Search

Self-assembly is particularly important for soft condensed matter. It may lead to manifold equilibrium or non-equilibrium structures and macroscopic properties of soft materials. The self-organization may be induced by changes in environmental conditions such as temperature, pH and irradiation by light. Among the different polymer families, the stimuli-responsive polymers are particularly sensitive to external stimuli. A structural instability, which is usually related to a demixing phase transition, commonly occurs for stimuli-responsive polymer systems. For such aqueous polymer solutions and hydrogels, a demixing transition of the Lower Critical Solution Temperature (LCST) type often happens, this means that the segregation occurs upon heating. Its macroscopic order parameter is attributed to the difference in mass concentration within the segregated state. Since the variation in mass density is a closely related quantity, the transition is also called a volume phase transition. In case of hydrogels, the order parameter also is the macroscopic deformation. In consequence the related susceptibility is the isothermal compressibility and the demixing transition is denoted as being ferroelastic. In this thesis, basic aspects of the static, kinetic and dynamical nature of the LCSTtype demixing transition are analyzed. Aqueous solutions of the thermo-responsive model homopolymer poly(N-isopropylacrylamide) (PNIPAM) are studied. Part of the phase diagram is probed by varying the polymer concentration in solution and the temperature. In part unconventional experimental techniques were used to access the macroscopic order parameter susceptibilities, like the dynamical volume expansion coefficient, and linear and nonlinear elastic properties at GHz frequencies. The major experimental technique is Temperature Modulated Optical Refractometry (TMOR), which has recently been developed in collaboration with the company Anton Paar (Seelze, Germany) and patented in 2012 by the University of Luxembourg. First studies by Brillouin spectroscopy were carried out on the segregation of aqueous PNIPAM solutions. The linear and in particular nonlinear elastic moduli are much more affected than the thermal expansion coefficient by this phase transition. Furthermore, it could be shown that the specific refractivity is astonishingly sensitive, probably to the changes in molecular interactions, during segregation. This allows for a novel perspective on the microscopic order parameters of the transition. The key investigations of this thesis focus on kinetics and thermo-mechanical relaxation processes related to the segregation, studying optical and mechanical quantities by TMOR. Sinusoidal temperature perturbations were therefore applied around the demixing temperature of different PNIPAM solutions. First direct indications for the location of the binodal and spinodal lines could be

Isostructural phase transitions occurring under non-equilibrium conditions are investigated using technologically relevant epoxies. The evolution of the hypersonic and optical properties during the genesis of the polymeric network leads to deeper insight into the chemically induced sol-gel transition and glass transition, as demonstrated e.g. by the elastic anharmonicity and the generalised Cauchy relation. During gelation the refractive index versus chemical conversion behaves in an unexpected manner, indicating that in addition to the mass density an excess polarisability seems to contribute to the optical polarisability. The clarification of the isostructural phase transitions is impeded by the demixing tendency of the epoxy components which leads to different types of epoxy inhomogeneities on the nano- to mesoscopic scale. Taking benefit from a sample arrangement where both epoxy components are layered, the spatio-temporal evolution of acoustic properties gives supplementary information about trans-interfacial transport and structure formation processes. Of special technological relevance, but also of fundamental interest, is the influence of nanoscopic disturbances placed into the epoxy matrix. So-called interphases surrounding the nanoparticles modify and complicate the epoxy network formation, leading to long-lived metastable morphologies and properties. The role of the mixing sequence of the epoxy resin, the hardener and the nanoparticles for the polymerised epoxy state and the transient states during network formation, as well as the isostructural phase transitions is further elucidated.