0000000000007290
AUTHOR
Burkhard Geil
Viscoelasticity of pore-spanning polymer membranes derived from giant polymersomes
We show how the viscoelastic properties of membranes formed from poly(butadiene)-block-poly(ethylene oxide) (PB130-b-PEO66) block copolymers can be locally accessed by atomic force microscopy. Polymer membranes are spread on microstructured porous silicon substrates from PB130-b-PEO66 vesicles by decreasing the osmotic pressure of the solution. Local viscoelastic properties of the pore-spanning polymer membranes were obtained from site-specific indentation experiments. Elastic moduli of these membranes were in the order of few MPa, while the elastic moduli of cross-linked membranes considerably increased to few GPa. Furthermore, the energy dissipation and velocity dependence of the hysteres…
Correlation of primary relaxations and high-frequency modes in supercooled liquids. I. Theoretical background of a nuclear magnetic resonance experiment
The question regarding a possible correlation of the time scales of primary and secondary relaxations in supercooled liquids is formulated quantitatively. It is shown how this question can be answered using spin-lattice relaxation weighted stimulated-echo experiments, which are presented in an accompanying paper [A. Nowaczyk, B. Geil, G. Hinze, and R. Böhmer, Phys. Rev. E 74, 041505 (2006)]. General theoretical expressions relevant for the description of such experiments in the presence of correlation effects are derived. These expressions are analyzed by Monte Carlo integration for various correlation scenarios also including exchange processes, which are the hallmark of dynamical heteroge…
Correlation of primary relaxations and high-frequency modes in supercooled liquids. II. Evidence from spin-lattice relaxation weighted stimulated-echo spectroscopy
Using spin-lattice relaxation weighted stimulated-echo spectroscopy, we report evidence for a correlation of the primary and secondary relaxation times. The experiments are performed using deuteron nuclear magnetic resonance somewhat above the calorimetric glass-transition of ortho-terphenyl, D-sorbitol, and cresolphthalein-dimethylether. The data analysis is based on the procedure outlined in the accompanying theoretical paper [B. Geil, G. Diezemann, and R. B\"ohmer, Phys. Rev. E 74, 041504 (2006)]. Direct experimental evidence for a modified spin-lattice relaxation is obtained from measurements on a methyl deuterated acetyl salicylic acid glass. The limitations of the present experimental…
Dynamic heterogeneity in supercooled ortho-terphenyl studied by multidimensional deuteron NMR
Using deuteron NMR, we have studied molecular reorientation rates and rate exchange processes in supercooled ortho-terphenyl. We monitor the re-equilibration of differently selected subensembles through four-time stimulated echo experiments. A comparison of the two-time with the four-time echoes suggests that the characteristic time scales for reorientation and dynamical exchange are relatively similar. The four-time correlation functions were described using various multi-state rate exchange models.
Statistics of reversible bond dynamics observed in force-clamp spectroscopy
We present a detailed analysis of two-state trajectories obtained from force-clamp spectroscopy (FCS) of reversibly bonded systems. FCS offers the unique possibility to vary the equilibrium constant in two-state kinetics, for instance the unfolding and refolding of biomolecules, over many orders of magnitude due to the force dependency of the respective rates. We discuss two different kinds of counting statistics, the event-counting usually employed in the statistical analysis of two-state kinetics and additionally the so-called cycle-counting. While in the former case all transitions are counted, cycle-counting means that we focus on one type of transitions. This might be advantageous in p…
Correlation of primary and secondary relaxations in a supercooled liquid
The widespread assumption that primary and secondary relaxations in glass-forming materials are independent processes is scrutinized using spin-lattice relaxation weighted stimulated-echo spectroscopy. This nuclear magnetic resonance (NMR) technique is simultaneously sensitive to the dynamics on well-separated time scales. For the deeply supercooled liquid sorbitol, which exhibits a strong secondary relaxation, the primary relaxation (that is observable using NMR) can be modified by suppressing the contributions of those subensembles which are characterized by relatively slow secondary relaxations. This is clear evidence for a correlation between primary and secondary relaxation times. In t…
Nature of the non-exponential primary relaxation in structural glass-formers probed by dynamically selective experiments
Several experimental methods feature the potential to distinguish between slow and fast contributions to the non-exponential, ensemble averaged primary response in glass-forming materials. Some of these techniques are based on the selection of subensembles using multi-dimensional nuclear magnetic resonance, optical bleaching, and non-resonant spectral hole burning. Others, such as the time-dependent solvation spectroscopy, measure microscopic responses induced by local perturbations. Using several of these methods it could be demonstrated for various glass-forming materials that the non-exponential relaxation results from a superposition of dynamically distinguishable entities. The experime…
2H NMR Time Domain Analysis of Ultraslow Reorientations in Supercooled Liquids
A method for evaluating 2H NMR stimulated echo experiments in the time domain is presented. It exhibits a high sensitivity to molecular reorientation mechanisms for small angles. Reorientations with jump angles below 25degrees can be resolved with a precision of approximately 1degrees so that, e.g., rotational diffusion and finite jump angle mechanisms become distinguishable. The method, applicable to isotropic reorientation models, is thought to extend the domain of 2D exchange spectroscopy where the best resolution is obtained in the large angle range of anisotropic reorientational mechanisms. Application to reorientation in the supercooled melt of ortho-terphenyl is presented. These data…