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Phase transitions in dense thermo-responsive microgel suspensions: A Monte Carlo study

机译:致密热响应微凝胶悬浮液中的相变:蒙特卡罗研究

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Aqueous suspensions of sub-micron sized monodisperse particles exhibit structural ordering analogous that observed in atomic systems. Deionised suspensions of colloidal charged polystyrene particles exhibit long-range order for volume fraction Φ> 0.001, whereas suspensions of hard-spheres undergo crystallization at Φ> 0.48. In these dispersions the particle size is fixed and the temperature is not a controllable parameter to investigate the phase transitions like fluid to crystal (melting/freezing) and glass transition. Whereas aqueous suspensions of thermo-responsive poly(N- isopropylacrylamide) (PNIPAM) particles exhibit rich phase behaviour upon varying the temperature as well as osmotic pressure due to the variation in particle size as well as interparticle interaction U(r). Recently, Bergman et al [1]have proposed a Multi-Hertzian (MH) pair potential U(r), for PNIPAM microgels which are known to have an inhomogeneous dense polymer core and a thin shell of dangling polymer chains. MH pair-potential is expected to represent the interparticle interaction between PNIPAM microgel spheres up to their volume phase transition (VPT) temperature (VPT Φ 34°C. The applicability of this potential in predicting the phase behaviour, is verified only in the fluid region (i.e. volume fractions upto Φ=0.49) of PNIPAM microgels. Its applicability for understanding the ordering, dynamics and the phase behaviour of microgels under dense conditions needs to be investigated. With this as the motivation, we have performed Monte Carlo (MC) simulations with MH potential over a wide range of volume fractions and results are reported here. Quite surprisingly, we found that that the fluid phase freeze in to a glassy state instead of a crystalline state upon increasing Φ.
机译:亚微米尺寸单分散颗粒的水性悬浮液表现出在原子系统中观察到的结构性排序。胶体带电聚苯乙烯颗粒的去离子悬浮液表现出体积分数φ> 0.001的远程顺序,而硬球的悬浮液在φ> 0.48处经历结晶。在这些分散体中,粒度是固定的,并且温度不是可控参数,以研究流体(熔化/冷冻)和玻璃化转变等相变。而热响应性聚(N-异丙基丙烯酰胺)(泊普)颗粒的水悬浮液在改变温度和由于粒度的变化而在改变温度以及渗透压术后,并且颗粒粒度的变化以及颗粒间相互作用u(R),但是在渗透压下表现出富相行为。最近,Bergman等人[1]提出了一种多峰(MH)对电位U(R),用于彼皮姆微凝胶,其已知具有不均匀的致密聚合物核和悬垂聚合物链的薄壳。预计MH对电位将代表泊地姆微凝胶球体之间的颗粒间相互作用,其上阴部的体积相变(VPT)温度(VPTφ34℃。这种电位在预测相行为中的适用性,仅在流体区域中验证(即泊地米帕米氏菌的体积分数达到φ= 0.49)。它用于了解在密集条件下理解微胶质的顺序,动力学和阶段行为的适用性。随着这种动机,我们已经进行了Monte Carlo(MC)模拟在这里报道了在广泛的体积分数和结果范围内的MH潜力。非常令人惊讶的是,我们发现,在增加φ时,流体相冻结在玻璃状状态而不是结晶状态。

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