Structure and properties of chitosan enhanced cellulose nanofiber-montmorillonite composite membrane
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摘要: 利用纤维素和无机物模仿天然贝壳中高度有序的“砖-砂浆”结构制备高强度功能复合材料，是制备绿色包装膜的优秀选择，二者的界面结合是获得理想结构与性能的关键。本文以羧基化纤维素纳米纤维(CNFMG)和蒙脱土(MTM)纳米片制备膜材料，采用壳聚糖(CS)通过静电作用增强界面结合。研究了CS与CNFMG和MTM之间的静电相互作用对纳米复合材料结构、力学性能和热稳定性的影响。结果表明，复合膜中MTM以纳米片状形态有序地分散于CNFMG网络间。与CNFMG-MTM二元膜相比，CS加入后的三元膜拉伸强度达到119.2 MPa，强度提升一倍；断裂能达到10.9 MJ/m3，韧性提升四倍。复合膜为半透明状，具有良好的紫外屏蔽性，CS的加入也提升了复合膜的热稳定性。本文的研究结果可为纤维素基珍珠层仿生材料的研究和应用提供思路。Abstract: The way of mimicking the ordered “brick and mortar” structure in natural shells to prepare high-strength functional composite materials with cellulose and inorganic substances of which the interface bonding is the key to achieving ideal structure and performance is a potential excellent choice for producing naturally degradable packaging films. The single interfacial binding force between nanocellulose and montmorillonite results in insufficient mechanical properties. In this work, carboxymethyl cellulose nanofibers (CNFMG) and montmorillonite (MTM) nanosheets were used to prepare pearl layer films in which chitosan (CS) enhanced interface bonding through electrostatic interaction. The effects of electrostatic interactions between CS, CNFMG, and MTM on the structure, mechanical properties, and thermal stability of nanocomposites were studied. The results indicate that MTM in the composite membrane was orderly dispersed in nanosheet form between CNFMG networks. Compared with the CNFMG-MTM binary film, the tensile strength of the ternary film with the addition of CS reached 119.2 MPa, which doubled the strength. The fracture energy reached 10.9 MJ/m3, and the toughness was increased by four times. The composite film was semitransparent and had good UV shielding properties. The addition of CS also enhanced the thermal stability of the composite film. The research results of this article can provide ideas for the research and application of cellulose based pearl layer biomimetic materials.
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Key words:
- nanocellulose /
- montmorillonoid /
- chitosan /
- composite membrane /
- biomimetic pearl layer structure
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图 1 壳聚糖(CS)-羧基化纤维素纳米纤维(CNFMG)-蒙脱土(MTM)复合膜的实物图和静电增强示意图
Figure 1. Photo and diagrammatic sketch about electrostatic enhancement of chitosan (CS)- carboxymethyl cellulose nanofibers (CNFMG)- montmorillonite (MTM) composite membrane
图 2 MTM 纳米片性状表征：(a，b)AFM图、胶体丁达尔效应(b 插图)；(c)厚度尺寸统计；(d)AFM三维示意；(e，f)透射电镜图
Figure 2. Characterization of MTM nano sheets: (a,b) AFM images、the colloidal Dingdall effect(illustrations in figure b); (c) thickness dimension statistics; (d) AFM 3 D schematic diagram; (e,f) TEM images
图 3 (a) CNFMG的 AFM图；(b)对应(a)图中纤维直径高度示意图；(c，d) CNFMG的透射电镜图
Figure 3. AFM image (a) ; schematic diagram of fiber diameter and height corresponding to figure (b) and TEM images (c,d) of CNFMG
图 4 纯 CNFMG膜(a-d)；CCM-0.5(e-h)表面和拉伸断面；(j)贝壳 Semicassis bisulcate[1] ；(k)贝壳Fissurella crassa [1]的扫描电子显微镜(SEM)图像，EL(external layer)指外部层，ML 指中间层(middle layer)，IL 指内部层(initial layer)
Figure 4. SEM iamges of surface and stretch section of pure CNFMG membrane (a-d); CCM-0.5 (e-h) and facture for Semicassis bisulcate(j) and Fissurella crassa (k), EL, external layer; ES, external surface of the shell; IL, internal layer;ML, middle layer
图 5 不同 CS 添加量(0-30wt%)复合膜的小角 度 X射线衍射图谱(XRD )
Figure 5. XRD patterns of composite membranes with different CS additive rate(0-30wt%)
图 6 MTM粉末、CNFMG膜和纳米复合膜的FTIR谱图
Figure 6. FITR patterns of MTM powder,CNFMG membrane and nano composite membranes.
图 7 (a)纯CNFMG和复合薄膜的应力应变曲线；(b)孔隙率；(c)拉伸强度；(d)模量；(e)断裂伸长率；(f)断裂能
Figure 7. Stress-strain cureves (a);porosity(b);tensile strength (c);modulus (d); elongation at break (e) and fracture energy (f) of pure CNFMG membrane and composite membranes
图 8 原料及复合膜的热重谱图：(a) TGA曲线；(b) DTG曲线
Figure 8. TGA patterns (a) and DTG (b) patterns of raw materials and composite membranes
图 9 (a,b)不同CS含量的CS-CNFMG -MTM混合液；(c,d)复合膜的紫外-可见光光谱图
Figure 9. UV-vis spectrums of CS-CNFMG-MTM mixed liquids (a,b) and composite membranes (c,d) with different CS rate
表 1 试样的配比与命名
Table 1. Naming of membrane with different CS ratio
Name CS/wt% CNFMG/MTM(mass ratio) CNFMG — — CCM-0 0 1∶1 CCM-0.25 0.25 1∶1 CCM-0.5 0.5 1∶1 CCM-0.75 0.75 1∶1 CCM-1.0 1.0 1∶1 CCM-10 10 1∶1 CCM-20 20 1∶1 CCM-30 30 1∶1 Notes: CCM—CS-CNFMG-MTM 
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