Search results for "Glass transition"
showing 10 items of 372 documents
Theory of glass transition in spin glasses, orientational glasses and structural glasses
2008
Theoretical concepts about the glass transition are briefly reviewed, and the test of these ideas by Monte Carlo simulations of simple lattice models is described, with an emphasis on isotropic and anisotropic orientational glasses, and the bond fluctuation model of polymer melts. It is suggested that orientational glasses do have an equilibrium phase transition at zero temperature (in d = 3 dimensions!) only, in contrast to the Ising spin glass which orders at nonzero temperature. A diverging glass correlation length is identified that is responsible for the anomalous slowing down. For the Potts glass, the divergence seems to be exponential, implying that the model is at its lower critical…
Small-Angle Excess Scattering: Glassy Freezing or Local Orientational Ordering?
1996
We present Monte Carlo simulations of a dense polymer melt which shows glass-transition-like slowing-down upon cooling, as well as a build up of nematic order. At small wave vectors q this model system shows excess scattering similar to that recently reported for light-scattering experiments on some polymeric and molecular glass-forming liquids. For our model system we can provide clear evidence that this excess scattering is due to the onset of short-range nematic order and not directly related to the glass transition.
Anisotropic motion of toluene above and below the glass transition studied by 2H NMR
1995
Abstract 2 H nuclear magnetic resonance spin-lattice relaxation experiments on two selectively deuterated toluene molecules have been performed over a wide temperature range, spanning liquid and glassy states, to examine anisotropic molecular dynamics. In the liquid regime, the relaxation data are analyzed by the model of anisotropic rotational diffusion. A more phenomenological ansatz is used for the whole temperature regime to obtain information about anisotropic reorientation and its temperature dependence. We find that the anisotropy is reduced in the supercooled state and the motion becomes approximately isotropic below 140 K which is interpreted as the onset of cooperative reorientati…
Intramolecular caging in polybutadiene due to rotational barriers
2003
We present molecular dynamics simulations of a chemically realistic model of 1,4-polybutadiene and a freely rotating chain model derived from the first model by neglecting all dihedral potentials. We show that the presence of energy barriers hindering dihedral rotation leads to an intermediate plateau regime in the tagged particle mean-squared displacement reminiscent of the cage effect underlying the mode-coupling description of the liquid-glass transition. This intramolecular caging, however, occurs already at temperatures well above the glass transition regime. Because of its different physical origin, it also does not comply with the theoretical predictions of the mode-coupling theory. …
Anomalous diffusion of polymers in supercooled melts near the glass transition
2007
Two coarse-grained models for polymer chains in dense melts near the glass transition are investigated: the bond fluctuation lattice model, where long bonds are energetically favored, is studied by dynamic Monte Carlo simulation, and an off-lattice bead-spring model with Lennard-Jones forces between the beads is treated by Molecular Dynamics. We compare the time-dependence of the mean square displacements of both models, and show that they become very similar on mesoscopic scales (i.e., displacements larger than a bond length). The slowing down of motions near the glass transition is discussed in terms of the mode coupling theory and other concepts.
Entropy of glassy polymer melts: Comparison between Gibbs-DiMarzio theory and simulation.
1996
We calculate the free energy of a model for a polymer melt in a computer simulation of the bond-fluctuation model and determine the entropy of the melt over a wide range of temperatures, including the region close to the glass transition. The results are compared with the Gibbs-DiMarzio theory, a theory by Flory for semiflexible polymers, and a modification of their theories due to Milchev. We can describe the data within the framework of the Flory theory with Milchev's correction and discuss the consequences for the understanding of the glass transition. \textcopyright{} 1996 The American Physical Society.
Dynamic Anomalies and their Relation to the Glass Transition: A Neutron Scattering Study of the Glass Forming Van der Waals Liquid Ortho-terphenyl
1991
Neutron scattering experiments on the molecular glass former ortho-terphenyl reveal a dynamic anomaly at a temperature Tc ≈ 290 K well above the calorimetric glass temperature Tg = 243 K. Close above Tc the density autocorrelation function ΦQ(t) shows a two step decay over 4–5 decades in time. The slower component obeys the time-temperature superposition principle. Its line shape can be well parametrized by a Kohlrausch law and is strongly temperature dependent as its relaxation time scales with the shear viscosity. Thus this component is identified with the structural relaxation (α-process). The faster component (β-process) is much less temperature dependent. Its line shape factorizes in a…
Nonexponential 2H spin-lattice relaxation as a signature of the glassy state
1990
Abstract High-precision measurements of 2H spin-lattice relaxation on several molecular glass-forming liquids have been performed. As a general feature the following can be stated: At temperatures more than ten to twenty degrees above the calorimetric glass transition temperature Tg the 2H spin-lattice relaxation is exponential; below that temperature regime the relaxation is nonexponential. This crossover from exponential to nonexponential magnetization recovery implies that no common spin temperature caused by spin diffusion exists in a 2H glass. This contrasts 1H spin-lattice relaxation which is found to be strictly monoexponential throughout. The occurrence of nonexponential 2H relaxati…
Glass transition of hard spheres in high dimensions
2009
We have investigated analytically and numerically the liquid-glass transition of hard spheres for dimensions $d\to \infty $ in the framework of mode-coupling theory. The numerical results for the critical collective and self nonergodicity parameters $f_{c}(k;d) $ and $f_{c}^{(s)}(k;d) $ exhibit non-Gaussian $k$ -dependence even up to $d=800$. $f_{c}^{(s)}(k;d) $ and $f_{c}(k;d) $ differ for $k\sim d^{1/2}$, but become identical on a scale $k\sim d$, which is proven analytically. The critical packing fraction $\phi_{c}(d) \sim d^{2}2^{-d}$ is above the corresponding Kauzmann packing fraction $\phi_{K}(d)$ derived by a small cage expansion. Its quadratic pre-exponential factor is different fr…
Modified mode-coupling theory for the collective dynamics of simple liquids
2011
Recently it has been shown that mode-coupling theory, which accounts for the salient features of glassy relaxation near the liquid–glass transition, is also capable of describing the collective excitations of simple liquids away from the glass transition. In order to further improve the agreement between theory and computer simulations on Lennard-Jones argon we modify MCT by taking binary collisions into account. This, in fact, improves the agreement. We also show that multiplying the memory function of the original theory with a reduction factor leads to similar results.