PubMed · 13211796
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F W DICK, D P JACKSON, C L CONLEY. 1954. Surface as a quantitative factor in prothrombin utilization.. https://doi.org/10.1172/jci103020
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We report on an extensive study of craze formation in glassy polymers. Molecular dynamics simulations of a coarse-grained bead-spring model were employed to investigate the molecular level processes during craze nucleation, widening, and breakdown for a wide range of temperature, polymer chain length N, entanglement length N(e), and strength of adhesive interactions between polymer chains. Craze widening proceeds via a fibril-drawing process at constant drawing stress. The extension ratio is determined by the entanglement length, and the characteristic length of stretched chain segments in the polymer craze is N(e)/3. In the craze, tension is mostly carried by the covalent backbone bonds, and the force distribution develops an exponential tail at large tensile forces. The failure mode of crazes changes from disentanglement to scission for N/N(e) approximately 10, and breakdown through scission is governed by large stress fluctuations. The simulations also reveal inconsistencies with previous theoretical models of craze widening, which were based on continuum level hydrodynamics.
We study a random heteropolymer model with Langevin dynamics, in the supersymmetric formulation. Employing a procedure similar to one that has been used in static calculations, we construct an ensemble in which the affinity of the system for a native state is controlled by a "selection temperature" T0. In the limit of high T0, the model reduces to a random heteropolymer, while for T0-->0 the system is forced into the native state. Within the Gaussian variational approach that we employed previously for the random heteropolymer, we explore the phases of the system for high and low T0. For high T0, the system exhibits a (dynamical) spin-glass phase, like that found for the random heteropolymer, below a temperature T(g). For low T0, we find an ordered phase, characterized by a nonzero overlap with the native state, below a temperature T(n) proportional to 1/T(0)>T(g). However, the random-globule phase remains locally stable below T(n), down to the dynamical glass transition at T(g). Thus, in this model, folding is rapid for temperatures between T(g) and T(n), but below T(g) the system can get trapped in conformations uncorrelated with the native state. At a lower temperature, the ordered phase can also undergo a dynamical glass transition, splitting into substates separated by large barriers.
The mobilization of an oil bank in a packed bed of glass beads saturated with an aqueous phase has been studied both theoretically and experimentally. The size of the glass beads was varied in the range between 0.5 and 5mm. Two oils (hexadecane and hexane) with viscosities different for an order of magnitude and densities smaller than that of water have been used. A few more runs have been carried out using perchloroethylene (PCE), with density greater than that of water. The interfacial tension in the aqueous phase was varied in a quite large range (0.38-39.1 dyn/cm) by adding surfactants to the water. The glass assembly made it possible to follow the evolution of the dyed oily phase by the use of a digital camera. A very simple stochastic model for describing the porous structure of the packed bed made it possible to set a criterion for determining the probability of mobilization of ganglia which are produced by the fragmentation of the oil bank. The same model permits also to estimate the probability function of the velocity of a ganglion of an assigned size.