Nestor Jérémie, Obiols-Rabasa Marc, Esquena Jordi, Solans Conxita, Levecke Bart, Booten Karl, Tadros Tharwat F
Departament de Tecnologia de Tensioactius, Institut d'Investigacions, Químiques i Ambientals de Barcelona, CSIC, Jordi Girona 18-26, 08034 Barcelona, Spain.
J Colloid Interface Sci. 2008 Mar 1;319(1):152-9. doi: 10.1016/j.jcis.2007.10.049. Epub 2007 Nov 12.
Recently, steric repulsive forces induced by a new graft copolymer surfactant, which is based in inulin (polyfructose), have been described. Previous investigations by atomic force microscopy between solid surfaces covered with adsorbed surfactant indicated strong repulsive forces even at high electrolyte concentration, due to the steric repulsion produced by the surfactant hydration. In the present paper, the colloidal stabilization provided by this surfactant is studied by rheology. The measurements were carried out on sterically stabilized polystyrene (PS) and poly(methyl methacrylate) (PMMA) containing adsorbed surfactant (INUTEC SP1). Steady-state shear stress as a function of shear rate curves was established at various latex volume fractions. The viscosity volume fraction curves were compared with those calculated using the Doughtry-Krieger equation for hard sphere dispersions. From the experimental eta r-phi curves the effective volume fraction of the latex dispersions could be calculated and this was used to determine the adsorbed layer thickness Delta. The value obtained was 9.6 nm, which is in good agreement with that obtained using atomic force microscopy (AFM). Viscoelastic measurements of the various latex dispersions were carried out as a function of applied stress (to obtain the linear viscoelastic region) and frequency. The results showed a change from predominantly viscous to predominantly elastic response at a critical volume fraction (phi c). The effective critical volume fraction, phi eff, was calculated using the adsorbed layer thickness (Delta) obtained from steady-state measurements. For PS latex dispersions phi eff was found to be equal to 0.24 whereas for PMMA phi eff=0.12. These results indicated a much softer interaction between the latex dispersions containing hydrated polyfructose loops and tails when compared with latices containing poly(ethylene oxide) (PEO) layers. The difference could be attributed to the stronger hydration of the polyfructose loops and tails when compared with PEO. This clearly shows the much stronger steric interaction between particles stabilized using hydrophobically modified inulin.
最近,有人描述了一种基于菊粉(多聚果糖)的新型接枝共聚物表面活性剂所诱导的空间排斥力。先前通过原子力显微镜对覆盖有吸附表面活性剂的固体表面之间进行的研究表明,即使在高电解质浓度下,由于表面活性剂水合作用产生的空间排斥,也存在很强的排斥力。在本文中,通过流变学研究了这种表面活性剂提供的胶体稳定性。测量是在含有吸附表面活性剂(INUTEC SP1)的空间稳定化聚苯乙烯(PS)和聚甲基丙烯酸甲酯(PMMA)上进行的。在不同的胶乳体积分数下建立了稳态剪切应力与剪切速率曲线的函数关系。将粘度体积分数曲线与使用硬球分散体的Doughtry-Krieger方程计算得到的曲线进行了比较。从实验得到的ηr-φ曲线可以计算出胶乳分散体的有效体积分数,并用于确定吸附层厚度Δ。得到的值为9.6nm,这与使用原子力显微镜(AFM)得到的值非常吻合。对各种胶乳分散体进行了粘弹性测量,测量结果是施加应力(以获得线性粘弹性区域)和频率的函数。结果表明,在临界体积分数(φc)下,响应从主要为粘性转变为主要为弹性。使用从稳态测量中获得的吸附层厚度(Δ)计算有效临界体积分数φeff。对于PS胶乳分散体,发现φeff等于0.24,而对于PMMA,φeff = 0.12。这些结果表明,与含有聚环氧乙烷(PEO)层的胶乳相比,含有水合聚果糖环和尾部的胶乳分散体之间的相互作用要弱得多。这种差异可归因于与PEO相比,聚果糖环和尾部的水合作用更强。这清楚地表明了使用疏水改性菊粉稳定的颗粒之间更强的空间相互作用。