氧化纳米纤维素增强再生纤维素全纤维素复合薄膜的制备及性能

周可可; 唐亚丽; 卢立新; 潘嘹; 丘晓琳

doi:10.13801/j.cnki.fhclxb.20191120.003

氧化纳米纤维素增强再生纤维素全纤维素复合薄膜的制备及性能

doi: 10.13801/j.cnki.fhclxb.20191120.003

江南大学　机械工程学院，无锡 214122

基金项目: 国家自然科学基金(31671909)

详细信息

通讯作者:
唐亚丽，博士，副教授，硕士生导师，研究方向为食品包装材料与制品　E-mail：tangyali35@126.com

中图分类号: TB324；TB332
计量
- 文章访问数: 1323
- HTML全文浏览量: 418
- PDF下载量: 98
- 被引次数: 0
出版历程
- 收稿日期: 2019-08-04
- 录用日期: 2019-11-12
- 网络出版日期: 2019-11-21
- 刊出日期: 2020-07-15

Preparation and properties of all-cellulose composite films with oxidized cellulose nanofibrils reinforcing regenerated cellulose

School of Machanical Engineering, Jiangnan University, Wuxi 214122, China

摘要

摘要: 以2,2,6,6-四甲基哌啶-氮-氧化物(TEMPO)氧化松木粉纳米纤维素(TOCNs)为增强相、α-纤维素粉制备再生纤维素(RC)为基体，采用溶胶-凝胶法制备氧化纳米纤维素增强再生纤维素(TOCNs/RC)全纤维素复合薄膜。对不同TOCNs添加量下TOCNs/RC全纤维素复合薄膜的力学性能、光学性能、氧气阻隔性能和热稳定性能进行研究，并通过FTIR、SEM、TEM、XRD和流变仪对TOCNs和TOCNs/RC全纤维素复合薄膜的结构、形貌及纤维素溶液流变性能进行表征。结果表明，TOCNs添加量对TOCNs/RC全纤维素复合薄膜的力学性能有显著影响，当TOCNs添加量(与纤维素基体的质量比)为1.0%时，TOCNs/RC全纤维素复合薄膜的拉伸强度和断裂能分别可达134.3 MPa和21.51 MJ·m⁻³，具有最佳的综合力学性能；TOCNs/RC全纤维素复合薄膜的透光率随TOCNs添加量的增加而下降，雾度随TOCNs添加量的增加而增大，但仍保持较高的透光率(>85%)和较低的雾度(<14%)；TOCNs/RC全纤维素复合薄膜还具有优异的氧气阻隔性，TOCNs添加量为1.6%时，其透氧系数仅为1.47×10⁻¹⁷cm³·cm/cm²·s·Pa。TOCNs/RC全纤维素复合薄膜有优于一般塑料薄膜的拉伸强度和氧气阻隔性，并有可媲美于塑料薄膜的透明度，可作软包装复合材料的强度层和阻隔层，在绿色高性能包装材料领域具有广阔的应用前景。
- 纳米纤维素 /
- 全纤维素复合材料 /
- 力学性能 /
- 光学性能 /
- 氧气阻隔性能 /
- 复合薄膜
Abstract: The oxidized cellulose nanofibrils reinforcing regenerated cellulose (TOCNs/RC) all-cellulose composite films were prepared with 2,2,6,6-tetramethylpiperidinooxy (TEMPO) oxidized cellulose nanofibrils of pine powder as the reinforcments and RC of α-cellulose powder as the matrix by the sol-gel method. The properties of mechanical, optical, oxygen barrier, thermal stability of TOCNs/RC all-cellulose composite films with different mass ratios of TOCNs to RC were investigated. The structure, morphology of TOCNs/RC all-cellulose composite films and the rheology of cellulose solution were characterized by FTIR, SEM, TEM, XRD and rheometer. The results show that TOCNs have significant effects on the mechanical properties of TOCNs/RC all-cellulose composite films. The tensile strength and fracture energy of TOCNs/RC all-cellulose composite films reach at 134.3 MPa and 21.51 MJ·m⁻³ respectively with TOCNs content of 1.0% (mass ratio to cellulose matrix ) , which has the best comprehensive mechanical properties. The transmittance decreases and haze increases as the augment of the mass ratios of TOCNs, but TOCNs/RC all-cellulose composite films still maintain high transmittance (>85%) and low haze (<14%). The TOCNs/RC all-cellulose composite films also have excellent oxygen barrier property and the oxygen transmission coefficient reaches a minimum of 1.47×10⁻¹⁷cm³·cm/cm²·s·Pa at 1.6% TOCNs. The TOCNs/RC all-cellulose composite films have better tensile strength and oxygen barrier property than general plastic films and also have comparable transparency, which can be used as the strength or barrier layer for the flexible packaging composites and have profound application prospects in the field of green and high-performance packaging meterials.
- cellulose nanofibrils /
- all-cellulose composites /
- mechanical property /
- optical property /
- oxygen barrier property /
- composite film

HTML全文

图 1 不同TOCNs添加量的TOCNs/再生纤维素(RC)复合膜的力学性能

Figure 1. Mechanical properties of TOCNs/regenerated cellulose(RC) composite films with different mass ratios of TOCNs

下载: 全尺寸图片幻灯片

图 2 不同TOCNs添加量的TOCNs/RC复合膜的应力-应变曲线和断裂能

Figure 2. Stress-strain curves and fracture energies of TOCNs/RC composite films with different mass ratios of TOCNs

下载: 全尺寸图片幻灯片

图 3 不同TOCNs添加量的TOCNs/RC复合膜在900~200 nm波长的透光率(a)、雾度及800 nm波长处透光率(b)

Figure 3. Transmittance at 900–200 nm wavelength(a), haze and transmittance at 800 nm wavelength(b) of TOCNs/RC composite films with different mass ratios of TOCNs

下载: 全尺寸图片幻灯片

图 4 不同TOCNs添加量的TOCNs/RC复合膜的宏观光学照片

Figure 4. Macro optical photos of TOCNs/RC composite films with different mass ratios of TOCNs

下载: 全尺寸图片幻灯片

图 5 不同TOCNs添加量的TOCNs/RC复合膜的TG(a)和DTG(b)曲线

Figure 5. TG(a) and DTG(b) curves of TOCNs/RC composite films with different mass ratios of TOCNs

下载: 全尺寸图片幻灯片

图 6 不同TOCNs添加量的TOCNs/RC复合膜的FTIR图谱

Figure 6. FTIR spectra of TOCNs/RC composite films with different mass ratios of TOCNs

下载: 全尺寸图片幻灯片

图 7 不同TOCNs添加量的TOCNs/RC复合膜的XRD图谱

Figure 7. XRD patterns of TOCNs/RC composite films with different mass ratios of TOCNs

下载: 全尺寸图片幻灯片

图 8 TOCNs和TOCNs/RC复合膜的TEM和SEM图像

Figure 8. TEM and SEM images of TOCNs and TOCNs/RC composite films

下载: 全尺寸图片幻灯片

图 9 纤维素溶液黏度随剪切速率变化

Figure 9. Viscosity of cellulose solution changing with shear rate

下载: 全尺寸图片幻灯片

图 10 纤维素溶液的应变扫描曲线(a)和频率扫描曲线(b)

Figure 10. Oscillation strain curves(a) and oscillation frequency curves(b) of cellulose solution

下载: 全尺寸图片幻灯片

表 1 氧化纳米纤维素(TOCNs)与纤维素基体的质量比

Table 1. Mass ratios of oxidized cellulose nanofibrils (TOCNs) to cellulose matrix

Sample	Mass ratio of TOCNs/%	TOCNs/DMAc solution/%	Cellulose solution/%
TOCNs_0.0/RC	0	0	100
TOCNs_0.5/RC	0.5	5	100
TOCNs_1.0/RC	1.0	10	100
TOCNs_1.6/RC	1.6	16	100
TOCNs_2.4/RC	2.4	24	100
Notes: RC—Regenerated cellulose; DMAc—N,N-dimethylace-tamide.

下载: 导出CSV

表 2 不同TOCNs添加量的TOCNs/RC复合膜的透氧量(OP)和透氧系数(OPC)

Table 2. Oxygen permeanbility(OP) and oxygen permeability coefficient(OPC) of TOCNs/RC composite films with different mass ratios of TOCNs

Mass ratio of TOCNs/%	OP/ (10⁻⁶ cm³·m⁻²·d·Pa)	OPC/ 10⁻¹⁷ (cm³·cm·cm⁻²·s·Pa)
0	4.79±0.8	2.21±0.4
0.5	4.20±0.6	1.93±0.1
1.0	4.14±0.4	1.51±0.2
1.6	3.98±1.0	1.47±0.8
2.4	4.31±1.6	1.81±1.0

下载: 导出CSV

表 3 不同TOCNs含量的TOCNs/RC复合膜的热重数据

Table 3. Thermogravinmetric data of TOCNs/RC composite films with different mass ratios of TOCNs

Mass ratio of TOCNs/%	T_d/℃	T_max /℃
0	276.35	295.82
0.5	273.42	291.05
1.0	280.16	298.54
1.6	274.02	291.90
2.4	273.61	289.28
Notes: T_d—Epitaxial initial decomposition temperature; T_max—Maximum decomposition temperature.

下载: 导出CSV

参考文献(30)

[1]	SOYKEABKAW N, ARIMOTO N, NISHINO T, et al. All-cellulose composites by surface selective dissolution of aligned ligno-cellulosic fibres[J]. Composites Science and Technology,2008,68(10-11):2201-2207.
[2]	CHENG J F, WANG H L, KANG S L, et al. An active packaging film based on yam starch with eugenol and its application for pork preservation[J]. Food Hydrocolloids,2019,96:546-554. doi: 10.1016/j.foodhyd.2019.06.007
[3]	JANCIKOVA S, JAMROZ E, KULAWIK P, et al. Furcellaran/gelatin hydrolysate/rosemary extract composite films as active and intelligent packaging materials[J]. International Journal of Biological Macromolecules,2019,131:19-28. doi: 10.1016/j.ijbiomac.2019.03.050
[4]	KAMDEM D P, SHEN Z, NABINEJAD O, et al. Development of biodegradable composite chitosan-based films incorporated with xylan and carvacrol for food packaging application[J]. Food Packaging and Shelf Life,2019,21:100344.
[5]	DUCHEMIN B J C, MATHEW A P, OKSMAN K. All-cellulose composites by partial dissolution in the ionic liquid 1-butyl-3-methylimidazolium chloride[J]. Composites Part A: Applied Science and Manufacturing,2009,40(12):2031-2037. doi: 10.1016/j.compositesa.2009.09.013
[6]	盛超. 壳聚糖基纳米纤维素增强席夫碱型水凝胶的制备和性能研究[D]. 杭州: 浙江理工大学, 2017. SHENG C. Preparation and properties of chitosan-based nanocellulose-enhanced schiff hydrogels[D]. Hangzhou: Zhejiang Institute of Technology, 2017(in Chinese).
[7]	李静. 纳米纤维素的疏水改性及其在制浆造中的应用[D]. 济南: 齐鲁工业大学, 2014. LI J. Hydrophobic modification of nanocellulose and its application in pulping[D]. Ji’nan: Qilu University of Technology, 2014(in Chinese).
[8]	YADAV C, SAINI A, MAJI P K. Cellulose nanofibres as biomaterial for nano-reinforcement of poly[styrene-(ethylene-co-butylene)-styrene] triblock copolymer[J]. Cellulose,2018,25:449-461. doi: 10.1007/s10570-017-1567-4
[9]	NAGTANI A. Characteristics & applications of cellulose nanofiber reinforced rubber composites[J]. International Polymer Science and Technology,2017,44(7):1-8.
[10]	杨鑫, 李学敏, 王奉强, 等. 木质素-木粉/高密度聚乙烯复合材料的制备及阻燃性能[J]. 复合材料学报, 2020, 37(3):530-538. YANG X, LI X M, WANG F Q, et al. Preparation and flame retardancy of lignin-wood fiber/high density polyethylene composites[J]. Acta Materiae Compositae Sinica,2020,37(3):530-538(in Chinese).
[11]	韩青, 杨革生, 于敏敏, 等. 玉米秸秆纤维素增强聚乳酸复合材料的制备及其界面改性[J]. 纤维素科学与技术, 2019, 27(1):17-22, 30. HAN Q, YANG G S, YU M M, et al. Preparation and interfacial modification of corn stalk cellulose reinforced polylactic acid composites[J]. Journal of Cellulose Science and Technology,2019,27(1):17-22, 30(in Chinese).
[12]	NISHINO T, MATSUDA I, HIRAO K. All-cellulose composites[J]. Macromolecules,2004,37(20):7683-7687.
[13]	YOUSEFI H, MASHKOUR M, YOUSEFI R. Direct solvent nanowelding of cellulose fibers to make all cellulose nanocomposite[J]. Cellulose,2015,22:1189-1200.
[14]	LI J Y, NAWAZ H, WU J, et al. All-cellulose composites based on the self-reinforced effect[J]. Composites Communications,2018,9:42-53.
[15]	TANPICHAI S. A comparative study of nanofibrillated cellulose and microcrystalline cellulose as reinforcements in all-cellulose composites[J]. Journal of Metals, Materials and Minerals,2018,28(1):10-15.
[16]	曹静. 基于纤维素溶解工艺调控的全纤维素复合材料制备[D]. 成都: 西南交通大学, 2018. CAO J. Preparation of all-cellulose composites based on the regulation of cellulose dissolution process[D]. Chengdu: Southwest Jiaotong University, 2018(in Chinese).
[17]	YANG Q L, SAITO T, BERLUND L A, et al. Cellulose nanofibrils efficiently improve mechnical, thermal and oxygen-barrier properties of all-cellulose composites by nano-reinforcement mechanism and nanofibril-induced crystallization[J]. Nanoscale,2015,7(42):17957-17963.
[18]	巩筱. 纳米纤维素纤丝的改性及其应用研究[D]. 无锡: 江南大学, 2018. GONG X. Modification of nanocellulose fibrils and its application[D]. Wuxi: Jiangnan University, 2018(in Chinese).
[19]	程国阳, 杨黎明, 黄亚峰, 等. 基于DIC方法的车用PP+EPDM-TD10材料动态力学性能研究[J]. 塑料工业, 2017, 45(5):116-119. doi: 10.3969/j.issn.1005-5770.2017.05.028 CHENG G Y, YANG L M, HUANG Y F, et al. Dynamic mechanical properties of vehicle PP+EPDM-TD10 material based on DIC method[J]. China Plastics Industry,2017,45(5):116-119(in Chinese). doi: 10.3969/j.issn.1005-5770.2017.05.028
[20]	ZHAO J Q, HE X, WANG Y R, et al. Reinforcement of all-cellulose nanocomposite films using nativecellulose nanofibrils[J]. Carbohydrate Polymers,2014,104:143-150.
[21]	鲍文毅. 纤维素/壳聚糖共混透明膜的制备及其阻隔抗菌性能研究[J]. 高分子学报, 2015(1):49-56. BAO W Y. Preparation of cellulose_chitosan co-blended transparent films and its barrier antibacterial properties[J]. Acta Polymerica Sinica,2015(1):49-56(in Chinese).
[22]	YANG Q L, SAITO T, ISOGAI A. Facile fabrication of transparent cellulose films with high water repellency and gas barrier properties[J]. Cellulose,2012,19:1913-1921.
[23]	FERRER A, PAL L, HUBBE M. Nanocellulose in packaging: Advances in barrier layer technologies[J]. Industrial Crops and Products,2017,95:574-582.
[24]	HAN Q Q, GAO X, ZHANG H, et al. Preparation and comparative assessment of regenerated cellulose films from corn(Zea mays) stalk pulp fines in DMAc/LiCl solution[J]. Carbohydrate Polymers,2019,218:315-323.
[25]	吕芳兵, 张传杰, 王潮杰, 等. 壳聚糖/纤维素生物质发泡复合材料多孔结构的表征[J]. 复合材料学报, 2015, 32(3):632-639. LV F B, ZHANG C J, WANG C J, et al. Porous structural characterization of chitosan/cellulose biomass foaming composites[J]. Acta Materiae Compositae Sinica,2015,32(3):632-639(in Chinese).
[26]	ZHU Q, ZHOU X F, MA J X, et al. Preparation and characterization of novel regenerated cellulose films via sol-gel technology[J]. Industrial & Engineering Chemistry Reasearch,2013,52(50):17900-17906.
[27]	王玮. 基于再生纤维素新型膜的构建_结构和性能[D]. 无锡: 江南大学, 2017. WANG W. Construction_structure and performance based on a new film of regenerated cellulose[D]. Wuxi: Jiangnan University, 2017(in Chinese).
[28]	吴波, 邵发宁, 何文, 等. TEMPO 氧化纤维素纳米纤丝对多壁碳纳米管分散性的影响[J]. 复合材料学报, 2019, 36(9):2212-2219. WU B, SHAO F N, HE W, et al. Dispersion effect of TEMPO oxidized cellulose nanofibrils on multi-walled carbon nanotubes[J]. Acta Materiae Compositae Sinica,2019,36(9):2212-2219(in Chinese).
[29]	马红燕. 纤维素_碱尿素水溶液的制备与再生及其流动行为特征研究[D]. 广州: 华南理工大学, 2018. MA H Y. Preparation and regeneration of cellulose-alkali urea aqueous solution and its flow behavior characteristics[D]. Guangzhou: South China University of Technology, 2018(in Chinese).
[30]	徐春江. 基于纤维素纳米晶的生物可降解复合材料的结构与性能[D]. 扬州: 扬州大学, 2018. XU C J. Structure and properties of biodegradable composites based on cellulose nanocrystals[D]. Yangzhou: Yangzhou University, 2018(in Chinese).