Beneficial use of mussel shell as a bioadditive for TPU green composites by the valorization of an aqueous waste

Sedef Şişmanoğlu, Yasin Kanbur, Carmen-Mihaela Popescu, Diana Kindzera, Ümit Tayfun
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Abstract

Scientific studies have focused on environmentally friendly solutions as effective as the reuse of crop products owing to plastic-waste problems in recent years. This issue is the main driving force for upcoming academic research attempts in waste valorization-related studies. Herein, we integrated an aqua-waste, mussel shell (MS), as a bioadditive form into green thermoplastic polyurethane (TPU) green composites. Tuning of the MS surface was performed to achieve strong adhesion between composite phases. The surface functionalities of MS powders were evaluated via infrared spectroscopy and scanning electron microscopy (SEM) images. Composite samples were prepared by melt-compounding followed by injection molding techniques. It was confirmed by morphological analysis that relatively better adhesion between the phases was achieved for composites involving surface-modified MS compared to unmodified MS. Tensile strength and Young’s modulus of surface-modified MS-filled composites were found to be higher than those of unmodified MS, whereas the elongation at break shifted to lower values with MS inclusions. The shore hardness of TPU was remarkably improved after being incorporated with silane-treated MS (AS-MS). Stearic acid-treated MS (ST-MS) additions resulted in an enhancement in the thermal stability of the composites. Thermo-mechanical analysis showed that the storage moduli of composites were higher than those of unfilled TPU. ST-MS additions led to an increase in the characteristic glass transition temperature of TPU. Melt flow index (MFI) of neat TPU was highly improved after MS loading regardless of modification type. According to the wear test, surface modification of MS displayed a positive effect on the wear resistance of TPU. As the water absorption data of the composites were evaluated, the TPU/AS-MS composite yielded the lowest water absorption. The silane layer on MS inclusion promoted water repellency of composites due to the hydrophobicity of silane. The results of the biodegradation investigation demonstrated that adding unmodified and/or modified MS to the TPU matrix increased the biodegradation rate. The test results at the end of a 7-week period of biodegradation with a soft-rot fungus implied that the composite materials were more biodegradable than pure TPU. Silane modification of MS exhibited better performance in terms of the characterized properties of TPU-based composites.

Graphical abstract

Abstract Image

贻贝壳作为TPU绿色复合材料生物添加剂的有益利用
近年来,由于塑料废物问题,科学研究的重点是环境友好型解决方案,其效果与作物产品的再利用一样有效。这一问题是即将进行的与废物价值相关的学术研究尝试的主要推动力。在此,我们将水生废物贻贝(MS)作为生物添加剂形式整合到绿色热塑性聚氨酯(TPU)绿色复合材料中。对质谱表面进行了调整,以实现复合相之间的强粘附。通过红外光谱和扫描电镜(SEM)图像对质谱粉末的表面功能进行了评价。采用熔融复合和注射成型技术制备复合材料样品。形态学分析证实,与未改性MS相比,表面改性MS填充复合材料的相间附着力相对较好,抗拉强度和杨氏模量高于未改性MS,而断裂伸长率则随着MS夹杂物的加入而降低。硅烷处理的质谱(AS-MS)掺入后,TPU的邵氏硬度显著提高。硬脂酸处理的质谱(ST-MS)的添加导致复合材料的热稳定性增强。热力学分析表明,复合材料的储存模量高于未填充的TPU。ST-MS的加入导致TPU的特征玻璃化转变温度升高。无论改性方式如何,纯TPU的熔体流动指数(MFI)在MS加载后都得到了很大的改善。磨损试验表明,MS的表面改性对TPU的耐磨性有积极的影响。对复合材料的吸水率进行了评价,发现TPU/ As - ms复合材料的吸水率最低。由于硅烷的疏水性,MS包合物上的硅烷层提高了复合材料的拒水性。生物降解研究结果表明,在TPU基质中添加未经修饰和/或修饰的MS可提高TPU基质的生物降解率。在7周的软腐菌生物降解期结束时的测试结果表明,复合材料比纯TPU更具可生物降解性。在tpu基复合材料的表征性能方面,硅烷改性的MS表现出更好的性能。图形抽象
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