离子液体中纤维素/纳米层状ZnO复合抗菌纤维的制备及性能

doi:10.7503/cjcu20170206

摘要/Abstract

摘要：

以表面活性剂十二烷基磺酸钠(SDS)为模板, Zn(NO₃)₂·6H₂O和NaOH为锌源和沉淀剂, 通过改进的模板法在温和条件下制得纳米层状ZnO. 以离子液体1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)为溶剂, 木浆纤维素和纳米层状ZnO为原料, 采用溶液共混方法, 通过干湿法纺丝制备了ZnO质量分数分别为3%, 5%, 7%及9%的纤维素/ZnO纳米复合纤维. 采用X射线衍射(XRD)、 X射线光电子能谱(XPS)、透射电子显微镜(TEM)、场发射扫描电子显微镜(SEM)及热重分析(TG)等方法对纳米层状ZnO及纤维素/ZnO复合纤维进行了表征, 并探讨了ZnO的加入对复合体系流变性的影响, 同时对复合纤维进行了力学和抗菌性能测试. 研究结果表明, 所制备氧化锌纯度高, 且呈现出重复周期为3.58 nm的层状结构, 抗菌性能优异. 纳米层状ZnO的加入提高了纤维素纤维的热稳定性和机械强度, 同时赋予纤维对金黄色葡萄球菌和大肠杆菌的抑菌性. ZnO片层被纤维素链剥离, 并均匀分散于纤维素/ZnO复合物中. ZnO的加入增大了纤维素溶液的黏度, 当ZnO含量达到5%以上时, 在整个频率范围内, 弹性模量大于损耗模量, 纳米粒子可稳定悬浮.

关键词: 纤维素, 离子液体, 纳米层状氧化锌, 纳米复合纤维, 抗菌性

Abstract:

Lamellar superstructured ZnO was synthesized via an improved template method in which sodium dodecyl sulfonate(SDS), Zn(NO₃)₂·6H₂O and NaOH were used as supramolecular template, Zn source and precipitant, respectively. Cellulose/nano lamellar ZnO composite fibers with ZnO 3%, 5%, 7%, 9% loading were processed from wood pulp and nano lamellar ZnO in the solution of 1-allyl-3-methylimidazolium chloride([Amim]Cl) by blending method via dry-jet wet spinning. The lamellar ZnO and its nanocomposites with cellulose were examined by X-ray powder diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscope(TEM), field emission scanning electron microscopy(FESEM), and thermogravimetric analysis(TG). The influence of ZnO on the rheological property of composite systems was discussed. Besides, the strength and antibacterial activity of the composite fibers were tested. The results indicated that the as-synthesized ZnO presented a pure and well crystallized hexagonal wurtzite phase ZnO, as well as a periodic of 3.58 nm lamellar superstructure. Due to the addition of nano lamellar ZnO, the cellulose/ZnO nanocompo-sites exhibit better thermal stability and mechanical properties than original cellulose. Furthermore, antimicrobial assessment show that the composite fiber possess excellent antibacterial activities against S. aureus and E. coli. ZnO was exfoliated by cellulose chains. The ZnO platelets were homogeneously dispersed in cellulose/ZnO compounds. Besides, the rheology results showed that the presence of nano ZnO increased the viscosity of cellulose solution. When the ZnO content was 5% or above, in the whole frequency range, elasticity modulus was greater than the loss modulus, which inferred that nanoparticles could suspend steadily.

Key words: Cellulose, Ionic liquid, Nano lamellar ZnO, Nanocomposite fiber, Antibacterial activity

中图分类号:

TrendMD:

付冉冉, 纪秀杰, 刘超, 任燕飞, 汪港, 程博闻. 离子液体中纤维素/纳米层状ZnO复合抗菌纤维的制备及性能. 高等学校化学学报, 2017, 38(12): 2344.

FU Ranran, JI Xiujie, LIU Chao, REN Yanfei, WANG Gang, CHENG Bowen. Fabrication of Cellulose/Nano Lamellar ZnO Composite Antibacterial Fibers Using Ionic Liquid^†. Chem. J. Chinese Universities, 2017, 38(12): 2344.

图/表 12

Fig.1 Small(A) and wide(B) angle XRD patterns of Lα-ZnO(a) and TF-ZnO(b)

Fig.2 TEM images of Lα-ZnO viewed through perpendicular direction(A) and parallel direction(B)

Fig.3 SEM image(A) and the size distribution histogram(B) of Lα-ZnO

Fig.4 Digital photograph of inhibition zone for Lα-ZnO samples against E. coli(A—C) and S. aureus(D—E)(A) Control to E. coli; (B) TF-ZnO against E. coli; (C) Lα-ZnO against E. coli; (D) control to S. aureus;(E) TF-ZnO against S. aureus; (F) Lα-ZnO against S. aureus.

Fig.5 Steady shear flow curves for the cellulose solutions with different content of Lα-ZnO at 40 ℃

Fig.6 Changes of storage(G') and loss moduli(G″) as a function of angular frequency for the cellulose solutions with different content of nano-ZnO at 40 ℃

Fig.7 Tensile strength of cellulose fibers as a function of Lα-ZnO content

Fig.8 WAXD patterns of raw cellulose(a), regenerated cellulose fiber(b) and cellulose/ZnO composite fiber containing 7% ZnO(c)

Fig.9 XPS spectra of cellulose/ZnO composite fiber containing 7% nano-ZnO (A) Survey; (B) Zn2p.

Fig.10 TGA curves of cellulose fiber(a) and cellulose composite fiber containing 7% Lα-ZnO(b) The inset displays differential thermogravimetric analysis(DTG) curves.

Fig.11 SEM images of side surface sections(A, C) and cross sections(B, D) of cellulose fiber(A, B) and cellulose/Lα-ZnO composite fiber(C, D)(E) Magnified image of cellulose/Lα-ZnO composite fiber; (F) digital photograph of cellulose/Lα-ZnO composite fiber.

Table 1 Antibacterial properties of composite fibers with different nano-ZnO content against E. coli and S. aureus

Sample	E. coli		S. aureus
Sample	10^-7 Microbial concentration/ (cfu·mL^-1)^*	Reduction in viability(%)	10^-3 Microbial concentration/ (cfu·mL^-1)	Reduction in viability(%)
ZnO	8.5		69
ZnO/3%	4.2	50.6	9	87.0
ZnO/5%	3.2	62.4	7	89.9
ZnO/7%	2.4	71.8	5	92.8
ZnO/9%	2.1	75.3	4	94.2

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