CN109563649A - 用于制备碳纳米管纤维的方法和由此制备的碳纳米管纤维 - Google Patents
用于制备碳纳米管纤维的方法和由此制备的碳纳米管纤维 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 143
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 143
- 239000000835 fiber Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 34
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- C01B32/178—Opening; Filling
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- D—TEXTILES; PAPER
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- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/08—Processes in which the treating agent is applied in powder or granular form
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Abstract
本发明涉及用于制备碳纳米管纤维的方法和由此制备的碳纳米管纤维,所述方法包括:在催化剂和催化活化剂的存在下由碳源制备碳纳米管聚集体(S1);使所述碳纳米管聚集体与氧化石墨烯接触(S2);以及使与所述氧化石墨烯接触的所述碳纳米管聚集体纤维化(S3)。
Description
技术领域
相关申请的交叉引用
本申请要求于2017年2月3日提交的韩国专利申请第10-2017-0015343号的优先权和权益,其公开内容通过引用整体并入本文。
技术领域
本发明涉及用于制备能够增强拉伸强度的碳纳米管纤维的方法和由此制备的碳纳米管纤维。
背景技术
碳纳米管(CNT)是碳的同素异形体,并且是直径为数纳米至数十纳米且长度为数百微米至数毫米的材料。自从1991年Iijima博士在Nature杂志上报道了这样的碳纳米管,由于优异的热特性、电特性和物理特性以及高的纵横比,已经在各个领域中对这些材料进行了研究。碳纳米管的固有特性起因于碳原子的sp2杂化,并且碳纳米管比铁更强,比铝更轻,并且表现出与金属类似的导电性。
根据纳米管的壁数,碳纳米管主要分类为单壁碳纳米管(SWNT),双壁碳纳米管(DWNT)和多壁碳纳米管(MWNT),并且根据不对称/旋转角度(手性)分为锯齿形结构、扶手椅形结构和手性结构。迄今为止,通常进行的大多数研究是分散粉末型碳纳米管以用作复合材料的增强剂,或者使用碳纳米管分散溶液制备透明导电膜,并且碳纳米管已经在一些领域商业化。
然而,为了在复合材料和透明导电膜中使用碳纳米管,碳纳米管的分散是重要的,但是由于通过碳纳米管的强范德华力产生的内聚力,碳纳米管在高浓度下不易分散并且不易保持分散性。另外,在使用碳纳米管作为增强材料的复合材料的情况下,难以充分表现碳纳米管的优异特性。
因此,近年来,已经进行了各种各样的用于制备碳纳米管纤维的研究以制造充分表现碳纳米管的特性的碳纳米管结构。
在用于使碳纳米管纤维化的方法中,直接纺丝是如下获得纤维的方法:将气相或液相碳源、催化剂和促进剂前体与载气一起注入垂直站立式高温加热炉的上部入口以在加热炉中合成碳纳米管,并且在加热炉内部或外部卷绕在加热炉中和载气一起流下的碳纳米管聚集体。
在通过上述方法制备的碳纳米管纤维的情况下,作为碳纳米管纤维的组分的碳纳米管聚集体之间没有直接相互作用。因此,当向所述碳纳米管纤维施加张力时,碳纳米管聚集体滑动,从而使纤维破裂。因此,为了增强碳纳米管纤维的拉伸强度,正在进行在碳纳米管聚集体之间形成特定键的研究。
发明内容
技术问题
本发明提供了一种用于制备能够增强拉伸强度的碳纳米管纤维的方法和由此制备的碳纳米管。
技术方案
为了解决上述问题,本发明提供了用于制备碳纳米管纤维的方法,其包括:在催化剂和催化活化剂的存在下由碳源制备碳纳米管聚集体(S1);使碳纳米管聚集体与氧化石墨烯接触(S2);以及使与氧化石墨烯接触的碳纳米管聚集体纤维化(S3)。
此外,本发明提供了通过用于制备碳纳米管纤维的方法制备的碳纳米管。
有益效果
根据本发明的用于制备碳纳米管纤维的方法,由于在制备碳纳米管纤维的过程中使碳纳米管与氧化石墨烯接触,所以氧化石墨烯不仅可以存在于碳纳米管纤维的表面上,而且可以容易地渗透到构成碳纳米管纤维的碳纳米管内部。因此,构成碳纳米管纤维的每根碳纳米管的拉伸强度增强,碳纳米管之间的结合力由于存在于碳纳米管表面上的氧化石墨烯而增加,并因此作为最终产品的碳纳米管纤维的拉伸强度可以显著增强。此外,由于制备碳纳米管聚集体和与氧化石墨烯接触的连续过程可以使用常规的用于制备碳纳米管纤维的设备来实现而不需要单独的设备和另外的过程,因此制备时间减少,并且该过程容易进行。
附图说明
图1是进行根据本发明的一个示例性实施方案的用于制备碳纳米管纤维的方法的用于制备碳纳米管纤维的设备的示意图。
具体实施方式
在下文中,将更详细地描述本发明以帮助理解本发明。
说明书和权利要求中使用的术语和词语不应被解释为限于常规或字面含义,而应基于本发明人已经适当地定义术语的概念以便以最佳方式描述本发明的原则,用与本发明的技术范围一致的含义和概念进行解释。
同时,在根据本发明的一个示例性实施方案的用于制备碳纳米管纤维的方法中使用的制备设备可以是可以在本发明的领域中使用的任何设备而没有特别限制,并且将参照图1描述实例以帮助理解本发明。
参照图1,在本发明的用于制备碳纳米管纤维的方法中使用的制备设备1可以包括:包括反应区12的反应器10、位于反应器10上部的入口11、用于加热反应器10的加热装置13、位于反应器10下部并且用于排出碳纳米管的水容器14、和位于反应器10下部并且用于排出未反应气体的出口15。另外,可以包括位于水容器14中并且便于碳纳米管回收的卷绕装置141。
根据本发明的一个示例性实施方案的用于制备碳纳米管纤维的方法包括在催化剂和催化活化剂的存在下由碳源制备碳纳米管聚集体(S1)。
步骤S1可以在反应器10中的反应区12中进行。具体地,可以将催化剂和催化活化剂注入反应区12中,并且可以通过入口11将气态(在下文中称为“气相”)碳源或气相碳源以及还原气体(例如氢气等)和载气(例如氮气等)的混合气体在至少为气相碳源的热解温度且至多为催化剂的熔化温度的温度下注入反应器中。碳纳米管可以由注入的气相碳源制备。具体地,可以通过经由气相碳源的分解通过化学气相合成来生长碳纳米管聚集体而制备碳纳米管聚集体。通过这样的化学气相合成制备的碳纳米管聚集体具有几乎平行于管轴的生长方向,并且具有石墨结构在管长度方向上的高结晶度。因此,单元体具有较小的直径,并且导电性和强度高。
此外,化学气相合成可以在1000℃或更高温度,并且具体地1000℃至1500℃,并且更具体地1100℃至1300℃下进行。为了满足上述温度,可以通过加热装置13升高反应区12的温度。当满足上述温度时,可以增加碳纳米管聚集体的生长速率,并且可以增强碳纳米管聚集体的结晶度和强度。
另外,催化剂可以是可以用于制备碳纳米管聚集体的任何催化剂而没有特别限制,并且可以为选自以下的一者或更多者:含二茂铁的茂金属、铁、镍、钴、铂、钌、钼、钒及其氧化物。催化活化剂可以是可以用于制备碳纳米管聚集体的任何活化剂而没有特别限制,并且可以为硫(S)或噻吩(C4H4S)。
作为碳源,可以使用可以提供碳并且在300℃或更高温度下以气相存在的任一者而没有特别限制。具体地,碳源可以是具有6个碳原子或更少碳原子的基于碳的化合物,并且更具体地,可以为选自以下的一者或更多者:一氧化碳、甲烷、乙烷、乙烯、乙醇、乙炔、丙烷、丙烯、丁烷、丁二烯、戊烷、戊烯、环戊二烯、己烷、环己烷、苯和甲苯。
根据本发明的一个示例性实施方案的用于制备碳纳米管纤维的方法包括使碳纳米管聚集体与氧化石墨烯接触(S2)。
具体地,步骤S2中制备的碳纳米管聚集体可以通过包含其中分散有氧化石墨烯的分散溶液的水容器14以将碳纳米管聚集体与还原气体和载气分离并允许碳纳米管聚集体与氧化石墨烯接触而排出到外部。
更具体地,紧接在制备碳纳米管聚集体之后,即,在构成碳纳米管聚集体的每根碳纳米管的内部变得密实之前,可以使碳纳米管聚集体与氧化石墨烯接触。因此,氧化石墨烯可以渗透通过的大孔可以存在于碳纳米管中,并且氧化石墨烯可以容易地渗透到存在于每根碳纳米管中的孔中并且可以保留在其中。因此,可以显著增强构成碳纳米管纤维的每个碳纳米管聚集体的拉伸强度。
另外,由于氧化石墨烯可以容易地渗透到构成碳纳米管聚集体的各碳纳米管聚集体之间,因此氧化石墨烯可以存在于每个碳纳米管聚集体的表面上。由于氧化石墨烯,可以增加碳纳米管之间的结合强度,并因此可以显著增强作为最终产品的碳纳米管纤维的拉伸强度。
碳纳米管聚集体和氧化石墨烯可以彼此接触1秒至5分钟,并且具体地1.2秒至2分钟。当满足上述条件时,氧化石墨烯可以充分地地渗透到各碳纳米管聚集体之间,以及渗透到碳纳米管聚集体中并保留在其中。
同时,氧化石墨烯的平均颗粒尺寸可以为10nm至1000nm,具体地10nm至500nm,并且更具体地40nm至100nm。当满足上述范围时,氧化石墨烯可以有效地渗透到构成碳纳米管聚集体的每根碳纳米管中并保留在其中,具体地,渗透到孔中并保留在其中。为了使氧化石墨烯具有上述平均颗粒尺寸,可以进行研磨过程,并且研磨过程可以是常规研磨过程,例如球磨。
分散溶液可以是包含10mg/L至5000mg/L,具体地10mg/L至100mg/L,并且更具体地10mg/L至50mg/L的氧化石墨烯的水溶液。当满足上述范围时,适量的氧化石墨烯可以容易地渗透到碳纳米管中并保留在其中。另外,碳纳米管的内部和表面可以均匀地涂覆有氧化石墨烯。
同时,可以使用存在于水容器14中的卷绕装置141通过卷绕收集碳纳米管聚集体,然后将其排出到外部。卷绕装置141可以是选自旋转、卷轴、滚筒和输送机中的一者或更多者。
根据本发明的一个示例性实施方案的用于制备碳纳米管纤维的方法包括使与氧化石墨烯接触的碳纳米管聚集体纤维化(S3)。
用于使碳纳米管聚集体纤维化的方法没有特别限制,只要其可以在本发明的领域中进行即可,并且可以为收缩、拉伸或加捻(twisting)。
根据本发明的一个示例性实施方案的用于制备碳纳米管纤维的方法还可以包括在步骤S2与步骤S3之间对碳纳米管纤维进行热处理。
热处理可以在含氧气氛中进行,并且具体地在包含20体积%或更多的氧的气氛中进行。
此外,热处理可以在150℃至500℃,具体地200至400℃,并且更具体地200至300℃下进行。当满足上述范围时,碳纳米管表面可以被部分氧化,并且可以在氧化的碳纳米管的表面上形成诸如羟基(-OH)的官能团。形成在碳纳米管表面上的官能团可以通过氢键与氧化石墨烯表面上的官能团键合,并因此,可以增强作为最终产品的碳纳米管纤维的拉伸强度。
同时,当在惰性气体气氛中而不是在含氧气氛中进行热处理时,碳纳米管表面不被氧化,因此碳纳米管纤维的拉伸强度的增强程度可能不显著。因此,可以优选在可能时调节热处理气氛。
根据本发明的另一个示例性实施方案的碳纳米管纤维通过用于制备碳纳米管纤维的方法制备,并且包含在其表面上和在其中含有氧化石墨烯的碳纳米管。结果,与仅在其表面上存在氧化石墨烯的常规碳纳米管纤维相比,本发明的碳纳米管纤维具有显著优异的拉伸强度。
实施例
在下文中,将详细地描述本发明的实施例,以便本发明所属领域的普通技术人员容易实施。然而,本发明可以以各种不同的形式实现,并且不限于本文将描述的实施例。
[实施例1至6和比较例1至3:碳纳米管纤维的制备]
使用用于制备碳纳米管纤维的设备通过以下方法制备碳纳米管纤维,所述设备包括:包括反应区的反应器主体;位于主体上部并允许碳源和载气流入反应区中的入口;用于加热反应区的加热装置;和配备在主体下部的用于将碳纳米管纤维排出到设备外部的水容器。
在氮气气氛下,将反应区中的温度升高至1200℃。将作为催化剂前体的Fe(C5H5)2和作为催化活化剂的硫(S)放入与入口相邻的反应区中。分别以0.07g/小时和0.02g/小时的平均速率通过汽化来添加Fe(C5H5)2和催化活化剂S,并且通过以2.0小时-1的气时空度(GHSV)进给作为碳源的甲烷并且分别以25小时-1和13小时-1的GHSV进给氢气和作为载气的氮气,进行合成3小时,从而获得碳纳米管聚集体。
GHSV是指供应气体的体积流量与反应器体积的比率,其在标准条件(0℃,1巴)下测量,并且是以小时作为单位时间表示的值。
使碳纳米管聚集体通过包含其中以下表1所示的含量含有氧化石墨烯的水溶液的水容器持续0.5分钟,以排出到用于制备碳纳米管纤维的设备的外部。随后,通过在下表1中所述的条件下热处理获得碳纳米管纤维。
[表1]
[比较例4:碳纳米管纤维复合材料的制备]
通过将比较例1的碳纳米管纤维浸入包含100mg/L的氧化石墨烯的水溶液中12小时并在室温和大气压下干燥所得溶液来制备碳纳米管纤维复合材料。
[实验例1:碳纳米管纤维和碳纳米管纤维复合材料的特性评估]
使用FAVIMAT+(制造商:TEXTECHNO)测量实施例1至6和比较例1至3的碳纳米管纤维以及比较例4的碳纳米管纤维复合材料的拉伸强度。根据ASTM D1577测量纤维的线性密度,并且在纤维拉伸测试之后,将纤维的断裂强度除以线性密度,从而测量拉伸强度。详细的测量条件如下。基于比较例1,将拉伸强度评估为相对于比较例1的相对值,并且值示于下表2中。
测量条件:测力传感器为210cN,计量长度为2cm,以及速度为2mm/分钟
[表2]
分组 | 拉伸强度 |
实施例1 | 118.3 |
实施例2 | 133.6 |
实施例3 | 138.9 |
实施例4 | 167.9 |
实施例5 | 129.0 |
实施例6 | 126.0 |
比较例1 | 100.0 |
比较例2 | 94.7 |
比较例3 | 110.7 |
比较例4 | 63.6 |
参照表2,在根据本发明的实施例1至6的碳纳米管纤维的情况下,与比较例1至3的碳纳米管纤维相比,可以看出拉伸强度显著优异。另外,在制备碳纳米管纤维之后,与混合有氧化石墨烯的比较例4的碳纳米管纤维复合材料相比,可以看出,实施例1至6的碳纳米管纤维具有显著优异的拉伸强度。
另外,在实施例1至6的碳纳米管纤维的情况下,可以看出,当与包含高浓度氧化石墨烯的水溶液接触时,拉伸强度变得高得多。另外,在使碳纳米管纤维与氧化石墨烯接触之后进一步进行热处理时,可以看出拉伸强度进一步改善,并且具体地,相对于氩气氛,当在含氧气氛中进行热处理时,拉伸强度进一步改善。
[附图标记说明]
1:用于制备碳纳米管纤维的设备
10:反应器
11:入口
12:反应区
13:加热装置
14:水容器
141:卷绕装置
15:出口
Claims (9)
1.一种用于制备碳纳米管纤维的方法,包括:
在催化剂和催化活化剂的存在下由碳源制备碳纳米管聚集体(S1);
使所述碳纳米管聚集体与氧化石墨烯接触(S2);以及
使与所述氧化石墨烯接触的所述碳纳米管聚集体纤维化(S3)。
2.根据权利要求1所述的方法,其中步骤S2通过使所述碳纳米管聚集体通过其中分散有所述氧化石墨烯的分散溶液来进行。
3.根据权利要求2所述的方法,其中所述氧化石墨烯的平均颗粒尺寸为10nm至1000nm。
4.根据权利要求2所述的方法,其中所述分散溶液包含10mg/L至5000mg/L的所述氧化石墨烯。
5.根据权利要求1所述的方法,还包括:
在步骤S2与步骤S3之间进行热处理。
6.根据权利要求5所述的方法,其中所述热处理在含氧气氛中进行。
7.根据权利要求5所述的方法,其中所述热处理在150℃至500℃下进行。
8.根据权利要求1所述的方法,其中反应是化学气相合成。
9.一种碳纳米管纤维,包含:
碳纳米管,所述碳纳米管通过根据权利要求1所述的用于制备碳纳米管纤维的方法制备并且其中氧化石墨烯存在于所述碳纳米管的内部和表面上。
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CN109563649B (zh) | 2021-12-31 |
KR102060566B1 (ko) | 2019-12-30 |
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