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TBP induced double cloud point in aqueous EO13PO30EO13 solutions: investigating the evolution of associated micellar characteristics as a function of temperature

机译:TBP引起EO13PO30EO13水溶液中的双浊点:研究相关胶束特性随温度的变化

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摘要

Pluronics are considered as potential materials for the removal of tributyl phosphate (TBP) from nuclear fuel reprocessing plants. Recent studies showed that solubilization of TBP in aqueous solution of Pluronic L64 reduces its cloud point (CP) and in addition, induces a second CP at low temperature. In this manuscript we have attempted to understand the origin of this lower CP (LCP) by carrying out DLS, SANS, viscosity and fluorescence measurement studies on 10% aqueous L64 solutions containing 60 mM TBP. The studies show that on approaching both LCP (approximate to 25 degrees C) and the conventional or upper CP (UCP approximate to 42.5 degrees C), the copolymer solution exhibits a large increase in light scattering intensity and apparent micellar radius. Detailed studies suggest that whereas the copolymer micelles undergo a progressive growth on heating to the UCP, they form a micellar cluster upon cooling down to the LCP due to the onset of an inter-micellar attractive interaction. Although such clusters are known to form in micellar solutions of non ionic surfactants on approaching the UCP, their formation upon cooling is the first of its kind for them. The observed unusual behavior has possibly been triggered by dehydration of micellar corona caused by relocation of TBP from micellar core to corona upon cooling down to the LCP.
机译:Pluronics被认为是从核燃料后处理厂去除磷酸三丁酯(TBP)的潜在材料。最近的研究表明,TBP在Pluronic L64的水溶液中溶解会降低其浊点(CP),此外,还会在低温下诱导第二个CP。在本手稿中,我们试图通过对含60 mM TBP的10%L64水溶液进行DLS,SANS,粘度和荧光测量研究来了解这种较低CP(LCP)的起源。研究表明,在接近LCP(大约25摄氏度)和常规或更高CP(UCP大约42.5摄氏度)的情况下,共聚物溶液的光散射强度和表观胶束半径都有很大的提高。详细的研究表明,尽管共聚物胶束在加热至UCP时会逐渐生长,但由于胶束间吸引相互作用的发生,它们在冷却至LCP时会形成胶束簇。尽管已知这些团簇在接近UCP时会在非离子型表面活性剂的胶束溶液中形成,但冷却时它们的形成尚属首次。观察到的异常行为可能是由冷却到LCP时TBP从胶束芯迁移到电晕所引起的胶束电晕脱水引起的。

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