Günther Scherf | PubMed Health

PubMed2003

Dynamic and static properties of the concentrated micellar solution and gel phase of a triblock copolymer in water.

The dynamic and static behavior of the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer "P94" is studied in aqueous solution. This polymer forms transparent micellar phase structures through the whole phase diagram. The characteristics of these structures can be tuned by variation of temperature and concentration. The transparent gel at high concentrations and at ambient temperatures is the main interest in this study. The transition from the ergodic solution to this nonergodic gel or glass state can be reached in two ways: at constant temperature with an increase of concentration or at constant concentration with increasing temperature. We characterize the system in both ways with dynamic and static light scattering and with small-angle x-ray scattering experiments. At 40 degrees C, no concentration dependent change in the micellar structure of the system can be detected from the small-angle x-ray scattering results. Even in the gel we find globular particles. This is important for the evaluation and interpretation of the dynamic light scattering measurements. In the ergodic phase region at constant temperature, we find that a ratio of 2.17 gives a perfect fit to the experimental data when we allow the effective volume fraction to be proportional to the mass fraction. In the gel region we find two diffusional decays in the intensity correlation functions and an arrested part. The diffusion coefficients from the faster decay stay constant inside the gel and the nonergodicity parameter increases linearly with concentration. Both, the fast and slow diffusional modes show no angular dependence of their scattering intensities, indicating their origin from small objects, while the arrested mode comes, as expected, from structures larger than the resolution of the experiments.

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PubMed2001

Sugar-Ester Nonionic Microemulsion: Structural Characterization.

Surfactants containing sugar components and fatty acids satisfy the quality standards for food application. The food grade sugar ester in this study is a commercial sucrose monoester of stearic acid (abbreviated SES), the oil phase consists of a 1:1 mixture of n-tetradecane and l-butanol. The originally planned food grade oil, a medium chain triglyceride, is substituted by tetradecane because tetradecane is available as a fully deuterated product, which is necessary for some structural investigations. The investigated system is solid at room temperature, but liquefies and structures into a homogeneous microemulsion when heated to above 37 degrees C. The structural characterization of such microemulsions is the aim of this work. The established methods for this purpose are scattering methods, such as small-angle scattering of X-rays and neutrons and dynamic light scattering. These scattering techniques can be used to obtain valuable information on the size, shape, and internal structure of colloids and complex fluids. We started our investigation with the pseudobinary system SES, tetradecane and l-butanol, varying the SES content. The scattering results show that the sugar ester form inverse globular micelles in the oil phase. The size of these micelles is about 6 nm. While the size is nearly constant in a wide SES concentration regime (5 up to 40% surfactant), the volume or aggregation number increases significantly with SES. This is explained by an increasing replacement of l-butanol molecules by sugar-ester molecules in the micelles formed. Moreover, it can be shown that these micelles strongly overlap. Their center-to-center distance is about 3.8 nm at 40% SES at a micellar diameter of 6 nm. The micellar overlap leads to a highly reduced diffusion of the micelles as was found with dynamic light scattering. When incorporating water in the micellar core, the micelles swell up to about 10 nm and the shape of the aggregates becomes more and more elongated with higher water content. Copyright 2001 Academic Press.

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