环形体。
8.根据权利要求1至4中任一项所述的方法，进一步包括研磨所述碳复合材料以形成粉末。
9.一种用于制造包括碳复合材料的片材的方法，所述方法包括：
热轧包括粘结剂和膨胀石墨的组合物以形成片材；
其中所述粘结剂包括以下的一种或者多种：SiO2、Si、B、B2O3、硒；以及
在热轧之后将所述片材加热至高于所述粘结剂的熔点的温度，并且
其中所述组合物包括20wt.％至95wt.％的所述膨胀石墨、5wt.％至80wt.％的所述粘结剂，以及任选地以下的一种或者多种：碳纤维、碳黑、云母、黏土、玻璃纤维、陶瓷纤维、或者陶瓷中空结构。
10.一种用于制造包括碳复合材料的粒料的方法，所述方法包括：
挤出包括粘结剂和膨胀石墨的组合物以形成粒料；
其中所述粘结剂包括以下的一种或者多种：SiO2、Si、B、B2O3、硒；以及
在挤出之后将所述粒料加热至高于所述粘结剂的熔点的温度，并且
其中所述组合物包括20wt.％至95wt.％的所述膨胀石墨、5wt.％至80wt.％的所述粘结剂，以及任选地以下的一种或者多种：碳纤维、碳黑、云母、黏土、玻璃纤维、陶瓷纤维、或者陶瓷中空结构。
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