铝塑复合包装的应用及废弃物回收利用新技术

doi:10.11949/0438-1157.20220699

摘要/Abstract

摘要：

包装是商品使用、储存、运输的重要保障，不可或缺。塑料包装轻质、易加工、性价比高，增长极快，成为现代社会主要的包装材料，其中铝塑复合包装通过材料优势互补，可满足阻隔性、抗菌性、力学性能和印刷性能等多功能要求，应用广泛，但即用即弃，废弃物难分离难回收利用，无法降解，也难焚烧处理，污染环境，浪费资源，亟待治理。本文综述了铝塑复合包装结构性能和应用，以及废弃物回收利用难点，重点介绍了本团队采用自主创新的固相剪切碾磨加工装备和技术，实现废弃铝塑复合包装的室温超细粉碎和均匀分散，改善加工性和力学性能，制备可拆卸物流包装箱及导热导电功能制品的研究工作。

关键词: 固相剪切碾磨加工, 铝塑复合包装, 高值回收, 复合材料

Abstract:

Packaging is an important guarantee for the use, storage and transportation of products. Due to the lightweight, easy processing and high performance, plastic packaging become the main packaging material in modern society. Aluminum-plastic packaging has the advantages of plastic and aluminum, which meet the barrier, antimicrobial, mechanical and printing performance for multi-functional requirements. However, the fast development and single-use of aluminum-plastic packaging cause serious environmental problems and waste of resources. Aluminum-plastic packaging waste is difficult to separate for recycling, unable to degrade, and difficult to burn, so the caused pollution becomes an urgent problem to be solved. This article introduced the structure, properties and application of aluminum-plastic packaging, and the challenges in waste recycling. We emphatically introduced the works focused on self-designed solid-state shear milling equipment and technology, which achieved ultra-fine grinding and excellent dispersion of waste aluminum-plastic packaging at room temperature. We further produced removable logistics packages and thermal conductive function products by aluminum-plastic packaging powder with improved processability and mechanical properties.

Key words: solid state shear milling, aluminum-plastic packaging, value-added recycling, composites

中图分类号:

TQ 32

杨双桥, 韦宝杰, 徐大伟, 李莉, 王琪. 铝塑复合包装的应用及废弃物回收利用新技术[J]. 化工学报, 2022, 73(8): 3326-3337.

Shuangqiao YANG, Baojie WEI, Dawei XU, Li LI, Qi WANG. Application of aluminum-plastic packaging and new recycling technology of the waste[J]. CIESC Journal, 2022, 73(8): 3326-3337.

图/表 15

表1 常见塑料包装氧气和水蒸气的透过率［5］

Table 1 Oxygen and moisture permeability of common plastic packaging［5］

Materials	Thickness/μm	Oxygen permeability/(cm³/(m²·d·(0.1 mPa)))	Water vapor permeability/ (g/(m²·d))
PE	50	2187.7	7.8
BOPP	50	582.5	3.0
PET	50	25.2	7.0
PA	15	41.2	290.6
PET/PE	50	88.7	5.6
PET/CPP	50	75.4	5.8
PET/Al/PE	60	0.13	0.48
BOPA/Al/CPP	60	0.07	0.51
PET/Al/CPP	60	0.12	0.45

图1 磨盘盘面示意图(a)，动磨盘和静磨盘剪切区示意图 (b)，高分子材料在磨盘中的运动轨迹(c) [26]

Fig.1 Schematic diagram of mill pan (a), shear region of milling and static pan (b) and trajectory route of polymer during pan milling (c) [26]

图2 固相剪切碾磨加工工业化装备

Fig.2 Industrial equipment of solid-state shear milling

表2 固相剪切碾磨加工制备的聚合物微纳粉体极限粒径［21， 28-31］

Table 2 Particle size of micro/nano polymer powder prepared by solid-state shear milling ［21， 28-31］

Polymer type	Particle size
PA6	~80 nm
PP, PS	0.3—2 µm
PC, PPS	10—50 µm
PES, PEEK	1—10 µm
HDPE, waste rubber, SBS	micro-scale

图3 固相剪切碾磨加工技术回收多组分废弃塑料[22,32-35]

Fig.3 Multicomponent plastics waste recycled by solid-state shear milling technology[22,32-35]

图4 废弃铝塑复合包装初破碎照片(a)，力化学研磨粉体照片(b)，废弃铝塑复合包装超细粉体SEM形貌[(c)、(d)]，不同碾磨次数铝元素示踪[1次(e)，10次(f)]

Fig.4 Photos of pre-crushed aluminum plastic packaging waste (APPW) (a), powders prepared by solid-state shear milling technology (b), SEM morphology of APPW powders [(c),(d)] and the distribution of aluminum after 1 (e) and 10 (f) milling cycles

图5 废弃铝塑复合包装力化学研磨1次(a)和10次(b)粒径分布及平均粒径(c)，粉体粒径Rosin-Rammler Bennet拟合曲线(d)

Fig.5 Particle size distribution of APPW after 1(a) and 10 (b) milling cycles, mean particle size (c) and Rosin-Rammler Bannet fitting curve of particle size (d)

表3 固相剪切碾磨过程Rosin-Rammler Bennet系数的变化

Table 3 Development of Rosin-Rammler Bennet coefficient during the solid-state shear milling

Parameter	1 cycle	5 cycles	10 cycles
De/μm	321	152	106
b	1.03×10^-4	5.03×10^-5	5.09×10^-5
n	1.59	1.97	2.12

图6 研磨0次(a)、5次(b)和10次(c)后废弃铝塑复合包装粉体密炼加工数码照片，密炼加工过程转矩曲线(d)，密炼加工平衡扭矩时间(e)，熔体熔融指数(f)

Fig.6 Photos of APPW powders after 0 (a), 1 (b) and 10 (c) milling cycles during the mixing processing, torque curve (d), balance torque time (e) and melt index (f)

图7 废弃铝塑再生复合材料未研磨处理[(a)、(e)]、碾磨1次[(b)、(f)]、碾磨4次[(c)、(g)]和碾磨10次[(d)、(h)]SEM形貌，填料统计尺寸与碾磨次数的关系(i)，拉伸性能(j)

Fig.7 SEM images of reused APPW composites with 0 cycle [(a),(e)], 1 cycle [(b),(f)], 4 cycles[(c),(g)], and 10 cycles [(d),(h)], relation between filler size and milling cycle (i) and tensile strength (j)

表4 废弃铝塑再生复合材料性能

Table 4 Properties of recycled APPW composites

Samples	Tensile strength /MPa	Elongation at break/%	Electrical conductivity/ (S/cm)	Thermal conductivity/ (W/(m∙K))
after milling	22.1	47.1	10^-12	0.6
without milling	8.5	7.9	10^-14	—

图8 废弃铝塑复合包装超细粉体模压制品(a)，载荷加载试验(b)，注塑制备工业可折叠物流箱(c)，应力-应变曲线(d)，形变率和载荷的关系(e)

Fig.8 Molded APPW part (a), load test (b), industrial detachable logistics packer prepared by injection molding (c), stress-strain cure (d) and relation between deformation rate and load (e)

图9 废弃铝塑导热材料中铝箔透射电镜 (a)，导热绝缘机理示意图(b)，制备的工业散热板(c)，电导率与可膨胀石墨含量的关系(d)，热导率与电导率的关系(e)[40]

Fig.9 TEM of Al in APPW thermal conductive material (a), mechanism of thermal conductivity (b), prepared industrial cooling plates (c), relation between conductivity and expandable graphite loading (d) and relation between thermal conductivity and conductivity (e) [40]

图10 铝塑复合包装为基体制备的3D可打印丝条数码照片(a)，可打印丝条截面SEM图 (b)，3D打印过程示意图(c)，3D打印过程数码照片(d)，压缩强度与应变的关系(e)，E/η与剪切速率的关系(f)[41]

Fig.10 Photos of APPW filaments for 3D printing (a), SEM image of APPW filaments (b), schematic diagram of 3D printing process (c), photos of 3D printing process (d), relation between compressive strength and strain (e) and relation between E/η and shear rate (f) [41]

图11 废弃铝塑复合包装制备的3D打印散热器(a)，热导率与填料含量关系[(b)、(c)]，导热机理示意图(d)，复合材料散热效果对比(e)[41]

Fig.11 3D printed radiators from APPW (a), relation between thermal conductivity and filler loading [(b),(c)], schematic diagram of thermal conductive mechanism (d) and comparison of heat dissipation effect of composites (e) [41]

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