Preparation and properties of double crosslinked waste corrugated paper-based aerogel buffer materials
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摘要: 以废弃瓦楞纸(WCP)为原料，明胶(G)和植酸(PA)为改性剂，采用溶胶-凝胶法制备高吸能气凝胶。对明胶用量、植酸用量和反应温度对双交联改性废纸基气凝胶力学性能的影响进行了研究，并通过SEM、FTIR、XRD和TGA表征了明胶单一改性和明胶-植酸双交联改性前后气凝胶的结构与性能变化。结果表明：改性单体成功交联到废纸纤维上，双交联改性后的废纸基气凝胶呈现三维网状结构，相较于未改性和单一改性废纸基气凝胶具有较高的热稳定性、优异的隔热性能(0.045 W·m−1·K−1)和超强的吸能性(应变70%时，单位体积吸收能为253.45 kJ/m3)，吸能性分别为珍珠棉(EPE)和乙烯-醋酸乙烯酯共聚物(EVA)的11.26和2.7倍。作为包装运输过程中的一种绿色缓冲材料，具有广阔的应用前景。Abstract: Waste corrugated paper (WCP) was used as raw material, gelatin (G) and phytic acid (PA) were used as modifiers, and high energy absorption aerogel was prepared by sol-gel method. The effects of G dosage, PA dosage, and reaction temperature on the mechanical properties of dual-crosslinked modified waste paper-based aerogels were investigated. The structural and performance changes of aerogels before and after single modification with G and dual modification with G and PA were characterized by SEM, FTIR, XRD and TGA. The results show that the modified monomer is successfully crosslinked onto the waste paper fiber, and the double crosslinked waste paper based aerogel presents a three-dimensional network structure. Compared with the unmodified and single modified waste paper based aerogel, it has higher thermal stability, excellent thermal insulation (0.045 W·m−1·K−1) and super energy absorption (Absorption energy per unit volume is 253.45 kJ/m3 at 70% strain). The energy absorption capacity is 11.26 and 2.7 times higher than that of expanded polyethylene (EPE) and ethylene vinyl acetate (EVA), respectively. As a green cushioning material in the packaging and transportation process, it has broad application prospects.
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图 1 双交联废纸基气凝胶制备过程示意图
Figure 1. Schematic diagram of preparation process of double cross-linked waste paper-based aerogel
图 2 改性前后废纸基气凝胶微观形貌
Figure 2. Micromorphologies of waste paper based aerogel before and after modification
图 3 明胶(G)-植酸(PA)/瓦楞纸(WCP)气凝胶密度、孔隙率和体积收缩率随废纸和明胶质量比的变化
Figure 3. Changes of density, porosity, and volume shrinkage in gelatin (G)-phytic acid (PA)/waste corrugated paper (WCP) aerogel with mass ratio of the waste paper and gelatin
图 4 废纸和明胶不同质量比下：(a) G-PA/WCP气凝胶的压缩应力-应变曲线；(b) G-PA/WCP气凝胶的吸能曲线；(c) G-PA/WCP气凝胶在压缩应变为50%和70%处的单位体积吸能值
Figure 4. Different mass ratios of waste paper and gelatin: (a) Compression stress-strain curves of G-PA/WCP aerogel; (b) Energy absorption curves of G-PA/WCP aerogel; (c) Unit volume energy absorption values of G-PA/WCP aerogel at 50% and 70% compression strain
图 5 废纸明胶不同质量比的宏观图
Figure 5. Macroscopic image of waste paper to gelatin at different mass ratios
图 6 G-PA/WCP气凝胶密度、孔隙率和体积收缩率随植酸添加量的变化
Figure 6. Changes in density, porosity, and volume shrinkage rate of G-PA/WCP aerogel with different phytic acid addition amount
图 7 不同植酸添加量下：(a) G-PA/WCP气凝胶的压缩应力-应变曲线；(b) G-PA/WCP气凝胶的吸能曲线；(c) G-PA/WCP气凝胶在压缩应变为50%和70%处的单位体积吸能值
Figure 7. Different phytic acid contents: (a) Compressive stress-strain curves of G-PA/WCP aerogel; (b) Energy absorption curves of G-PA/WCP aerogel; (c) Energy absorption per unit volume of G-PA/WCP aerogel at compression strain of 50% and 70%
图 8 双交联废纸基气凝胶反应机制
Figure 8. Reaction mechanism of double cross-linked waste paper-based aerogel
图 9 G-PA/WCP气凝胶密度、孔隙率和体积收缩率随反应温度的变化
Figure 9. Variation of G-PA/WCP aerogel density, porosity, and volume shrinkage with reaction temperatures
图 10 不同反应温度下：(a) G-PA/WCP气凝胶的压缩应力-应变曲线；(b) G-PA/WCP气凝胶的吸能曲线；(c) G-PA/WCP气凝胶在压缩应变为50%和70%处的单位体积吸能值
Figure 10. At different reaction temperatures: (a) Compressive stress-strain curves of G-PA/WCP aerogel; (b) Energy absorption curves of G-PA/WCP aerogel; (c) Energy absorption per unit volume of G-PA/WCP aerogel at 50% and 70% compression strain
图 11 双交联废纸基气凝胶的红外图谱
Figure 11. Infrared spectra of a double-crosslinked aerogel made from waste paper
图 12 双交联废纸基气凝胶的XRD图谱
Figure 12. XRD patterns of a double-crosslinked waste paper aerogel
图 13 不同湿度条件下：(a) G-PA/WCP气凝胶的压缩应力-应变曲线；(b) G-PA/WCP气凝胶的吸能曲线；(c) G-PA/WCP气凝胶的缓冲系数
Figure 13. Under different humidity conditions: (a) Compression stress-strain curves of G-PA/WCP aerogels; (b) Energy absorption curves of G-PA/WCP aerogels; (c) Buffering coefficient of G-PA/WCP aerogels
EPE—Expanded polyethylene
图 14 改性前后废纸基气凝胶的TGA (a)和DTG (b)曲线
Figure 14. TGA (a) and DTG (b) curves of waste paper based aerogel before and after modification
图 15 改性前后废纸基气凝胶导热系数对比
Figure 15. Comparison of thermal conductivity of waste paper based aerogel before and after modification
EVA—Ethylene vinyl acetate; EPS—Extracellular polymeric substances
图 16 常用的缓冲包装材料和改性前后废纸基气凝胶的力学性能对比
Figure 16. Comparison of mechanical properties of commonly used buffer packaging materials and waste paper based aerogel before and after modification
图 17 常用的缓冲包装材料和改性前后废纸基气凝胶缓冲系数对比
Figure 17. Comparison of buffering coefficients among commonly used buffer packaging materials and waste paper based aerogel before and after modification
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