CN112976705B - 一种复合碳纳米材料及其制备方法 - Google Patents

一种复合碳纳米材料及其制备方法 Download PDF

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CN112976705B
CN112976705B CN201911280075.9A CN201911280075A CN112976705B CN 112976705 B CN112976705 B CN 112976705B CN 201911280075 A CN201911280075 A CN 201911280075A CN 112976705 B CN112976705 B CN 112976705B
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曾培源
何占宇
李建稳
王帝
沈健民
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Nanjing Yuanchang New Material Co ltd
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Abstract

本发明公开了一种复合碳纳米材料及其制备方法，复合碳纳米材料包括依次叠合的碳纳米材料层、金属缓冲层及基体层，所述金属缓冲层与碳纳米材料层以固溶体结构连接，与基体层以合金结构连接。本发明利用某些金属材料可以与碳纳米材料形成固溶体这一特性，使该金属材料充当缓冲层，在不使用粘结剂的条件下，将碳纳米管薄膜与一些不能与碳纳米材料形成固溶体的金属材料结合在一起。解决了碳纳米材料在不使用粘结剂的情况下与金属材料的结合难题。

Description

一种复合碳纳米材料及其制备方法
技术领域
本发明涉及碳纳米材料技术领域，具体涉及一种复合碳纳米材料及其制备方法。
背景技术
随着科学技术的迅速发展，对材料性能也提出了更高的要求。传统的单一材料已经不能满足市场需要。复合材料是由两种或两种以上物理或化学性质不同的物质组合而成的一种多相固体材料，复合材料不仅保留了原有组分材料的特性，并且在各组分材料的协同作用下具有优于单一材料的综合性能。
自碳纳米管、石墨烯、富勒烯等碳纳米材料被发现以来，其独特的结构及其优异的性能引起科学工作者高度关注，碳纳米管、石墨烯、富勒烯等碳纳米材料与其他材料的复合也迅速成为纳米复合材料的研究热点并且取得了不错的进展。复合碳纳米材料优异的性能在复合材料中起到了多方面的作用，一方面，这些碳纳米材料优异的力学性能可以增强复合材料的强度和韧性；另一方面，还可以使原有材料的电导性质发生根本改变。此外，利用碳纳米材料独特的吸附性、吸波性和光电子发射等性能，可以制备电磁屏蔽、隐身材料、吸波材料等新型功能材料。
碳纳米材料与金属材料复合后，可以提高金属的强度、硬度、耐磨损性以及热稳定性，但是传统方法将碳纳米材料与金属复合需要在中间使用粘结剂，粘结剂的存在将会增大复合材料的电阻，且粘结剂的使用也使这种复合材料不能在较高温度下使用，以防粘结剂变性、碳化。
发明内容
为解决上述技术问题，本发明提供一种复合碳纳米材料及其制备方法，无需使用粘结剂，利用某些金属材料可以与碳纳米材料形成固溶体这一特性，使该金属材料充当缓冲层，将碳纳米材料与其他金属材料结合在一起。
本发明采用技术方案是：
一种复合碳纳米材料，包括依次叠合的碳纳米材料层、金属缓冲层及基体层，所述金属缓冲层与碳纳米材料层以固溶体结构连接，与基体层以合金结构连接。
作为本发明的进一步改进，所述碳纳米材料层由碳纳米管、石墨烯、或富勒烯制成。
作为本发明的更进一步改进，所述碳纳米材料层的厚度为40～100μm。
作为本发明的进一步改进，所述金属缓冲层由金属铁、金属钴、金属镍、或以铁、钴、镍中至少一种为主体的合金材料制成。
作为本发明的进一步改进，所述基体层由金属材料制成。
作为本发明的更进一步改进，金属缓冲层及金属基体层的形式为板材、片材、带材或箔材中的一种。
上述任意一种技术方案所述复合碳纳米材料的制备方法，包括以下步骤：
(1)制备碳纳米材料层；
(2)将碳纳米材料层、金属缓冲层、基体层依次叠层；
(3)将叠层材料置于真空热压炉内处理，使金属缓冲层与碳纳米材料层的接触面形成固溶体，金属缓冲层与基体层的接触面形成合金，既得复合碳纳米材料。
作为本发明的进一步改进，步骤(1)中所用碳纳米材料由化学气相沉积法或者浮动气相催化法或溶剂热方法制得。
作为本发明的进一步改进，真空热压炉的处理工艺为：真空热压炉的处理工艺为：抽真空至炉内压力小于10Pa，双向加压5～12MPa，缓慢升温升至200～850℃，保持0.5～2小时。
本发明的有益效果：本发明解决了碳纳米材料在不使用粘结剂的情况下与金属材料的结合难题。本发明通过利用金属材料可以与碳材料形成固溶体，金属材料之间在高压、高温下可以形成合金这一特性，将含铁、钴、镍的金属材料作为缓冲层，通过缓冲层可以结合不能与碳纳米材料形成固溶体的金属材料。因为缓冲层为金属材料，该结构不会影响复合材料的导电、导热、导磁性能。相比于使用粘结剂的方法，利用该方法制备的复合材料可以在高温下使用，不会出现高温条件下各层相互分离的情况。使用真空热压的方法，能够排除吸附气体、空气中的残留气体，使各种材料之间结合的更加紧密。在真空环境中热压要比在保护气中热压所需要的温度要低100～150℃，能够解决一些熔点低的金属在高温发生熔化的问题。
附图说明
图1是本发明复合碳纳米材料的叠层示意图。
图2是本发明复合碳纳米材料的结构示意图。
图3是钴-锌合金相图。
图4是铁-铜合金相图。
图5是铁-锡合金相图。
图6是钛-铅合金相图。
图7是钛-铜合金相图。
图8是铋-镍合金相图。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1
S1：利用气相浮动催化法制备出的厚度为40-50μm的碳纳米管薄膜；
S2：将锌箔平铺在实验台上，随后将钴箔平铺到锌箔表面，再将碳纳米管薄膜铺展在钴箔表面；
S3：将叠层材料置于真空热压炉内，抽真空至炉内压力小于10Pa，双向加压至5MPa，缓慢将炉温升至300℃并保持0.5小时，即得碳纳米管薄膜-钴-锌三层复合材料。碳纳米管薄膜和金属钴以钴-碳固溶体连接，锌箔和钴箔接触部分形成锌钴合金，使金属钴和金属锌紧密连接在一起，参见图3。
实施例2
S1：利用化学气相沉积法制备出的厚度为40-60μm的石墨烯薄膜；
S2：将铜箔平铺在实验台上，随后将铁箔平铺到铜箔表面，再将石墨烯薄膜铺展在铁箔表面；
S3：将叠层材料置于真空热压炉内，抽真空至炉内压力小于10Pa，双向加压至10Mpa，缓慢将炉温升至850℃并保持1小时，即得石墨烯薄膜-铁-铜三层复合材料。碳纳米管薄膜和金属铁以铁-碳固溶体连接，铁箔和铜箔接触部分形成铁铜合金，使金属铁和金属铜紧密连接在一起，参见图4。
实施例3
S1：利用碳纳米管分散液制备出的厚度为50μm的碳纳米管薄膜；
S2：将锡箔平铺在实验台上，随后将铁箔平铺到锡箔表面，再将碳纳米管薄膜铺展在铁箔表面；
S3：将叠层材料置于真空热压炉内，抽真空至炉内压力小于10Pa，双向加压至10MPa，缓慢将炉温升至200℃并保持2小时，即可碳纳米管薄膜-铁-锡三层复合材料。碳纳米管薄膜和金属铁以铁-碳固溶体连接，铁箔和锡箔接触部分形成铁铜合金，使金属铁和金属锡紧密连接在一起，参见图5。
实施例4
S1：利用化学气相沉积法制备出的厚度为10-20μm的富勒烯薄膜；
S2：将银箔平铺在实验台上，随后将铁箔平铺到银箔表面，再将富勒烯薄膜铺展在铁箔表面；
S3：将叠层材料置于真空热压炉内，抽真空至炉内压力小于10Pa，双向加压至8MPa，缓慢将炉温升至700℃并保持1小时，即得富勒烯薄膜-钛-铅三层复合材料。碳纳米管薄膜和金属铁以钛-铅固溶体连接，铁箔和银箔接触部分形成钛铅合金，使金属钛和金属铅紧密连接在一起，参见图6。
实施例5
S1：利用化学气相沉积法制备出的厚度为80μm的碳纳米管薄膜；
S2：先将铜箔平铺在实验台上，随后将钛箔平铺到铜箔表面，再将碳纳米管薄膜铺展在钛箔表面；
S3：将叠层材料置于真空热压炉内，抽真空至炉内压力小于10Pa，双向加压至12MPa，缓慢将炉温升至550℃并保持2小时，即得碳纳米管薄膜-钛-铜三层复合材料。碳纳米管薄膜和金属钛以钛-碳固溶体连接，钛箔和铜箔接触部分形成钛铜合金，使金属钛和金属铜紧密连接在一起，参见图7。
实施例6
S1：利用气相浮动催化法制备出的厚度为100μm的碳纳米管薄膜；
S2：先将铋箔平铺在实验台上，随后将镍箔平铺到铋箔表面，再将碳纳米管薄膜铺展在镍箔表面；
S3：将叠层材料置于真空热压炉内，抽真空至炉内压力小于10Pa，双向加压至12MPa，缓慢将炉温升至200℃并保持1小时，即得碳纳米管薄膜-镍-铋三层复合材料。碳纳米管薄膜和金属镍以镍-碳固溶体连接，镍箔和铋箔接触部分形成镍铋合金，使金属镍和金属铋紧密连接在一起，参见图8。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (5)

1.一种复合碳纳米材料，其特征在于，包括依次叠合的碳纳米材料层、金属缓冲层及基体层，所述金属缓冲层与碳纳米材料层以固溶体结构连接，与基体层以合金结构连接；所述金属缓冲层由金属铁、金属钴、金属镍，或以铁、钴、镍中至少一种为主体的合金材料制成；所述基体层由金属材料制成；
所述复合碳纳米材料的制备方法，包括以下步骤：
（1）制备碳纳米材料层；
（2）将碳纳米材料层、金属缓冲层、基体层依次叠层；
（3）将叠层材料置于真空热压炉内处理，使金属缓冲层与碳纳米材料层的接触面形成固溶体，金属缓冲层与基体层的接触面形成合金，即 得复合碳纳米材料；
真空热压炉的处理工艺为：抽真空至炉内压力小于10Pa，双向加压5～12 MPa，缓慢升温升至200～850°C，保持0.5～2小时。
2.根据权利要求1所述的复合碳纳米材料，其特征在于，所述碳纳米材料层由碳纳米管、石墨烯或富勒烯制成。
3.根据权利要求2所述的复合碳纳米材料，其特征在于，所述碳纳米材料层的厚度为10～100µm。
4.根据权利要求1所述的复合碳纳米材料，其特征在于，金属缓冲层及金属基体层的形式为片材。
5.根据权利要求1所述的复合碳纳米材料，其特征在于，步骤（1）所用碳纳米材料由化学气相沉积法或者溶剂热方法制得。
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Publication number Priority date Publication date Assignee Title
CN101189356A (zh) * 2005-05-18 2008-05-28 三菱化学株式会社 渗碳处理的金属材料及其制造方法
CN107150475A (zh) * 2017-06-07 2017-09-12 西北工业大学 无机复合材料与镍基高温合金材料间碳纳米管增韧连接层及方法
CN107170510A (zh) * 2014-12-31 2017-09-15 重庆元石石墨烯技术开发有限责任公司 金属纳米线—石墨烯桥架结构复合材料及其制备方法

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Publication number Priority date Publication date Assignee Title
CN101189356A (zh) * 2005-05-18 2008-05-28 三菱化学株式会社 渗碳处理的金属材料及其制造方法
CN107170510A (zh) * 2014-12-31 2017-09-15 重庆元石石墨烯技术开发有限责任公司 金属纳米线—石墨烯桥架结构复合材料及其制备方法
CN107150475A (zh) * 2017-06-07 2017-09-12 西北工业大学 无机复合材料与镍基高温合金材料间碳纳米管增韧连接层及方法

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