Mutch Kevin J, van Duijneveldt Jeroen S, Eastoe Julian, Grillo Isabelle, Heenan Richard K
School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom, Institut Max-Von-Laue-Paul-Langevin, BP 156-X, F-38042 Grenoble Cedex, France.
Langmuir. 2009 Apr 7;25(7):3944-52. doi: 10.1021/la802488f.
The phase behavior and structural properties of "protein limit" mixtures of small (radius 20-30 A) water-in-oil microemulsion droplets (colloids) and large (radius 130-580 A) nonadsorbing polymer chains have been investigated. Accepted theoretical scaling relations for describing correlations have been applied and do not account fully for the observations; solvency effects may account for the deviations. The polymer/colloid size ratio has been varied from around 4 to 19 by using three different molecular weights of polyisoprene. Small-angle neutron scattering (SANS) has been used to determine partial structure factors (PSF) through contrast variation. The structure factors describing colloid-colloid interactions for the three polymers at fixed polymer concentration are shown to exhibit the same scaling behavior as the phase boundaries, provided that samples are sufficiently far from the demixing phase transition. The structure factors show a dramatic increase at low wavevectors on approaching the phase boundary, and behavior in this region does not obey expected scaling relations. By calculating effective polymer Flory-Huggins parameters, the effect of apparent solvent properties on adding microemulsion are shown to be less dramatic for the higher molecular weight polymers. This study extends previous work carried out on microemulsion-polymer mixtures.
研究了小尺寸(半径20 - 30 Å)的油包水微乳液滴(胶体)与大尺寸(半径130 - 580 Å)非吸附性聚合物链的“蛋白质极限”混合物的相行为和结构性质。已应用用于描述相关性的公认理论标度关系,但这些关系并不能完全解释观测结果;溶剂化效应可能是偏差的原因。通过使用三种不同分子量的聚异戊二烯,聚合物/胶体尺寸比在约4至19之间变化。小角中子散射(SANS)已被用于通过对比变化确定部分结构因子(PSF)。结果表明,在固定聚合物浓度下,描述三种聚合物的胶体 - 胶体相互作用的结构因子与相边界表现出相同的标度行为,前提是样品离相分离相变足够远。结构因子在接近相边界时在低波矢处急剧增加,并且该区域的行为不遵循预期的标度关系。通过计算有效的聚合物弗洛里 - 哈金斯参数,结果表明,对于较高分子量的聚合物,添加微乳液对表观溶剂性质的影响较小。本研究扩展了先前对微乳液 - 聚合物混合物开展的工作。