多壁碳纳米管-细菌纤维素复合薄膜的制备及其力学性能

田萃钰; 陆赵情; 宁逗逗; 赵瑞霞; 耿博

doi:10.13801/j.cnki.fhclxb.20220512.002

多壁碳纳米管-细菌纤维素复合薄膜的制备及其力学性能

doi: 10.13801/j.cnki.fhclxb.20220512.002

陕西科技大学　轻工科学与工程学院，陕西省造纸技术及特种纸品开发重点实验室，轻化工程国家级实验教学示范中心，中国轻工业纸基功能材料重点实验室，西安 710021

基金项目: 国家自然科学基金(22178211)；陕西省重点研发计划(2021 ZDLGY14-05)；陕西省教育厅重点项目(20 JY002)

详细信息

通讯作者:
陆赵情，博士，教授，博士生导师，研究方向为高性能纤维和纸基功能材料　E-mail：luzhaoqing302@163.com

中图分类号: TB324
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出版历程
- 收稿日期: 2022-01-29
- 修回日期: 2022-04-26
- 录用日期: 2022-05-07
- 网络出版日期: 2022-05-13
- 刊出日期: 2023-02-15

Preparation and mechanical properties of multi-walled carbon nanotubes-bacterial cellulose composite films

Key Laboratory of Paper Based Functional Materials of China National Light Industry, National Demonstration Center for Experimental Light Chemistry Engineering Education, Shaanxi Province Key Laboratory of Paper-marking Technology and Specialty Paper, College of Bioresources Chemical and Materials Engineering, Shaanxi University of Science & Technology, Xi’an 710021, China

Funds: National Nature Science Foundation of China (22178211); Key Research and Development Program of Shaanxi Province of China (2021 ZDLGY14-05); Shannxi Province Education Department Key Project (20 JY002)

摘要

摘要: 开发和利用绿色生物质材料能够降低石油基聚合物的消耗，但与单根细菌纤维素(BC)相比，BC薄膜表现出较低的力学性能，限制了其应用领域。为协同提高BC复合薄膜的强度和韧性，本文以BC为基体，通过对其碱处理、2, 2, 6, 6-四甲基哌啶-氮-氧化物(TEMPO)氧化处理得到TEMPO氧化的BC(TOBC)，并引入羧基化多壁碳纳米管(CNT)作为增强体，采用真空抽滤技术制备出CNT-TOBC复合薄膜，着重探究了CNT的添加对TOBC薄膜力学性能和微观形貌的影响，并探讨其增强增韧机制。研究结果表明：当CNT的添加量为7.5wt%时，CNT-TOBC复合薄膜的力学性能最佳，其断裂应力、伸长率及韧性分别为174 MPa、10.83%和12.01 MJ·m⁻³，相比纯的TOBC薄膜分别提高了56.76%、144.47%和295.07%，这主要归因于CNT与TOBC间的氢键相互作用、CNT内在高强度及外在增韧机制。研究结果为提高复合材料的界面结合和力学性能提供了一种切实可行的方法，并进一步拓宽了TOBC在柔性电子衬底、智能包装等领域的应用。
- 纳米纤维 /
- 碳纳米管 /
- 复合薄膜 /
- 强度 /
- 韧性 /
- 绿色生物质材料
Abstract: Exploiting and utilizing green biomass materials can reduce the consumption of petroleum-based polymers. However, compared with the single bacterial cellulose (BC), BC film always exhibits the poor mechanical properties, which limits its application. In this study, in order to improve the strength and toughness of BC composite films synergistically, BC was treated by alkaline and 2, 2, 6, 6-tetramethyl-1-piperidinyloxy (TEMPO) oxidation to obtain TEMPO-oxidized BC (TOBC), which was utilized as matrix to prepare the TOBC-based composite films enhanced by carboxylic multi-walled carbon nanotubes (CNT) via vacuum filtrating technique. The effect of CNT amounts on the mechanical properties and microstructure of TOBC-based composite films were investigated emphatically and the strengthening and toughening mechanism was also discussed. The results show that: When CNT content is 7.5wt%, CNT-TOBC composite films exhibit the best mechanical properties. The tensile stress, elongation and toughness of CNT-TOBC-7.5wt% composite films are 174 MPa, 10.83% and 12.01 MJ·m⁻³, respectively, which are increased by 56.76%, 144.47% and 295.07% compared with the pure TOBC films, respectively. The improvement is attributed to the hydrogen bonding interaction between CNT and TOBC, the high strength of CNT, as well as the external toughening mechanism. This study provides a feasible method to improve the interface bonding and mechanical properties of composites, and further broadens the application of TOBC in flexible electronic substrates, intelligent packaging and other fields.
- nanofibers /
- carbon nanotubes /
- composite films /
- strength /
- toughness /
- green biomass materials

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图 1 CNT-TOBC复合薄膜的制备流程图

Figure 1. Schematic diagram of CNT-TOBC composite films

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图 2 TOBC水分散液和CNT水分散液的光学照片、SEM图像和直径分布

D—Diameter

Figure 2. Optical photographs, SEM images and diameter distribution of TOBC water dispersion and CNT water dispersion

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图 3 不同CNT添加量的CNT-TOBC复合薄膜的光学照片

Figure 3. Optical photograph of CNT-TOBC composite films with different CNT content

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图 4 不同CNT添加量的CNT-TOBC复合薄膜的FTIR图谱

Figure 4. FTIR spectra of CNT-TOBC composite films with different CNT content

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图 5 纯的TOBC薄膜 (a) 和CNT-TOBC-7.5wt%复合薄膜 (b) 的高分辨率C1s XPS图谱

Figure 5. High resolution C1s XPS spectra of pure TOBC film (a) and CNT-TOBC-7.5wt% composite film (b)

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图 6 CNT薄膜 (a) 和不同CNT添加量的CNT-TOBC复合薄膜 (b) 的XRD图谱

Figure 6. XRD patterns of CNT film (a) and CNT-TOBC composite films with different CNT content (b)

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图 7 不同CNT添加量的CNT-TOBC复合薄膜的应力-应变曲线 (a)、断裂应力 (b)、断裂伸长率 (c) 和断裂韧性 (d)

Figure 7. Stress-strain curves (a), tensile stress (b), tensile strain (c) and toughness (d) of CNT-TOBC composite films with different CNT content

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图 8 纯TOBC薄膜和不同CNT添加量的CNT-TOBC复合薄膜断裂截面的SEM图像

Figure 8. Cross-sectional SEM images of pure TOBC film and CNT-TOBC composite film with different CNT content

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表 1 不同CNT添加量的羧基化多壁碳纳米管-TEMPO氧化的细菌纤维素(CNT-TOBC)复合薄膜的配方

Table 1. Formulations of carboxylic multi-walled carbon nanotubes-TEMPO-oxidized bacterial cellulose (CNT-TOBC) composite films with different CNT contents

Sample	TOBC/wt%	CNT/wt%
TOBC	100.0	0.0
CNT-TOBC-2.5wt%	97.5	2.5
CNT-TOBC-5wt%	95.0	5.0
CNT-TOBC-7.5wt%	92.5	7.5
CNT-TOBC-10wt%	90.0	10.0
Note: TEMPO—2, 2, 6, 6-tetramethyl-1-piperidinyloxy.

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表 2 不同CNT添加量的CNT-TOBC复合薄膜的厚度和紧度

Table 2. Thickness and tightness of CNT-TOBC composite films with different CNT contents

Sample	Thickness/μm	Tightness/(g·cm⁻³)
TOBC	28	1.43
CNT-TOBC-2.5wt%	30	1.33
CNT-TOBC-5wt%	31	1.29
CNT-TOBC-7.5wt%	32	1.25
CNT-TOBC-10wt%	34	1.18

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表 3 TOBC薄膜和CNT-TOBC-7.5wt%复合薄膜XPS分峰对应的结合能

Table 3. XPS peak binding energy assignments of TOBC film and CNT-TOBC-7.5wt% composite film

	Functional group	Binding energy/eV
TOBC	C—C	284.6
	C—OH	286.4
	C—O—C	287.8
	O—C═O	288.8
CNT-TOBC-7.5wt%	C—C	284.6
	C═C	285.1
	C—OH	286.6
	C—O—C	288.0
	O—C═O	289.2

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表 4 不同CNT添加量下的TOBC基体的结晶指数

Table 4. Crystalline indexes of TOBC matrix with different CNT content

Sample	Crystalline index/%
TOBC	90.42
CNT-TOBC-2.5wt%	89.74
CNT-TOBC-5wt%	91.71
CNT-TOBC-7.5wt%	93.35
CNT-TOBC-10wt%	94.02

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