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基于微流控技术的载银螺旋海藻复合纤维的绿色连续制备

刘辉灿 殷亚然 王之豪 陈秀芳 张先明

刘辉灿, 殷亚然, 王之豪, 等. 基于微流控技术的载银螺旋海藻复合纤维的绿色连续制备[J]. 复合材料学报, 2024, 42(0): 1-12.
引用本文: 刘辉灿, 殷亚然, 王之豪, 等. 基于微流控技术的载银螺旋海藻复合纤维的绿色连续制备[J]. 复合材料学报, 2024, 42(0): 1-12.
LIU Huican, YIN Yaran, WANG Zhihao, et al. Green continuous preparation of silver-loaded helical alginate composite fibers based on microfluidic technology[J]. Acta Materiae Compositae Sinica.
Citation: LIU Huican, YIN Yaran, WANG Zhihao, et al. Green continuous preparation of silver-loaded helical alginate composite fibers based on microfluidic technology[J]. Acta Materiae Compositae Sinica.

基于微流控技术的载银螺旋海藻复合纤维的绿色连续制备

基金项目: 浙江省“尖兵”“领雁”研发攻关计划项目 (2023 C01095);国家自然科学基金 (22008220);浙江省自然科学基金 (LQ21 B060009);浙江理工大学绍兴柯桥研究院项目 (KYY2022002 B)。
详细信息
    通讯作者:

    殷亚然,博士,副教授,硕士生导师,研究方向为微化工技术, E-mail: yryin@zstu.edu.cn

  • 中图分类号: TB333

Green continuous preparation of silver-loaded helical alginate composite fibers based on microfluidic technology

Funds: Zhejiang Provincial “Top Soldier” and “Le ading Wild Goose” R&D Program (2023 C01095); National Natural Science Foundation of China (22008220); Natural Science Foundation of Zhejiang Province (LQ21 B060009); Fundamental Research Funds of Shaoxing Keqiao Research Institute of Zhejiang Sci-Tech University (KYY2022002 B)
  • 摘要: 提高螺旋海藻纤维抗菌性可保障纤维应用安全及稳定性,然而由于抗菌剂和海藻纤维制备过程中试剂间的相容性等问题难以克服,致使共混纺丝过程步骤繁琐,复合纤维的螺旋形貌和性能难以保证。鉴于此,本文以绿色柠檬酸钠 (TSC) 作为纳米银粒子 (AgNPs) 抗菌剂的还原稳定剂和海藻纤维螺旋形貌的成型促进剂,基于微流控技术构建了载银螺旋海藻复合纤维的连续纺丝系统,并对螺旋复合纤维的形貌、力学、热稳定、银元素释放和抑菌等性能进行了表征。结果表明,AgNPs呈球形,粒径较为均一,在4~12 nm之间。在抗菌剂‒纤维连续制备下,AgNPs能够均匀分布在纤维内部,且增大AgNPs负载量,不仅有利于增强纤维断裂强度和热稳定性,还促进了螺旋复合纤维形成,使断裂伸长率和弹性显著高于线形复合纤维。当AgNPs负载量大于200 mg/kg时,抗菌率可达99.9%以上,且具有长效、高效的抗菌潜力。本研究为抗菌螺旋海藻纤维性能调控提供了理论基础,为复合材料的连续化精准构筑提供了技术指导。

     

  • 图  1  载银螺旋海藻复合纤维连续制备示意图:(a) 纳米银粒子 (AgNPs)制备系统;(b) 纺丝液混合系统;(c) 微流控纺丝系统

    Figure  1.  Schematic illustration of continuous preparation of silver-loaded helical alginate composite fibers: (a) silver nanoparticles (AgNPs) synthesis; (b) spinning solution mixing; (c) microfluidic spinning.

    图  2  不同条件下AgNPs溶液的UV-vis谱图 (a,d,g)、DLS粒径图 (b,e,h) 和AgNPs溶液的直观图 (c,f,i)

    (a~c:不同AgNO3浓度 (mmol/L);d~f:不同TSC浓度 (mmol/L);g~i:不同紫外照射时间 (min) )

    Figure  2.  UV–vis spectroscopy (a,d,g) , DLS particle size diagram (b,e,h) , and visual images of AgNPs solutions (c, f, i) under different conditions

    (a~c: different AgNO3 concentrations (mmol/L) ; d~f: different TSC concentrations (mmol/L) ; g~I: different UV irradiation time (min) )

    图  3  AgNPs的TEM照片及粒径分布图

    Figure  3.  TEM images and particle size distributions of AgNPs

    图  4  AgNPs的XRD图

    Figure  4.  XRD pattern of AgNPs ([Ag+] 1 mmol/L, [TSC] 18 mmol/L, UV 17 min)

    图  5  载银海藻复合纤维的SEM和EDS-mapping图: (a) 纤维的SEM图; (b~d) 纤维表面C、O、Ag元素的分布图

    Figure  5.  SEM and EDS-mapping image of silver-loaded alginate composite fiber: (a) SEM image of the fiber; (b~d) distribution of C, O, Ag on the surface of the fibers

    图  6  载银海藻复合纤维显微图像和形态分布图: (a) 线形纤维图; (b) 螺旋纤维图; (c) 波浪纤维图; (d) 形态分布图

    Figure  6.  Microscopic images and morphology distribution of silver-loaded alginate composite fibers: (a) linear fiber image; (b) helical fiber image; (c) wavy fiber image; (d) morphology distribution

    图  7  TSC促进螺旋纤维成形示意图

    Figure  7.  Schematic diagram of TSC promoting helical fiber formation

    图  8  载银海藻复合纤维的应力应变曲线

    Figure  8.  Stress-strain curves of silver-loaded alginate composite fibers

    图  9  载银螺旋海藻复合纤维的回弹性测试

    Figure  9.  Resilience testing of silver-loaded helical alginate composite fibers

    图  10  不同AgNPs负载的螺旋海藻复合纤维的TG曲线

    Figure  10.  TG curves of helical alginate composite fiber with different loads of AgNPs

    图  11  载银螺旋海藻复合纤维在水中银元素的释放曲线

    Figure  11.  Release curve of silver element from silver-loaded helical alginate composite fibers in water

    图  12  载银螺旋海藻复合纤维对大肠杆菌 (上) 和金黄色葡萄球菌 (下) 的抑菌圈实验结果图

    Figure  12.  Inhibition zone experiment results of of silver-loaded helical alginate composite fibers against E. coli (above) and S. aureus (below)

    图  13  载银螺旋海藻复合纤维对大肠杆菌 (上) 和金黄色葡萄球菌 (下) 抗菌测试: (a) 实验照片; (b) 抗菌率

    Figure  13.  Antibacterial testing of silver-loaded helical alginate composite fibers against E. coli (above) and S. aureus (below): (a) experimental photographs; (b) antibacterial rate

    表  1  载银海藻复合纤维的拉伸力学性能

    Table  1.   Tensile mechanical properties of silver-loaded alginate composite fibers

    Sample Linear
    F-0
    Linear
    F-100
    Linear
    F-200
    Linear
    F-400
    Helical
    F-0
    Helical
    F-100
    Helical
    F-200
    Helical
    F-400
    Fracture strength/
    (cN·dtex-1)
    0.23 ± 0.10a 0.49 ± 0.23b 0.63 ± 0.11c 0.74 ± 0.11d 0.22 ± 0.01a 0.49 ± 0.07b 0.64 ± 0.09c 0.73 ± 0.09d
    Elongation/% 12.47 ± 3.27 12.79 ± 4.65 13.25 ± 2.14 12.56 ± 1.33 132.66 ± 4.70a 137.00 ± 7.29b 142.28 ± 5.93c 148.2 ± 4.56d
    Initial Modulus/
    (cN·dtex-1)
    5.11 ± 2.51a 16.25 ± 4.21b 22.38 ± 4.23c 23.78 ± 3.40d 0.08 ± 0.04 0.10 ± 0.02 0.09 ± 0.02 0.10 ± 0.02
    Notes: All data are expressed as a mean ± standard deviation. Data in a row labeled with the different symbols were significantly different from each other (P < 0.05) .
    下载: 导出CSV

    表  2  载银螺旋海藻复合纤维的抑菌圈直径

    Table  2.   Inhibition zone diameters of silver-loaded helical alginate composite fibers

    Strain Average inhibition zone diameters (mm)
    Silver-loaded alginate composite fibers
    F-0 F-100 F-200 F-400
    E. coli 0 1.5 1.95 2.4
    S. aureus 0 1.43 3.15 4.8
    下载: 导出CSV
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  • 收稿日期:  2024-01-15
  • 修回日期:  2024-03-14
  • 录用日期:  2024-03-22
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