CN107651667A - 包含碳纳米管的固体碳产物以及其形成方法 - Google Patents

包含碳纳米管的固体碳产物以及其形成方法 Download PDF

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CN107651667A
CN107651667A CN201710778634.3A CN201710778634A CN107651667A CN 107651667 A CN107651667 A CN 107651667A CN 201710778634 A CN201710778634 A CN 201710778634A CN 107651667 A CN107651667 A CN 107651667A
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sintering solid
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D·B·诺伊斯
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Abstract

形成固体碳产物的方法包括将多个纳米管设置于压力机中并且将热量施加于所述多个碳纳米管上以形成所述固体碳产物。进一步加工可包括烧结所述固体碳产物，以形成多个共价结合的碳纳米管。所述固体碳产物在所述碳纳米管之间包括多个具有小于约100 nm的中值最小尺寸的孔隙。一些方法包括压缩包含碳纳米管的材料，在非反应性环境中加热所压缩的材料以在相邻碳纳米管之间形成共价键以形成烧结的固体碳产物，以及将所述烧结的固体碳产物冷却至碳纳米管的碳不会氧化的温度，之后去除所得的固体碳产物以用于进一步加工、运输或使用。

Description

包含碳纳米管的固体碳产物以及其形成方法
优先权声明
本申请要求2012年7月12日提交的美国临时专利申请序列号61/671,022“SolidCarbon Products Comprising Carbon Nanotubes and Methods of Forming Same”的申请日的权益，其公开内容在此以引用的方式整体并入本文。
领域
本公开的实施方案涉及用于由碳纳米管形成固体碳产物的方法和系统，所述固体碳产物包含不同类型的碳纳米管的混合物以及碳纳米管与其它物质的混合物。
背景
各自以Dallas B.Noyes名义公布的以下文献公开了关于本申请的背景信息并且各自在此均以引用的方式整体并入本文：
1. 2012年2月9日公布的美国专利公布号2012/0034150A1；
2. 2013年3月15日提交的国际申请号PCT/US2013/000071；
3. 2013年3月15日提交的国际申请号PCT/US2013/000072；
4. 2013年3月15日提交的国际申请号PCT/US2013/000073；
5. 2013年3月15日提交的国际申请号PCT/US2013/000075；
6. 2013年3月15日提交的国际申请号PCT/US2013/000076；
7. 2013年3月15日提交的国际申请号PCT/US2013/000077；
8. 2013年3月15日提交的国际申请号PCT/US2013/000078；
9. 2013年3月15日提交的国际申请号PCT/US2013/000079；以及
10. 2013年3月15日提交的国际申请号PCT/US2013/000081。
在工程材料中使用CNT(“碳纳米管”)的常规方法一般依赖于将CNT嵌入到基体材料中。CNT目前是使用金属、塑料、热固性树脂、环氧树脂以及其它物质作为保持CNT在一起的基体来在各种各样的复合结构中加工，从而创建固体物体。所述CNT用作改进材料性质的增强材料。在基体中使用碳纳米管的典型目的是为了增加强度、减小重量或者提高复合物的导电性和导热性。
制造主要由碳纳米管构成的材料的方法包括将碳纳米管纺织到纤维中并且制成“巴克石(buckyrock)”。2005年5月31日授权并且名称为“Entangled single-wall carbonnanotube solid material and methods for making same”的美国专利号6,899,945公开了一种用于制造巴克石的方法。巴克石为包括单壁CNT缠结网络的三维、固体块状材料。巴克石为机械上强度大的、坚韧且抗冲击的，其中堆积密度为约0.72g/cm3(参见美国专利号6,899,945的实施例3)。巴克石形式的单壁CNT以不规则网络存在。CNT的不规则网络似乎通过CNT之间的范德华力并且通过CNT的物理缠结或干扰来保持在适当位置。一种类型的巴克石通过在水中形成CNT浆液，从所述浆液中缓慢除去水以生成糊料并且允许所述糊料非常缓慢地干燥来制成，以使得在溶剂蒸发期间维持所述糊料的CNT网络。巴克石可用于需要具有机械强度、韧性和抗冲击性的轻质材料的各种应用中，如弹道防护系统。
尽管包含CNT的常规材料具有令人感兴趣的和有用的性质，但是构成这些材料的单独的CNT具有显著不同的性质。因此，产生具有可与单独CNT的性质更加相当的性质的材料是有利的。
公开内容
形成固体碳产物的方法包括压力压实法如挤压、模压、辊压、注射模塑等，以形成包含多个碳纳米管的固体形状。碳纳米管可任选地与其它物质混合。此类固体形状可通过在惰性气氛下加热至足以烧结至少一些CNT的温度以使得在相邻CNT之间形成共价键来进一步加工。所述方法可包括形成多个纳米管，将所述多个纳米管设置于压力机中，以及将热量和压力施加于多个碳纳米管以形成固体碳产物。在烧结时，所得的材料为具有两种或更多种CNT(它们之间具有共价键)的新型物质组合物。
固体碳产物无论是否烧结，均包含限定遍及所述材料的多个孔隙的互锁CNT。填隙孔隙的尺寸可通过多种方法进行控制，所述方法包括控制构成固体碳产物的CNT的特征直径、纳入在从固体碳产物中去除时可生成孔隙的其它材料、以及在其下形成固体碳产物的压力和温度。
烧结的固体碳产物包含多个共价结合的碳纳米管。一些方法包括压缩含有碳纳米管的材料，在非反应性环境中加热所压缩的材料以在相邻碳纳米管之间形成化学键并且形成结合的碳纳米管结构，以及将结合的碳纳米管结构冷却至碳纳米管的碳不会与氧气反应的温度。
其它方法包括首先通过压缩含有碳纳米管的材料来形成固体碳产物并且随后将所得的固体碳产物放置于烧结条件下。烧结条件可包括惰性环境，如真空或惰性气氛(例如，氩气或氦气)。将固体碳产物加热至所需的温度，持续一段时间，以在相邻CNT之间诱导共价结合，之后将物体冷却至低于碳在空气中的氧化温度。然后可将所述产物从烧结条件中去除。
此类方法可包括多种标准工业加工方法中的任一种，如挤压、模压、注射模塑、等静压以及辊压。固体碳产物的烧结可在多种设备中进行，如常用于烧结的粉末冶金和烧结的陶瓷加工中的设备。固体碳产物的烧结可包括多种手段中的任一种，所述手段包括感应加热、等离子体电弧放电、高温高压釜和退火炉、以及其它相关装置及本领域中已知的方法。
附图简述
图1至图4为碳纳米管的简化图；
图5至图9为用于形成固体碳产物的压力机的简化截面图；
图10和图11为示出连接的碳纳米管的结构的简化图；以及
图12为示出通过压实和烧结形成的固体碳产物的堆积密度的图。
实施本发明的方式
本公开包括通过将压力施加于碳纳米管来形成固体碳产物的方法以及用于将热量施加于通过此类方法形成的固体产物的方法。固体碳产物可适用于以下各种应用，如过滤器、反应器、电组件(例如，电极、导线、电池)、结构(例如，梁、框、管道)、紧固件、模塑的零件(例如，齿轮、衬套、活塞、涡轮、涡轮叶片、发动机缸体)等。此类固体碳产物可相对于常规材料表现出增强的性质(例如，强度、导电性或导热性、比表面积、孔隙率等)。本公开包括含有在压力下成形为固体形状的多个CNT的一类新材料。当此类固体形状被烧结时，在所述CNT的至少一些之间形成共价键，从而形成固体形状。此材料具有众多有用的性质。
如本文所用的术语“烧结”意指并且包括在足以在至少一些相邻CNT之间、在它们的至少一些接触点之间诱导碳-碳共价键的温度和压力下退火或热解CNT。
如本文所用的术语“催化剂残留物”意指并且包括与CNT有关的任何非碳元素。此类非碳元素可包括在CNT生长尖端中的金属催化剂的纳米颗粒以及无规地或以其它方式分布遍及CNT和其表面上的金属原子或原子团。
如本文所用的术语“生坯”意指并且包括并未烧结的任何固体碳产物。
CNT可通过本领域已知的任何方法形成，所述方法包括电弧放电、激光烧蚀、烃类热解、Boudouard反应、Bosch反应以及相关的碳氧化还原反应、或湿式化学方法(例如，Diels-Alder反应)。本文所述的方法可应用于碳纳米管，无论是什么制造或合成方法。
CNT可作为具有直径范围从几纳米至100纳米或更大的不同直径的单壁及多壁碳纳米管出现。CNT可具有各种各样的长度和形态，并且可作为基本上平行的“林状物(forest)”、无规缠结的实体或者结构化聚集体的“枕状物(pillow)”出现。CNT还可形成或被混合来形成具有不同组合和以上特征分布(壁的数目、直径、长度、形态、定向等)的CNT的很多不同混合物。不同混合物当混合并用于形成本文所述的固体碳产物时，可产生具有特别工程化的性质的产物。例如，构成固体碳产物的CNT之间的填隙空间的中值孔隙尺寸通常与用于形成固体碳产物的CNT的特征性直径大致成比例。中值孔隙尺寸影响固体碳产物的总体孔隙率和密度。
在图1至图4中示出不同的CNT特征和构造。图1示出单壁CNT100，其中碳原子102以单一圆柱体形式连接在一起。碳原子102共价结合成六方晶格，并且因此形成表现为卷成管形式的单一石墨层的CNT 100。CNT 100可被概念化为“卷起的石墨烯片”格网图案，其被定向以使得碳原子102以相对于CNT 100的轴线的不同角度盘旋。所述角度被称为“手性”并且常见的命名形式包括扶手椅形和Z字形，如Mildred S.Dresselhaus&Phaedon Avouris,Introduction to Carbon Materials Research,in Carbon Nanotubes:Synthesis,Structure,Properties,and Applications,1,6(Mildred S.Dresselhaus,GeneDresselhaus,&Phaedon Avouris,编辑,2001)中所述，所述文献的全部内容以引用的方式并入本文。很多手性都是可能的；具有不同手性的CNT 100可表现出不同的性质(例如，CNT100可具有半导体或金属电学性质)。
CNT 100具有与圆周横截面中的碳原子102的数目相关的内径。图1所示的CNT 100具有Z字形图案，如在CNT 100末端所示。直径还可能影响CNT 100的性质。单壁CNT 100可具有很多不同的直径，如从大约1.0nm(纳米)至10nm或更大。CNT 100可具有的长度为约10nm至约1μm(微米)，如约20nm至约500nm或约50nm至约100nm。CNT 100通常具有约100:1至1000:1或更大的纵横比(即，CNT的长度与CNT的直径之比)。
具有多于一个壁的CNT被称为多壁CNT。图2示意性地示出具有通常围绕公共轴线同心地布置的多个石墨层122、124、126、128的多壁CNT 120。双壁和三壁碳纳米管偶尔被描述为不同的类别；然而，它们可被视为最小类别的多壁CNT 120。多壁CNT 120的直径范围可为大约3nm至大大超过100nm。具有约40nm或更大的外径的多壁CNT120在本领域有时被称为碳纳米纤维。
图3示出两种形式的多壁CNT 140、150。在CNT 140中，一个单壁CNT 142设置于较大直径的单壁CNT 144内，所述单壁CNT 144又可设置于另一个甚至更大直径的单壁CNT146内。此CNT 140与图2所示的CNT 120类似，但是包括三个而不是四个单壁CNT 142、144、146。图3所示出的另一种形式的多壁CNT为CNT 150，它可被概念化为卷成管的单个石墨烯片152。
图4示意性地示出具有连接的纳米芽182的单壁CNT 180。纳米芽182具有与球形巴克敏斯特富勒烯(buckminsterfullerene)(“巴克球(buckyball)”)类似的结构，并且通过碳碳键与单壁CNT 180结合。如通过图4所示的结构表明，可对单壁CNT 180的壁或者对多壁CNT的外壁进行修饰。在纳米芽182与CNT 180之间的结合点处，碳双键可破坏并且在CNT180的壁中形成“孔洞”。这些孔洞可能影响CNT 180的机械和电学性质。在单壁CNT中，当与未修饰的圆柱形CNT相比时，这些孔洞可能引入相对的弱点。在多壁CNT中，外壁可受到影响，但是任何内壁可能保持完整。
碳纳米管通常以使催化剂纳米颗粒嵌入碳纳米管的生长尖端的这种方式形成。此催化剂可任选地通过轻度洗涤(例如，通过酸洗涤)来去除。在不受到具体理论约束的情况下，认为如果所述催化剂保留在适当位置，则催化剂原子在烧结工艺期间被动员，并且可迁移到碳纳米管的表面上或其气孔内。此工艺可将催化剂原子无规地、均匀地或以其它方式分散遍及固体碳产物团块并且对固体碳产物的性质可具有显著的影响。例如，催化剂材料可能影响导电性或催化其它化学反应的能力。
催化剂颗粒还可被选来催化除形成固体碳之外的其它反应。催化剂颗粒可为任何材料，如过渡金属或其任何化合物或合金。例如，催化剂颗粒可包括镍、氧化钒、钯、铂、金、钌、铑、铱等。因为催化剂颗粒连接至CNT或另外与CNT相关联，所以每种催化剂颗粒可与其它催化剂颗粒物理地分离。因此，催化剂颗粒的表面积可以比具有相同质量的催化剂的散装材料大得多。连接至CNT的催化剂颗粒因此对于减少催化反应所需要的催化剂材料的量以及对于降低催化剂成本可为特别有利的。在很多应用中用作催化剂的压缩的固体碳产物可得益于CNT和嵌入在CNT生长尖端中的金属催化剂颗粒二者的催化活性。
用于本文的方法中的CNT可为单壁CNT、多壁CNT或其组合，包括CNT的双模尺寸的组合、单壁和多壁CNT的混合物、不同大小的单壁CNT的混合物、不同大小的多壁CNT的混合物等。所述CNT可为如薄片模塑的化合物、压力模塑的化合物或者可倾倒的液体的形式。所述CNT可设置于压力机或构造并配置来向所述材料提供压力的任何其它装置内。所述压力机可包括挤压模、模具、腔体等。
例如，在图5所示的压力机200中，CNT 202可置于配置来将材料输送穿过挤压模206的料斗204中。压力机200包括挤压筒208，其具有连接至驱动电机212的螺旋机构210，以将CNT 202携带穿过挤压筒208至挤压模206。挤压筒208可任选地包括用于在CNT 202经过挤压筒208时加热CNT 202的装置。挤压模206具有一个开口，其具有与有待在压力机200中形成的零件的截面形状相对应的形状。根据所需物体的形状，挤压模206可为可更换的。示出了挤压模的一些可能的形状206a、206b、206c。例如，挤压模206可具有成形为像圆形、正多边形、不规则多边形、I形梁等形状的开口。挤压模206可被构造来形成多种形状和大小的挤压的CNT的物体：对称或不对称的、小到大的。CNT 202可任选与压力机200之前或之内的另一种材料混合。
在一些实施方案中并且如图6的压力机220中所示，将CNT 202置于被配置来将材料输送到模具226的料斗224中。压力机220包括圆筒228，其具有连接至驱动电机232的螺旋机构230，以将CNT 202携带穿过圆筒228至模具226。圆筒228可任选地包括用于在CNT 202经过圆筒228时加热CNT 202的装置。模具226具有一个开口，其具有与有待在压力机220中形成的零件的外部形状相对应的内部形状。根据所需物体的形状，模具226可为可更换的。示出了模具的一些可能的形状226a和226b。例如，模具226可具有螺旋或螺旋桨的形状。CNT202可任选地与压力机200之前或之内的另一种材料混合，以改进流动性、脱模性或其它加工性质。此类材料可随后通过适合的手段如蚀刻、热解、蒸发等来去除。所得的固体碳产物可大体上不含另外的材料并且可基本上包含碳，并且在一些实施方案中包含残留的催化剂材料。
在其它实施方案中并且如图7的压力机240中所示，将CNT 202置于具有限定有待形成的产物的外部的内部形状的主体244中。可将CNT 202置于由主体244所包围的两个活塞246、248之间。主体244可具有限定内部腔室并且被配置来允许活塞246、248自由滑动的壁250。在其它实施方案中，单个活塞可被配置来抵靠着主体压制CNT。
在如图8的压力机260中所示的一个实施方案中，将CNT 202置于具有与有待形成的产物形状相对应的一个或多个表面的模具部分262中。一个或多个另外的模具部分264被配置来在通过活塞266、268压制时抵靠着模具部分262压制CNT 202，如图9所示。总之，模具部分262、264限定有待形成的产物的形状。
施加压力以使CNT成形为粘性“生坯”主体。例如，如图5和图6所示的螺旋机构210、230在CNT 202经过压力机200、220时将压力施加于CNT 202上。通过图5所示的冲模206进行的挤压可为连续的(理论上产生无限长的产物)或半连续的(产生很多部件)。挤压的材料的实例包括线材、管材、结构形状等。如在图6所示的压力机220中的模塑为通过使用刚性图案(模具226)来使柔韧的原材料(例如，CNT 202)成形的制造工艺。CNT 202采用所述模具的形状。
图8和图9所示的活塞266、268压向CNT 202，从而使CNT 202成形为生坯主体270。所形成的所得生坯主体270可通过相对弱的力保持在一起，以使得生坯主体270可容易进一步成形(例如，机器加工、钻孔等)，但在处理时仍保持其形状。生坯主体270的CNT可各自与一种或多种其它CNT物理地接触。
将热量施加于生坯主体，以将CNT连接在一起成为更有粘性的主体，其中至少一些相邻的CNT在彼此之间形成共价键。例如，可以约1℃/min至约50℃/min的加热速率将CNT加热到至少1500℃、1800℃、2100℃、2400℃、2500℃、2700℃或甚至仅低于碳的升华温度(大约3600℃)的温度。还可在施加热量的同时、之前或之后施加压力。例如，CNT可在10至1000MPa，如30MPa、60MPa、250MPa、500MPa或750Mpa下进行压制。生坯主体可在退火炉中经受加热的惰性环境，如氦气或氩气。烧结的CNT(即，使它们在无氧环境中经受加热)在接触时在CNT之间明显形成共价键。CNT的烧结通常出现在非氧化环境中，如真空或惰性气氛，以使得碳纳米管在烧结期间不会被氧化。在接触表面处诱导化学结合的烧结的CNT在与生坯材料相比时可改进固体结构产物中所需的材料性质，如强度、韧性、抗冲击性、导电性或导热性。CNT也可在另外的成分如形成复合结构的金属或陶瓷、有助于处理的润滑剂或粘合剂(例如，水、乙醇、聚乙烯醇、煤、焦油沥青等)存在下烧结。材料可作为粉末、切屑、液体等引入。适合的金属可包括例如铁、铝、钛、锑、巴氏金属(Babbitt metal)等。适合的陶瓷可包括诸如氧化物(例如，氧化铝、氧化铍、二氧化铈、氧化锆等)、碳化物、硼化物、氮化物、硅化物等的材料。在其中存在除CNT之外的材料的实施方案中，在至少一些CNT之间出现共价键，并且另外的材料可以变得被锁入到CNT的基体中。
在烧结的主体中的CNT具有彼此连接的化学键。通常比物理结合更强的化学键对CNT的集合赋予不同于物理结合的性质。也就是说，烧结的主体可具有比形成它的生坯主体更高的强度、导热性、导电性或其它性质。
当单壁CNT与相邻的单壁CNT共价结合时，在一些碳碳键破坏时可在CNT的表面上形成孔洞，从而改变每个单壁CNT的机械和电学性质。然而，烧结的单壁CNT通常在如强度、韧性、抗冲击性、导电性以及导热性的性质方面仍可超过未烧结的单壁CNT。在多壁CNT的情况下，通常仅外管的壁改变；而内壁保持完整。因此，在例如挤压和模塑工艺中使用多壁和双模尺寸的CNT可产生具有在很多方面超过单壁CNT的实际限制的性质的固体结构。
烧结似乎在CNT的壁之间的接触点处引起共价键的形成。即，任何给定的CNT可在两个CNT的物理接触点处与相邻CNT“交联”。已经过烧结的任何给定的CNT可与众多其它CNT(单壁CNT和多壁CNT两者)共价结合。这增加了所得结构的强度，因为CNT在结合点处不会滑动或滑开。未烧结的CNT(例如，在巴克石中)可相对于彼此滑动。因为通过烧结所引起的共价结合可出现于CNT团块的多个位点，所以烧结的主体具有比CNT的常规聚集体显著增加的强度、韧性、抗冲击性以及传导性。
图10示意性地示出通过烧结产生的两个共价结合的CNT 280、282的交联结构。当烧结时，CNT 280、282在其接触点284处共价结合。每个CNT可与在烧结期间与其接触的一些或所有其它CNT形成共价键。由于在多壁CNT中的内部分层，多壁CNT的单个壁之间的共价结合可能在烧结条件下出现。然而，此共价结合尚未在测试中获得确认。维持CNT在烧结工艺中的加热和任选加压，直到出现所需的交联水平为止。然后将烧结的CNT冷却至CNT将不会与氧气自发地反应的温度。此后，可将混合物暴露于空气中，以便进一步加工、保存、包装、运输、销售等。
在另一个实施方案中，在反应性环境中(例如，在氧气、氢气、烃类和/或另一种材料存在下)加热CNT混合物。在此实施方案中，按需要维持热量和压力，直到反应性环境中的反应物已彼此反应或者与CNT反应。然后冷却所述产物。在这个过程中，反应物可在CNT中形成另外的孔洞或气孔，从而增加烧结的主体的比表面积。可选地，反应物可使材料沉积于CNT的表面上而不影响下层的CNT结构。
在另一个实施方案中，最初在非反应性环境中(例如，在真空中、在氦气存在下或者在氩气存在下)加热并烧结CNT混合物。在烧结之后，将热量和压力改变成适合的反应条件并且将反应物添加到所述环境中。此类反应物可包括多种金属(作为液体或蒸气)、金属羰基合物、硅烷或烃类。反应物彼此或者与CNT的碳的反应可填充CNT晶格与反应产物的一些或所有间隙。在一些情况下，可在烧结期间进行使用另外的反应物的此类加工，但是也可单独地进行此类加工。维持热量和压力，直到出现所需的反应水平(在CNT内的交联和CNT与反应物之间的反应二者)为止。然后将反应混合物冷却并从反应环境中去除，以用于进一步加工、保存、包装、运输、销售等。
图11示意性地示出共价结合的CNT 302的团块300。CNT 302通过烧结经由共同的接触点304与其它CNT 302(多壁或单壁CNT)结合，从而使聚集体结合在一起成为高度交联的结构。所得的结合可形成具有显著强度、韧性、抗冲击性以及导电性和导热性的材料。
在烧结工艺期间，生坯主体可收缩，从而与CNT中的孔隙尺寸的减小相对应。然而，烧结主体可由于每个CNT的孔隙率(即，CNT的中心)和在CNT之间和之内的孔隙而保持为多孔的。烧结的主体可具有中值最小尺寸小于约1μm、小于约500nm、小于约100nm、小于约50nm或甚至小于约10nm的气孔或孔隙。即，每个孔隙可具有在不同方向上测量的两个或更多个尺寸(例如，长度、宽度和高度，各自彼此垂直，或者直径和长度)。所述孔隙不必为规则形状的。“最小尺寸”被定义为单个孔隙的两个或更多个尺寸的最小值。“中值最小尺寸”被定义为一组孔隙的这些最小尺寸的中值。
如本文所述的烧结的主体可由于CNT之间和CNT之内的孔隙而具有高的比表面积(即，因为CNT为空心的)。例如，烧结的主体的比表面积可为至少约100m2/g、至少约500m2/g、至少约750m2/g、至少约900m2/g或甚至至少约1000m2/g。比表面积可通过用于形成固体碳产物的CNT的特征性直径或直径混合物来控制。例如，小直径的单壁CNT的比表面积高达大约3000m2/g，而大直径的多壁CNT的比表面积为大约100m2/g。
烧结主体可具有高导电性。例如，烧结的主体的导电性可为至少约1x 105S/m(西门子每米)、至少约1x 106S/m、至少约1x 107S/m或甚至至少约1x 108S/m。导电性可通过所使用的CNT类型、所使用的CNT的手性、烧结条件以及固体碳产物中的所得共价键的数量来控制。例如，具有金属手性的单壁CNT具有比多壁CNT高很多的导电性。作为另一个实例，共价键数目的增加似乎与传导性的增加有关。
烧结主体还可具有高导热性。例如，烧结的主体的导热性可为至少约400W/m·K(瓦特每米每开尔文)、至少约1000W/m·K、至少约2000W/m·K或甚至至少约4000W/m·K。所得固体碳产物的导热性可通过所使用的CNT的类型和所使用的CNT的手性来控制。例如，具有金属手性的单壁CNT具有比大的多壁CNT高很多的导热性。
或者可以在烧结工艺之后通过例如挤压或模塑来压制CNT，如以上关于图5至图9所述的。在一些实施方案中，烧结工艺可为所需物体的形成的一部分。例如，挤压筒的区段可在惰性气氛下将CNT加热至烧结温度，持续引起烧结的适当时间量。此类加热可为例如感应加热或等离子体电弧加热。因此，可挤压烧结的CNT。烧结的CNT可任选地与另一种材料如金属、陶瓷或玻璃混合。所述材料可在极热或极冷下压制或拉伸经过冲模。持续一段时间并且在烧结的温度和压力下将压成给定形状的材料保持在适当位置，并且然后恢复到正常大气条件。所述产物可为连续的，如线材，或者可为不连续的部件，如螺栓、推进器、齿轮等。烧结的(sintered或sintering)CNT的模塑通常涉及以浓缩形式(即，具有最少杂质)使用CNT材料或与另一种材料如金属形成可模塑的复合物。将可模塑的材料置于或倾入刚性模具中，将其保持在特定的温度和压力下，并且然后冷却回到正常大气条件下。
在一些实施方案中，可采用增量制造法，其中将CNT(压缩或未压缩的)置于非反应性环境中，如惰性气体高压釜中。将CNT烧结以在表面层和下层中的CNT之间形成共价键。例如，激光可以一种图案照射CNT的一部分。另外的CNT沉积于烧结的CNT上并且进而烧结。烧结工艺根据需要重复多次，以实现所选择的烧结CNT的厚度。然后将烧结的CNT冷却至CNT不会与氧气或其它大气气体反应的温度。然后可将烧结的CNT从非反应性环境中去除，而不污染烧结的CNT。在一些实施方案中，将烧结的CNT在沉积每个另外部分的CNT之前冷却并从非反应性环境中去除。
在某些实施方案中，烧结的固体碳产物在带式铸造操作中形成。将CNT层置于可移动的带上。所述带将CNT移动到含有非反应性环境的腔室中。将CNT在所述腔室内烧结，然后冷却(例如，在一部分腔室内)并且从所述腔室中去除。可连续地重复所述过程，例如以形成烧结的CNT的薄片。
在一些实施方案中，通过电沉积来用另一种材料填充固体碳产物中的间隙，以进一步处理固体碳产物。制备具有有待沉积的材料的溶液。溶液的溶剂可为水、有机溶剂或无机溶剂。溶质可包括如金属盐、有机盐、金属有机盐等的材料。电镀溶液为本领域中已知的并且在本文中并未详细描述。有待处理的固体碳产物如通过将主体浸入溶液中来与所述溶液接触。将电势(直流电压或交流电压)施加于主体，以诱导一种或多种溶液组分的电沉积。维持组合物、电势、温度和/或压力，直到所选择的量的材料沉积于固体碳产物上。然后将固体碳产物从溶液中去除并且冲洗，以去除过量的溶液。
如本文所述形成的固体碳产物各自包括多个交联的CNT。CNT限定多个孔隙，这些孔隙的中值最小尺寸可小于约1μm、小于约500nm、小于约100nm、小于约50nm或甚至小于约10nm。一些或所有CNT可包含金属，如形成CNT的金属颗粒或者涂布在CNT上的金属。固体碳产物可为结构构件(例如梁)、紧固件(例如，螺钉)、移动零件(例如，推进器、曲轴等)、导电构件(例如，电极、电线等)或任何其它形式。固体碳产物可包含另一种材料，其分散于围绕CNT并与其接触的连续基体中。固体碳产物与常规材料相比可具有提高的强度、韧性、抗冲击性以及导电性和导热性。
在一些实施方案中，固体碳产物还包含散布有CNT或者以其它方式固定于CNT的其它形态的碳。例如，巴克球可连接至一些CNT。作为另一个实例，在所有或一部分固体碳产物上可形成一个或多个石墨烯片。
本文所述的压缩的固体碳产物和烧结的固体碳产物二者均具有各种各样的可能有用的应用。例如，压缩的固体碳产物在其中不需要通过烧结来实现另外的机械完整性的应用中可用作过滤器、分子筛、催化剂以及电极。烧结的固体碳产物可用于其中可使用压缩的固体碳产物的应用以及需要通过烧结实现另外的机械完整性、电学性质以及其它材料性质增强的各种各样的另外的应用中。
烧结的固体碳产物由于其机械完整性、吸收具有高弹簧常数的压缩负载的能力以及驱散热量的能力而可为装甲的有用组分。即，烧结的固体碳产物可用于形成防射弹的材料，如装甲板、防弹背心等。轻质的固体碳产物可以提高任务载荷、增加运输工具可行驶里程(vehicle range)并且改变重心。例如，包含烧结的固体碳产物的装甲材料可有益于防止有倾斜倾向的运输工具如防地雷反伏击车(“MRAP”)的乘坐者受伤和死亡。如本文所述的烧结的固体碳产物可有效于轻质军备系统，如迫击炮身管、枪筒、炮身以及其它组件。烧结的固体碳产物还可有益于航空运输工具，如飞机、宇宙飞船、导弹等。
实施例
实施例1：压实的CNT的烧结
如美国专利公布号2012/0034150A1中所描述形成CNT。使用100-吨(890-kN)压力机将大约1.0克至1.25克的CNT样品各自压成15-mm直径。将压制的样品置于惰性气体炉(型号1000-3060-FP20，可从CA Santa Rosa的Thermal Technology,LLC获得)中并且在真空下以25℃的速率加热，直到样品达到400℃为止。将此温度维持30分钟，以允许样品除去任何氧气、水或存在的其它物质。然后在大于大气压的3-5psi(21至34kPa)下用惰性气体(氩气或氦气)填充所述炉。以20℃/min的速率加热所述炉，直到样品达到1500℃为止。将此温度维持30分钟。以5℃/min持续加热至烧结温度，将此温度维持60分钟的停留时间。然后将样品以50℃/min冷却至1000℃，在此之后，关闭所述炉，直到样品达到环境温度为止。在以下表1中示出样品的样品质量、压实压力以及烧结温度。惰性气体对于在2400℃下烧结的样品为氦气并且对于其它样品为氩气。
表1：实施例1中制备的样品
样品 质量(g) 压实压力(MPa) 烧结温度(℃)
1 1.076 500 1800
2 1.225 750 1800
3 1.176 250 1800
4 1.113 500 2100
5 1.107 750 2100
6 1.147 250 2100
7 1.103 500 2400
8 1.198 750 2400
9 1.121 250 2400
10 1.128 250 1900
11 1.209 500 1900
12 1.212 750 1900
13 1.101 250 2000
14 1.091 500 2000
15 1.225 750 2000
16 1.078 250 1700
17 1.179 500 1700
18 1.157 750 1700
样品1至18比加热过程之前的样品更坚硬且更坚固。在最高烧结温度2400℃(样品7至9)下，烧结的小球比其它烧结的样品更薄。在实施例1中制备的所有样品均定性地观察为坚硬的。
测比重术测试显示对于在1800℃、2100℃和2400℃下烧结的样品，粗粉和粗压实物的骨架密度分别从2.2g/cm3减小至2.1g/cm3、2.08g/cm3和2.05g/cm3。堆积密度也在烧结之后减小，在几乎每种情况下减小至小于1.0g/cm3。在烧结期间小球厚度增加5％至9％，其中较高压力压实扩大超过较低压力压实。在表2和图12中示出样品1至9的堆积密度。
表2：实施例1中制备的样品的性质：
实施例2：CNT的火花等离子体烧结
如美国专利公布号2012/0034150A1中所描述地形成CNT。将石墨箔(从AZ Tucson的Mineral Seal Corp.获得)排列至20-mm直径的冲模中，并且将2.0g至4.0g CNT置于所述箔上。将样品置于火花等离子体烧结(SPS)系统(型号SPS 25-10，从CA Santa Rosa的Thermal Technology,LLC获得)中。将大约5Mpa的轴向压力施加于CNT样品并且然后将SPS系统抽空至小于3mTorr(0.4Pa)。将样品以150℃/min加热至650℃，并且将此温度维持一分钟，以允许真空泵将除气的任何材料再次抽空。将压力增加至30MPa或57MPa的压实压力，同时将温度以50℃/min的速率增加至1500℃。将温度和压力维持一分钟。然后将温度以50℃/min增加至烧结温度，并且维持10min或20min。在停留之后，压力减小至5MPa，并且允许样品以150℃/min冷却至1000℃，此后关闭所述炉，直到所述样品达到环境温度为止。
在以下表2中示出样品的样品质量、压实压力、压实速率、烧结温度以及停留时间。
表3：实施例2中制备的样品：
在实施例2中所形成的SPS烧结的小球为约10mm厚并且具有1.3g/cm3与1.5g/cm3之间的堆积密度。为了说明这些样品的强度，计划将样品#20烧结2100℃，但是在约1900℃下，冲模破裂。冲头显著行进，压碎石墨冲模。在完成测试之后，冲模从样品中剥离开。样品保持明显完整，尽管比预期稍微更薄。这可表明烧结发生于小于1900℃的温度下，SPS烧结的小球的强度为高的，甚至在极端温度下也是这样，并且烧结的样品为足够强的以抵抗所施加的力而不会破裂。
测定仍与石墨箔连接的样品的堆积密度。对于重约4g(即，样品#21、#22和#23)的样品，堆积密度在1.35g/cm3与1.50g/cm3之间。还测量样品的体积电阻率和导电率。这些数据在表4中示出。所述样品具有比无定形碳更大的传导性以及几乎与石墨一样的传导性。
表4：实施例2中制备的样品的性质：
虽然前述描述含有很多细节，但是这些不应理解为限制本发明的范围，而仅仅理解为提供某些实施方案。类似地，可设计不背离本发明范围的本发明的其它实施方案。例如，本文关于一个实施方案描述的特征也可在本文描述的其它实施方案中提供。因此，本发明范围仅由所附权利要求书及其法定等效物而非由前述描述来指示和限制。属于权利要求书的涵义和范围内的如本文公开的本发明的所有添加、删除和修改由本发明涵盖。

Claims (20)

1.一种包含金属和多个碳纳米管的烧结固体碳产品，其中多个碳纳米管中的至少一些共价键合到多个碳纳米管中的其它碳纳米管。
2.根据权利要求1所述的烧结固体碳产品，其中碳纳米管在其间限定具有小于约100nm的中值最小尺寸的多个孔隙。
3. 根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品的堆积密度大于约1.3 g/cm3。
4.根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品包含防射弹材料。
5.根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品包含导电性材料。
6. 根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品具有至少约1×105 S/m的导电率。
7. 根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品具有至少约1×107 S/m的导电率。
8.根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品包括电极。
9.根据权利要求1所述的烧结固体碳产品，其中金属包含选自由周期表第5族至第10族的元素组成的组的催化剂残余物。
10.根据权利要求1所述的烧结固体碳产品，其中至少一些碳纳米纤维在碳纳米纤维的生长尖端内含有金属。
11. 根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品具有小于约2.2 g/cm3的堆积密度。
12.根据权利要求1所述的烧结固体碳产品，还包括选自由陶瓷和润滑剂组成的组的至少一种材料，其中至少一种材料散布在围绕所述多个碳纳米纤维并与其接触的连续基质中。
13.根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品包括结构部件。
14. 根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品具有至少约400 W/m·K的热导率。
15. 根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品具有至少约2000 W/m·K的热导率。
16. 根据权利要求1所述的烧结固体碳产品，其中烧结固体碳产品具有至少约4000 W/m·K的热导率。
17.一种包含金属和多个碳纳米结构的烧结固体碳产品，其中碳纳米结构包含键合到六方晶格中的碳原子，其中多个碳纳米结构中的至少一些共价键合到多个碳纳米结构中的其它碳纳米结构。
18.根据权利要求17所述的烧结固体碳产品，其中多个碳纳米结构中的至少一些包含多壁碳纳米管。
19.根据权利要求17所述的烧结固体碳产品，其中多个碳纳米结构中的至少一些包含连接到碳纳米管的纳米芽。
20.根据权利要求17所述的烧结固体碳产品，其中多个碳纳米结构中的至少一些包含单壁碳纳米管。
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