熱塑性聚氨酯(TPU)主要是由硬鏈段及軟鏈段彼此交互連接所組成。由於其廣泛的硬度分布，使TPU發泡材能應用於許多領域，但因TPU複雜的結晶行為和收縮情形，難以控制不同種類TPU達到最佳之發泡效果。目前很少有文獻在ETPU泡珠製備方面，針對不同硬度TPU的發泡行為作詳細探討。
　　本研究採用三種不同硬度(85A、90A、95A)的聚醚系TPU，利用超臨界二氧化碳作為發泡劑，以一步法批次發泡製備泡材，對泡孔結構與發泡溫度和壓力的關係進行廣泛的研究。泡孔尺寸在50μm左右，膨脹率達6倍以上，收縮率10%左右。
　　首先以85A-TPU的軟化點作為參考溫度，在不同壓力(1100-2000 psi)下含浸，結果發現以Psat = 1100 psi的條件最符合用來製備泡珠(較佳的穩定膨脹比及較低的收縮率)，混煉會顯著改變泡孔型態，泡孔密度增加了近百倍。
　　因此在Psat = 1100 psi下，探討含浸溫度分別對三種不同硬度TPU泡孔型態之影響。另外透過熱分析及物性分析發現，相分離的趨勢會隨著硬度提高越來越明顯，使硬段的晶體堆疊，有更難以發泡的趨勢，其中尤以95A-PR的發泡效果下降最多。
接著我們嘗試以三種不同功能之添加劑-成核劑(talc),擴鏈劑(ADR),抗縮劑(ABS)，各別對發泡效果較佳的85A及90A-TPU之泡材進行分析及改善。結果發現，對硬度較低的85A-TPU，talc對發泡效果的改善較為顯著，原因可能與硬段含量及排列有關。
　　本實驗成功分析不同硬度之聚醚系TPU因混煉造成的發泡行為，並篩選出適合用於製備TPU泡珠的硬度種類及發泡條件。

Thermoplastic polyurethane (TPU) is mainly composed of different hard segments and soft segments, such a wide range of hardness, TPU foams are suitable for many applications. At the moment, very few studies have investigated the foaming behavior of different hardness TPU in expanded thermoplastic polyurethane (ETPU) bead foam manufacturing.
　　In this study, polyether TPUs (85A, 90A, and 95A) with different hardness were foamed through one-step batch foaming using super critical CO2 as the blowing agent. The cell size, expansion ratio, cell density, and shrinkage ratio versus foaming temperature and foaming pressure were studied intensively.
　　First, the softening temperature of 85A-TPU was applied as the reference temperature and the sample was saturated at various pressures from 2000 psi to 1100 psi. When the saturation pressure reduced to 1100 psi, the foam shrinkage phenomena was significantly alleviated and the highest expansion ratio was obtained. After compounding, the cell density was increased by almost two orders of magnitude.
　　Therefore, at Psat = 1100 psi, the influence of saturated temperature on the three different hardness of TPU’s cell morphology was investigated. In addition, through thermal analysis and physical property analysis, it was found that the phase separation became more obvious with increasing hardness. The crystallization of hardsegments made foaming more difficult.
In the second part of this study, three different functional additives - nucleating agent (talc), chain extender (ADR) and anti-shrinkage agent (ABS) were added to improve the cell structure of 85A and 90A-TPU. It was found that the improvement of foaming effect of additives was more significant for the low hardness TPU (85A-TPU), which may be related to arrangement of hard segments. In summary, we can choose optimum foaming conditions and hardness to prepare ETPU bead foam.

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