Intermittency in aging

The fluctuation-dissipation relation (FDR) is measured on the dielectric properties of a gel (Laponite) and of a polymer glass (polycarbonate). For the gel it is found that during the transition from a fluid-like to a solid-like state the fluctuation dissipation theorem is strongly violated. The amplitude and the persistence time of this violation are decreasing functions of frequency. Around $1Hz$ it may persist for several hours. A very similar behavior is observed in polycarbonate after a quench below the glass transition temperature. In both cases the origin of this violation is a highly intermittent dynamics characterized by large fluctuations. The relevance of these results for recent models of aging are discussed.Comment: Proceedings of "III workshop on non equilibrium phenomena" (Pisa 2002

Off-equilibrium fluctuation-dissipation relations in the 3d Ising Spin Glass in a magnetic field

We study the fluctuation-dissipation relations for a three dimensional Ising spin glass in a magnetic field both in the high temperature phase as well as in the low temperature one. In the region of times simulated we have found that our results support a picture of the low temperature phase with broken replica symmetry, but a droplet behavior can not be completely excluded.Comment: 9 pages, 11 ps figures, revtex. Final version to be published in Phys. Rev.

How glasses explore configuration space

We review a statistical picture of the glassy state derived from the analysis of the off-equilibrium fluctuation-dissipation relations. We define an ultra-long time limit where ``one time quantities'' are close to equilibrium while response and correlation can still display aging. In this limit it is possible to relate the fluctuation-response relation to static breaking of ergodicity. The resulting picture suggests that even far from that limit, the fluctuation-dissipation ratio relates to the rate of growth of the configurational entropy with free-energy density.Comment: To appear in the proceedings of the "3rd workshop on non-equilibrium phenomena in supercooled fluids, glasses and amorphous materials" Pisa 22-27 September 200

Catalytic living ring-opening metathesis polymerization

In living ring-opening metathesis polymerization (ROMP), a transition-metal–carbene complex polymerizes ring-strained olefins with very good control of the molecular weight of the resulting polymers. Because one molecule of the initiator is required for each polymer chain, however, this type of polymerization is expensive for widespread use. We have now designed a chain-transfer agent (CTA) capable of reducing the required amount of metal complex while still maintaining full control over the living polymerization process. This new method introduces a degenerative transfer process to ROMP. We demonstrate that substituted cyclohexene rings are good CTAs, and thereby preserve the ‘living’ character of the polymerization using catalytic quantities of the metal complex. The resulting polymers show characteristics of a living polymerization, namely narrow molecular-weight distribution, controlled molecular weights and block copolymer formation. This new technique provides access to well- defined polymers for industrial, biomedical and academic use at a fraction of the current costs and significantly reduced levels of residual ruthenium catalyst

Spatially heterogeneous ages in glassy dynamics

We construct a framework for the study of fluctuations in the nonequilibrium relaxation of glassy systems with and without quenched disorder. We study two types of two-time local correlators with the aim of characterizing the heterogeneous evolution: in one case we average the local correlators over histories of the thermal noise, in the other case we simply coarse-grain the local correlators. We explain why the former describe the fingerprint of quenched disorder when it exists, while the latter are linked to noise-induced mesoscopic fluctuations. We predict constraints on the pdfs of the fluctuations of the coarse-grained quantities. We show that locally defined correlations and responses are connected by a generalized local out-of-equilibrium fluctuation-dissipation relation. We argue that large-size heterogeneities in the age of the system survive in the long-time limit. The invariance of the theory under reparametrizations of time underlies these results. We relate the pdfs of local coarse-grained quantities and the theory of dynamic random manifolds. We define a two-time dependent correlation length from the spatial decay of the fluctuations in the two-time local functions. We present numerical tests performed on disordered spin models in finite and infinite dimensions. Finally, we explain how these ideas can be applied to the analysis of the dynamics of other glassy systems that can be either spin models without disorder or atomic and molecular glassy systems.Comment: 47 pages, 60 Fig