Preparation and strain sensitive performance of cellulose nanofiber-carbon nanotubes/ thermoplastic polyurethane composite films
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摘要: 采用2,2,6,6−四甲基哌啶−1−氧自由基(TEMPO)氧化法制备了不同羧基含量的纳米纤维素(CNF)，并将其用作碳纳米管(CNTs)的分散剂，通过超声、离心处理制备出稳定均一的CNF−CNTs分散液，然后通过朗伯−比尔定律测定CNF−CNTs分散液中CNTs的浓度，研究了不同CNF羧基含量对CNTs的分散效果。此外，利用静电纺丝法制备出柔性、多孔的热塑性聚氨酯(TPU)薄膜作为基体，以CNF−CNTs分散液作为导电填料，通过真空抽滤法将CNF−CNTs负载于TPU多孔膜上，制备出CNF−CNTs/TPU复合薄膜，并探究了不同CNF羧基含量对CNF−CNTs/TPU复合薄膜应变响应性能的影响规律。结果表明，羧基含量对CNF的分散性能具有重要影响。随着CNF羧基含量的提高，CNF对CNTs分散效果越好，CNF−CNTs/TPU复合薄膜具有更大的应变响应范围。当CNF羧基含量为1.698 mmol/g时，CNF−CNTs/TPU复合薄膜的应变响应范围高达507%，灵敏度系数为335，表现出优异的应变响应性能。Abstract: The 2,2,6,6−Tetramethylpiperidine−1−oxyl radical (TEMPO) oxidation was used for preparation of cellulose nanofibers (CNF) with different carboxyl contents. Then the prepared CNF was used as the dispersing agent to disperse carbon nanotubes (CNTs) and the concentration of CNF−CNTs dispersion was measured by Lambert−Beer’s law to study the dispersion effect of CNF with different carboxyl contents. In addition, the CNF−CNTs/thermoplastic polyurethanes (TPU) composite film was prepared by pumping CNF−CNTs fillers in the prepared electrospun TPU film through vacuum filtration. The influence of carboxyl content of CNF on the strain sensitive performance of CNF−CNTs/TPU composite film was investigated. The result shows that, with the increase of the carboxyl content of CNF, the CNF has a better dispersion effect on CNTs, and the prepared CNF−CNTs/TPU composite film possesses a larger workable strain range. When the carboxyl content of CNF achieves 1.698 mmol/g, the CNF−CNTs/TPU composite film displays a large workable strain range of 507% and a high gauge factor of 335, exhibiting excellent strain sensitive performance.
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图 1 纳米纤维素-碳纳米管/热塑性聚氨酯(CNF−CNTs/TPU)复合薄膜的制备示意图
Figure 1. Schematic diagram of preparation of cellulose nanofiber-carbon nanotubes/thermoplastic polyurethane(CNF−CNTs/TPU) composite film
DMF—N,N-dimethylformamide
图 2 CNF-CNTs/TPU复合薄膜的光学照片(插图为卷曲状态)
Figure 2. Optical photograph of CNF-CNTs/TPU composite film (Inset is bending state)
图 3 不同羧基含量的CNF分散液(1 mg/mL)的光学照片
Figure 3. Optical photograph of CNF dispersions (1 mg/mL) with different carboxyl contents
图 4 不同CNF羧基含量的CNF-CNTs分散液的紫外-可见吸收光图谱
Figure 4. UV-Vis absorption spectra of CNF-CNTs dispersion with different carboxyl contents of CNF
图 5 静电纺丝TPU多孔膜(a)和CNF−CNTs/TPU复合薄膜预拉伸前(b)、横截面(c)、预拉伸后(d)的SEM图像
Figure 5. SEM images of electrospun TPU porous film (a) and before pre-stretching (b), cross section (c) and after pre-stretching (d) of CNF−CNTs/TPU composite film
图 6 不同应变下CNF-CNTs/TPU复合薄膜电阻相对变化曲线
Figure 6. Relative change of resistance curves of CNF-CNTs/TPU composite films under different strains
图 7 CNF-CNTs/TPU复合薄膜拉伸至400%时的光学照片
Figure 7. Optical photographs of CNF-CNTs/TPU composite films under strain of 400% ((a) CNF-CNTs/TPU1; (b) CNF-CNTs/TPU2; (c) CNF-CNTs/TPU3; (d) CNF-CNTs/TPU4)
图 8 CNF−CNTs/TPU 复合薄膜拉伸-释放后的 SEM 图像
Figure 8. SEM images of CNF−CNTs/TPU composite films ((a) CNF−CNTs/TPU1, (b) CNF−CNTs/TPU2, (c) CNF−CNTs/TPU3, (d) CNF−CNTs/TPU4, (e) CNF−CNTs/TPU4’s crack, (f) Magnification of CNF−CNTs/TPU4’s crack)
表 1 不同CNF羧基含量的CNF-CNTs/TPU复合薄膜的编号及成分
Table 1. Serial numbers and component details of CNF-CNTs/TPU composite films with different carboxyl contents of CNF
No. Carboxyl content of CNF/(mmol·g−1) CNF/
wt%CNTs/
wt%TPU/
wt%CNF-CNTs/TPU1 0.663 2.4 1.2 96.4 CNF-CNTs/TPU2 0.947 2.4 1.2 96.4 CNF-CNTs/TPU3 1.348 2.4 1.2 96.4 CNF-CNTs/TPU4 1.698 2.4 1.2 96.4 
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