Soft-materials such as block copolymers, surfactant and liquid crystals exhibit variety of ordered microstructures. Among them, the phase diagrams of diblock copolymers have been extensively investigated both experimentally and theoretically. Matsen and Shick[1] calculated the phase diagram of diblock copolymer melts by using self-consistent field theory (SCFT) and predicted that the phase diagram contains four types of structures: sphere packed in body-center-cubic, hexagonally-packed cylinders, lamellar and double-gyroid network. Khandpur et al.

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Mechanochromic elastomers that exhibit forceinduced cross-linking reactions in the bulk state are introduced. The synthesis of segmented polyurethanes (SPUs) that contain difluorenylsuccinonitrile (DFSN) moieties in the main chain and methacryloyl groups in the side chains was carried out. DFSN was selected as the mechanophore because it dissociates under mechanical stimuli to form pink cyanofluorene (CF) radicals, which can also initiate the radical polymerization of methacrylate monomers. The obtained elastomers generated CF radicals and changed color by compression or extension; they also became insoluble due to the mechanically induced cross-linking reactions. Additionally, an SPU containing diphenylmethane units also exhibited highly sensitive mechanofluorescence. To the best of our knowledge, this is the first report to demonstrate damage detection ability and changes in the mechanical properties of bulk elastomers induced by simple compression or extension.

A difluorenylsuccinonitrile-(DFSN)-based linker, whose central C−C bond is readily cleaved under mechanical stress to generate a relatively stable pink radical species, was introduced into polymer networks. DFSN-based cross-linked polymers exhibit improved mechanical properties as compared to those of the corresponding covalently cross-linked polymers owing to the energy dissipation induced by cleavage of the central DFSN bond. The toughening mechanism of DFSN-based elastomers is qualitatively visualized by the intensity of the pink color and can be quantitatively characterized by electron paramagnetic resonance. These results demonstrate that the extent of DFSN cleavage is the main factor improving the mechanical properties of the polymer networks.

We present evidence that the transition between organic and third phases, which can be observed in the plutonium uranium reduction extraction (PUREX) process at high metal loading, is an unusual transition between two isotropic bicontinuous microemulsion phases. As this system contains so many components, however, we have been seeking first to investigate the properties of a simpler system, namely, the related metal-free, quaternary water/n-dodecane/nitric acid/tributyl phosphate (TBP) system. This quaternary system has been shown to exhibit, under appropriate conditions, three coexisting phases: a light organic phase, an aqueous phase, and the so-called third phase. In the current work, we focused on the coexistence of the light organic phase with the third phase. Using Gibbs ensemble Monte Carlo (GEMC) simulations, we found coexistence of a phase rich in nitric acid and dilute in n-dodecane (the third phase) with a phase more dilute in nitric acid but rich in n-dodecane (the light organic phase). The compositions and densities of these two coexisting phases determined using the simulations were in good agreement with those determined experimentally. Because such systems are generally dense and the molecules involved are not simple, the particle exchange rate in their GEMC simulations can be rather low. To test whether a system having a composition between those of the observed third and organic phases is indeed unstable with respect to phase separation, we used the Bennett acceptance ratio method to calculate the Gibbs energies of the homogeneous phase and the weighted average of the two coexisting phases, where the compositions of these phases were taken both from experimental results and from the results of the GEMC simulations. Both demixed states were determined to have statistically significant lower Gibbs energies than the uniform, mixed phase, providing confirmation that the GEMC simulations correctly predicted the phase separation. Snapshots from the simulations and a cluster analysis of the organic and third phases revealed structures akin to bicontinuous microemulsion phases, with the polar species residing within a mesh and with the surface of the mesh formed by amphiphilic TBP molecules. The nonpolar n-dodecane molecules were observed in these snapshots to be outside this mesh. The only large-scale structural differences observed between the two phases were the dimensions of the mesh. Evidence for the correctness of these structures was provided by the results of small-angle X-ray scattering (SAXS) studies, where the profiles obtained for both the organic and third phases agreed well with those calculated from simulations. Finally, we looked at the microscopic structures of the two phases. In the organic phase, the basic motif was observed to be one nitric acid molecule hydrogen-bonded to a TBP molecule. In the third phase, the most common structure was that of the hydrogen-bonded TBP-HNO-HNO chain. A cluster analysis provided evidence for TBP forming an extended, connected network in both phases. S...

The stability of the Fddd phase as an equilibrium phase in diblock copolymer melts was examined by using small-angle X-ray scattering and transmission electron microscopy. After 2 days of annealing at 150 °C where Fddd was found in a previous study (Takenaka et al. Macromolecules 2007, 40, 4399) for the poly(styrene-block-isoprene) (S−I), the Fddd structure still survived. The thermoreversibility in the order−order transitions (OOTs) between lamella (L) and Fddd and between gyroid (G) and Fddd was investigated. The long-time annealing at 150 °C induced the transformation from L and G to Fddd, indicating that Fddd is more stable than L and G at 150 °C. Fddd transformed into L and G, respectively, by annealing at 130 and 170 °C. These results supported that the OOTs between L and Fddd and between G and Fddd are thermoreversible. The stability of the Fddd structure after 2 days of annealing and the confirmation of the thermoreversibility in OOTs clarified that the Fddd phase exists as an equilibrium phase in S−I diblock copolymer melts.

A refined model for tri-n-butyl phosphate (TBP), which uses a new set of partial charges generated from our ab initio density functional theory calculations, has been proposed in this study. Molecular dynamics simulations are conducted to determine the thermodynamic properties, transport properties, and the microscopic structures of liquid TBP, TBP/water mixtures, and TBP/n-alkane mixtures. These results are compared with those obtained from four other TBP models, previously described in the literature. We conclude that our refined TBP model appears to be the only TBP model from this set that, with reasonable accuracy, can simultaneously predict the properties of TBP in bulk TBP, in organic diluents, and in aqueous solution. The other models only work well for two of the three systems mentioned above. This new TBP model is thus appropriate for the simulation of liquid-liquid extraction systems in the nuclear extraction process, where one needs to simultaneously model TBP in both aqueous and organic phases. It is also promising for the investigation of the microscopic structure of the organic phase in these processes and for the characterization of third-phase formation, where TBP again interacts simultaneously with both polar and nonpolar molecules. Because the proposed TBP model uses OPLS-2005 Lennard-Jones parameters, it may be used with confidence to model mixtures of TBP with other species whose parameters are given by the OPLS-2005 force field.