现代纺织技术 ›› 2023, Vol. 31 ›› Issue (5): 66-75.

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细菌纤维素纳米纤维膜及纤维的制备与性能

  

  1. 1.浙江理工大学材料科学与工程学院,杭州 310018;2.杭州万事利丝绸数码印花有限公司,杭州 310020
  • 收稿日期:2023-03-13 出版日期:2023-09-10 网络出版日期:2023-09-20
  • 基金资助:
    浙江省自然科学基金项目(LGC22E030006);浙江省清洁染整技术研究重点实验室开放基金项目(QJRZ2110);浙江省重点研发计划(2121069J);安徽省纺织结构复合材料国际合作研究中心项目(2021ACTC03)

Preparation and properties of bacterial cellulose nanofiber membranes and fibers

  1. 1. School of Materials Science & Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China; 2. Hangzhou WENSLI Silk Digital Printing Co., Ltd, Hangzhou 310020, China
  • Received:2023-03-13 Published:2023-09-10 Online:2023-09-20
  • About author:陈钦钦(1997—),女,杭州人,硕士研究生,主要从事细菌纤维素方面的研究。

摘要: 为改善细菌纤维素(BC)干燥薄膜(简称干膜)的力学性能,在保留BC原始结构的基础上,通过溶剂置换、热压工艺首先制得BC干膜,进而通过自上而下的机械剥离法制备高强度纳米纤维膜(NFM),对所得NFM的结构、形貌和物化性能进行了表征。进一步利用加捻NFM的方法制得BC纤维,并且通过在加捻前复合碳纳米管(CNT)得到了应变传感纤维。结果表明:一次(1st)、二次(2nd)和三次(3rd)机械逐层剥离得到的NFM厚度逐渐降低,分别为8.0、6.5、5.0 μm;3种NFM的吸水率较BC干膜均显著增加,其中3rd-NFM的吸水率最高,为2284%,是BC干膜的2.4倍;3rd-NFM的拉伸强度最高,可达338.0 MPa,为BC干膜的11.7倍;通过对人体运动(包括手指、手腕的弯曲和吞咽动作)的监测表明,CNT赋予了BC/CNT纤维良好的电阻响应性,使其在0~2%的相对电阻变化范围内,具有较好应变传感性能,拓宽了该纤维在可穿戴传感器领域的发展前景。

关键词: 细菌纤维素, 机械剥离, 纳米纤维膜, 加捻, 应变传感

Abstract: Bacterial cellulose (BC), as a suitable alternative to petroleum-based materials, has many inherent and unique properties such as biocompatibility, biodegradability, breathability and high-water holding capacity. But it is difficult to dissolve in common organic solvents because of its tight intramolecular and intermolecular hydrogen bonds. BC usually exists in the form of thin membranes, and the mechanical properties of BC dried membranes are poor. The current methods for preparing BC nanofiber membranes (NFMs) with BC fibers all inevitably destroy the original structure of BC. 
In this work, the hydrogen bonding between water and nanofibers in BC hydrogel membranes was weakened by the solvent replacement method, and the layer-by-layer peeling of BC dry membranes was achieved by hot-pressing drying combined with the top-down mechanical peeling method to produce high-strength BC-NFM, and BC fibers could be obtained by further twisting of NFMs. The morphology, structure and physicochemical properties of the BC dry membrane, NFMs and BC fibers were analyzed and studied by characterization means such as scanning electron microscopy, X-ray diffractometer, thermogravimetric analyzer, infrared spectrometer and tensile test. In addition, the strain sensing fiber BC/CNT can be achieved by embedding functional materials such as CNT into NFMs before twisting. The resistance change rate of the BC/CNT fiber obtained by this method can reach 2%. It is shown that the randomly distributed nanofibers on the surface of the BC dry membrane all have a network structure and exhibit a dense structure. As the mechanical peeling step proceeds, the nanofibers on the NFM surface become dispersed and the number of disordered nanofibers on the surface increases, which proves that NMP weakens the hydrogen bonds between the solvent and the BC nanofibers, thus facilitating the mechanical peeling of BC, and in turn leading to the appearance of microfibrils on the NFM surface. The crystallinity of all three mechanically exfoliated NFMs is lower than that of the dry BC membrane, and the crystallinity of 3rd-NFM is the smallest, demonstrating that the NMP treatment does not affect the BC crystal structure. The small-angle scattering patterns show that the arc diameter gradually becomes smaller with the increase of the stripping number, and the 3rd-NFM is the smallest, which proves that the stripping process breaks the hydrogen bonds inside BC and increases the disorder. The intensity of the tensile vibrational peak of the cellulose C−H bond decreases with the increase of the number of peeling, which proves that NMP can break the hydrogen bonds between BC molecules and form new hydrogen bonds with the hydroxyl groups in BC molecules. The NFMs with thickness in the range of 5.0 to 8.0 μm shows a maximum transmission of 23%, water absorption of 2,284% and tensile strength of 338.0 MPa, each of which is higher than that of the BC dry membrane. Compared with the maximum decomposition temperature of the BC dry membrane (359.7 °C), the main weight loss peak temperatures of all the three NFMs are reduced in the range of 333.7 to 339.5 °C, demonstrating the disruption of intermolecular and intramolecular hydrogen bonds of BC by NMP. Surface SEM images of BC fibers show that the 3rd-NFM-fiber has the smallest diameter and the tightest structure, proving that mechanical peeling effectively reduces the diameter of NFMs-fiber and enhances the structural denseness of the fiber. The monitoring of tiny human body movements by BC/CNT conductive fibers fully demonstrates their potential application in smart wearable devices. 
This paper provides scientific data for the preparation of BC-NFMs by top-down method of mechanical peeling, which provides new ideas for the development of high-strength NFMs.

Key words: bacterial cellulose, mechanical peeling, nanofiber membrane, twist, strain sensing

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