纳米ZnO/生物基尼龙612纳米复合抗菌薄膜的制备与性能

李霞; 刘跃军; 刘小超; 江南; 王雄刚; 莫智翔; 胡钰迪; 郑伟

doi:10.13801/j.cnki.fhclxb.20220208.001

纳米ZnO/生物基尼龙612纳米复合抗菌薄膜的制备与性能

doi: 10.13801/j.cnki.fhclxb.20220208.001

1.
湖南工业大学　先进包装材料与技术湖南省重点实验室，株洲 412007
2.
厦门长塑实业有限公司，厦门 361026

基金项目: 国家自然科学基金(11872179)；湖南省自然科学基金(2020JJ5137)；湖南省教育厅科学研究项目(19A138；19B152)

详细信息

通讯作者:
刘跃军，博士，教授，博士生导师，研究方向为高分子材料加工工程、先进包装材料与技术　E-mail: yjliu_2005@126.com

中图分类号: TB332
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出版历程
- 收稿日期: 2021-11-11
- 修回日期: 2021-12-27
- 录用日期: 2022-01-15
- 网络出版日期: 2022-02-08
- 刊出日期: 2023-01-15

Preparation and properties of nano-ZnO/bio-based nylon 612 nano-composite antibacterial film

1.
Hunan Provincial Key Laboratory of Advanced Packaging Materials and Technology, Hunan University of Technology, Zhuzhou 412007, China
2.
Xiamen Changsu Industrial CO., LTD., Xiamen 361026, China

Funds: National Natural Science Foundation of China (11872179); Natural Science Foundation of Hunan Province (2020JJ5137); Scientific Research Project of Education Department of Hunan Province (19A138; 19B152)

摘要

摘要: 细菌滋生将缩短食品货架周期，对人体健康产生负面影响，因此开展抗菌包装膜的研究十分重要。本文采用γ-氨丙基三乙氧基硅烷偶联剂(KH550)改性了纳米氧化锌(ZnO)，并将改性后的纳米氧化锌(m-ZnO)与尼龙612 (PA612)进行熔融共混制备复合材料，最终采用挤出流延制备了m-ZnO/PA612纳米复合抗菌薄膜。采用FTIR对改性前后的ZnO进行表征，证明了KH550成功接枝到ZnO上。通过SEM、DSC、TGA、平板计数法等测试手段对ZnO的分散及复合材料的结晶性能、热性能、抗菌性能进行了研究。结果表明：m-ZnO在PA612基体中分散良好。m-ZnO可以作为成核剂提高PA612的结晶度，m-ZnO的含量为2wt%时，其结晶度提高了4.1%。m-ZnO对PA612有增强作用，m-ZnO的添加量为2wt%时，m-ZnO/PA612纳米复合薄膜的拉伸强度较纯PA612提高了15%。m-ZnO的存在赋予了PA612抗菌性能，m-ZnO/PA612纳米复合薄膜对大肠杆菌和金黄色葡萄球菌均有很好的抗菌效果，且随着m-ZnO含量的增大，抗菌率增大，m-ZnO的质量分数为4wt%时，对大肠杆菌的抗菌率为93.25%，对金黄色葡萄球菌的抗菌率为91.03%。
- 尼龙612 /
- γ-氨丙基三乙氧基硅烷 /
- 纳米氧化锌 /
- 抗菌 /
- 纳米复合薄膜
Abstract: Bacterial growth can shorten the shelf life of food and exert a negative effect on human health, therefore it is of great importance to conduct research on anti-bacterial films. Herein, the γ-aminopropyltriethoxysilane coupling agent (KH550) was used to modify nano-zinc oxide, and the modified nano-zinc oxide (m-ZnO) was melt-blended with nylon 612 (PA612) to prepare m-ZnO/PA612 nanocomposite, followed by the fabrication of the antibacterial film through extrusion film casting process. The FTIR was used to characterize the nano-zinc oxide before and after the modification, which proved that KH550 was successfully grafted onto the nano-zinc oxide. Through SEM, DSC, TGA, plate counting method, and other test methods, the dispersibility of nano-zinc oxide and the crystallization performance, thermal performance, and antibacterial properties of composite materials were studied. The results show that the m-ZnO is well dispersed in the PA612 matrix. The m-ZnO can be used as a nucleating agent to increase the crystallinity of PA612. When the content of m-ZnO is 2wt%, the crystallinity is increased by 4.1%. Moreover, the m-ZnO exhibits a reinforcing effect on PA612. When the addition amount of m-ZnO is 2wt%, the tensile strength of the m-ZnO/PA612 nanocomposite film is 15% higher than that of pure PA612. The presence of m-ZnO gives PA612 antibacterial properties. m-ZnO/PA612 nanocomposite film has a good inhibitory effect on Escherichia coli and Staphylococcus aureus. With the increase of m-ZnO content, the antibacterial rate increases, when the mass fraction of m-ZnO is 4wt%, the antibacterial rate against Escherichia coli is 93.25%, and the antibacterial rate against Staphylococcus aureus is 91.03%.
- nylon 612 /
- γ-aminopropyltriethoxysilane /
- nano-zinc oxide /
- antibacterial /
- nanocomposite film

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图 1 ZnO和m-ZnO的FTIR光谱

Figure 1. FTIR spectra of ZnO and m-ZnO

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图 2 ZnO含量2wt%和不同m-ZnO含量的PA612纳米复合材料的脆断截面SEM图像及外观图片

Figure 2. Fracture cross section SEM images and appearance pictures of PA612 nanocomposites with different m-ZnO contents and ZnO content 2wt%

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图 3 2wt%m-ZnO/PA612的SEM图像和EDX映射元素Zn、Si、N和O图谱

Figure 3. SEM images of 2wt%m-ZnO/PA612 and EDX mapping elements Zn, Si, N and O

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图 4 PA612及不同m-ZnO含量的PA612纳米复合材料的DSC图谱：(a) 升温；(b) 降温

Figure 4. DSC curves of PA612 and PA612 nanocomposites with different m-ZnO contents: (a) Heating procedure; (b) Cooling procedure

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图 5 PA612及不同m-ZnO含量的PA612纳米复合材料的XRD图谱

Figure 5. XRD patterns of PA612 and PA612 nanocomposites with different m-ZnO contents

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图 6 PA612及不同m-ZnO含量的PA612纳米复合材料的TGA热重曲线

Figure 6. TGA curves of PA612 and PA612 nanocomposites with different m-ZnO contents

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图 7 PA612及不同m-ZnO含量的PA612纳米复合材料的拉伸应力-应变曲线

Figure 7. Tensile stress versus strain curves of PA612 and PA612 nanocomposites with different m-ZnO contents

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图 8 PA612及不同m-ZnO含量的PA612纳米复合材料的光学性能

Figure 8. Optical properties of PA612 and PA612 nanocomposites with different m-ZnO contents

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图 9 PA612及不同m-ZnO含量的PA612纳米复合材料对大肠杆菌的抗菌测试结果照片

Figure 9. Photos of antibacterial test results of PA612 and PA612 nanocomposites with different m-ZnO contents against Escherichia coli

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图 10 PA612及不同m-ZnO含量的PA612纳米复合材料对金黄色葡萄球菌的抗菌测试结果照片

Figure 10. Photos of antibacterial test results of PA612 and PA612 nanocomposites with different m-ZnO contents against Staphylococcus aureus

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表 1 不同ZnO含量的ZnO/PA612抗菌复合膜

Table 1. ZnO/PA612 antibacterial composite films with different ZnO content

Sample	Mass fraction/wt%
Sample	PA612	m-ZnO	ZnO
PA612	100	0	0
0.5wt%m-ZnO/PA612	99.5	0.5	0
2wt% ZnO/PA612	98	0	2
2wt%m-ZnO/PA612	98	2	0
4wt%m-ZnO/PA612	96	4	0
6wt%m-ZnO/PA612	94	6	0
Notes: m-ZnO—Modified nano zinc oxide; ZnO—Unmodified nano zinc oxide; PA612—Nylon 612.

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表 2 PA612及不同m-ZnO含量的PA612纳米复合材料的DSC热分析数据

Table 2. DSC thermal analysis data of PA612 and PA612 nanocomposites with different m-ZnO contents

Sample	T_m/℃	T_c/℃	ΔH_m/(J·g⁻¹)	X_c/%
PA612	222.86	186.26	61.22	23.73
0.5wt%m-ZnO/PA612	220.37	187.09	70.68	27.53
2wt%m-ZnO/PA612	221.67	187.34	70.36	27.83
4wt%m-ZnO/PA612	221.29	186.99	66.99	26.93
6wt%m-ZnO/PA612	220.97	186.14	65.61	26.88
Notes: T_m—Melting peak temperature; T_c—Crystallization peak temperature; △H_m—Melting enthalpy; X_c—Crystallinity.

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表 3 PA612及不同m-ZnO含量的PA612纳米复合材料的热稳定性

Table 3. Thermal stability of PA612 and PA612 nanocomposites with different m-ZnO contents

Sample	T_5%/℃	T_50%/℃	Char yield at 600℃/wt%
PA612	398.9	450.0	2.3
0.5wt%m-ZnO/PA612	400.4	446.0	2.7
2wt%m-ZnO/PA612	397.2	443.0	3.5
4wt%m-ZnO/PA612	399.3	446.7	4.7
6wt%m-ZnO/PA612	398.6	446.3	7.8
Notes: T_5% and T_50%—Temperature when the weight loss of the samples is 5wt% and 50wt%, respectively.

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表 4 PA612及不同m-ZnO含量的PA612纳米复合材料的拉伸性能

Table 4. Tensile properties of PA612 and PA612 nanocomposites with different m-ZnO contents

Sample	Tensile stress/MPa	Young’s modulus/MPa	Elongation at break/%
PA612	93.95±5.55	685.11±50.97	392.77±13.70
0.5wt%m-ZnO/PA612	93.06±4.56	543.66±39.20	378.30±11.08
2wt%m-ZnO/PA612	108.13±1.76	889.70±60.78	305.23±10.13
4wt%m-ZnO/PA612	84.31±8.35	422.97±94.12	371.85±27.97
6wt%m-ZnO/PA612	83.06±10.85	486.79±71.10	325.38±32.66

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表 5 PA612及不同m-ZnO含量的PA612纳米复合材料膜对大肠杆菌的抑菌活性

Table 5. Antibacterial activity of PA612 and PA612 nanocomposites with different m-ZnO contents membranes against Escherichia coli

Sample	Bacteria concentration/ (CFU·mL⁻¹)	Antibacterial rate R/%
PA612	5.48×10⁶	0.00
0.5wt%m-ZnO/PA612	3.89×10⁶	29.01
2wt%ZnO/PA612	1.43×10⁶	73.91
2wt%m-ZnO/PA612	5.30×10⁵	90.33
4wt%m-ZnO/PA612	3.70×10⁵	93.25
6wt%m-ZnO/PA612	2.50×10⁵	95.44

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表 6 PA612及不同m-ZnO含量的PA612纳米复合材料膜对金黄色葡萄球菌的抑菌活性

Table 6. Antibacterial activity of PA612 and PA612 nanocomposites with different m-ZnO contents membranes against Staphylococcus aureus

Sample	Bacteria concentration/ (CFU·mL⁻¹)	Antibacterial rate R/%
PA612	5.35×10⁶	0.00
0.5wt%m-ZnO/PA612	3.60×10⁶	32.71
2wt%ZnO/PA612	1.73×10⁶	67.66
2wt%m-ZnO/PA612	9.40×10⁵	82.43
4wt%m-ZnO/PA612	4.80×10⁵	91.03
6wt%m-ZnO/PA612	3.60×10⁵	93.27

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