Thermal glass transition beyond kinetics of a non-crystallizable glass-former.

A long-debated problem related to glass formation in amorphous materials is the interplay of thermodynamic, kinetic and α-relaxation processes. For the first time, low-frequency dynamics, as well as kinetic or quasi-static thermal expansion coefficients of a non-crystallizable glass-former are simultaneously measured. Based on the feedback between low-frequency dynamics and morphology, the study supports the viewpoint that glass formation can be observed in internal equilibrium, i.e. beyond kinetics, and might stem from spontaneous local-scale morphological changes.

phase instability and molecular kinetics provoked by repeated crossing of the demixing transition of PNIPAM solutions.

The demixing process of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions can occur either via a nucleation and growth process or via spinodal decomposition. The ensuing self-assembly, leading to heterogeneous morphologies within the PNIPAM solution, is codetermined by kinetic processes caused by molecular transport. By subjecting PNIPAM solutions to cyclic changes in temperature leading to repeated crossing of the demixing transition, we are able to assess the importance of kinetics as well as of overheating and supercooling of the phase transition within the metastable range delimited by the binodal and spinodal lines. First indications about the location of these stability limits for the low- and high-temperature phases, separated by about 1.6 K, could be gained by detailed kinetic studies of the refractive index. These investigations are made possible due to the novel technique of temperature-modulated optical refractometry.

Molecular versus macroscopic perspective on the demixing transition of aqueous PNIPAM solutions by studying the dual character of the refractive index.

The phase separation of aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions is known to strongly affect their volume expansion behaviour and the elastic moduli, as the latter are strongly coupled to the macroscopic order parameter. On the molecular scale, considerable changes in H-bonding and hydrophobic interactions, as well as in the structure govern the demixing process. However, the relationship between the molecular and macroscopic order parameters is unclear for such complex phase-separating solutions. We contribute to the clarification of this problem by relating optical to volumetric properties across the demixing transition of dilute to concentrated aqueous PNIPAM solutions. Far from the demixing temperature, the temperature dependence of the refractive index is predominantly determined by thermal expansion. In the course of phase separation, the refractive index is dominated by the anomalous behaviour of the specific refractivity, which reflects the spatio-temporally averaged changes in molecular interactions and the structural reorganization of the demixing solutions. Moreover, the presence of relaxation processes is studied by the complex expansion coefficient using the novel technique of temperature modulated optical refractometry.

From molecular dehydration to excess volumes of phase-separating PNIPAM solutions.

For aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions, a structural instability leads to the collapse and aggregation of the macromolecules at the temperature-induced demixing transition. The accompanying cooperative dehydration of the PNIPAM chains is known to play a crucial role in this phase separation. We elucidate the impact of partial dehydration of PNIPAM on the volume changes related to the phase separation of dilute to concentrated PNIPAM solutions. Quasi-elastic neutron scattering enables us to directly follow the isotropic jump diffusion behavior of the hydration water and the almost freely diffusing water. As the hydration number decreases from 8 to 2 for the demixing 25 mass % PNIPAM solution, only a partial dehydration of the PNIPAM chains occurs. Dilatation studies reveal that the transition-induced volume changes depend in a remarkable manner on the PNIPAM concentration of the solutions. The excess volume per mole of H2O molecules expelled from the solvation layers of PNIPAM during phase separation probably strongly increases from dilute to concentrated PNIPAM solutions. This finding is qualitatively related to the immense strain-softening previously observed for demixing PNIPAM solutions.

Mixing behavior and interphase formation in the diethylene triamine-water system studied by optical imaging and spatially resolved Brillouin scattering.

The injection of water beneath liquid diethylene triamine in a glass cuvette leads to an unexpected phase evolution behavior of the two liquids. The space and time dependent developments of the molecular structure and the underlying transport associated with mixing of the two liquids are monitored by optical imaging and scanning Brillouin microscopy. Apparently, results obtained by either experimental technique lead to disparate interpretations. Whereas optical imaging suggests the existence of a two phase structure, which disappears within a few hours, acoustic microscopy indicates the evolution of a more gradually evolving and longer-lived three phase structure. According to molecular acoustics, the transport of diethylene triamine into water and vice versa behaves strongly asymmetric in time. An attempt is made to reconcile the observed optical and acoustic manifestations of the mixing process on the basis of molecular complex formation.