Compositional dependence of the microphase separation transition in styrene-butadiene-styrene triblock copolymer/polystyrene blends

The change in the microphase separation transition (MST) temperature of a styrene-butadiene-styrene (SBS) triblock copolymer induced by the addition of polystyrene (PS) was investigated by small-angle X-ray scattering. It was found that the transition temperature was determined from the molecular weight (M(H)) Of the added PS in relation to that of the corresponding blocks (M(A)) in the copolymer. The MST temperature decreased with added PS if M(H)/M(A) < 1/4, while it increased with added PS when M(H)/M(A) > 1/4 Analysis of the theoretical expression based on the random phase approximation showed exactly the same tendency of change in the transition temperatures as that observed experimentally. The interaction parameter, chi(SB), obtained by nonlinear fitting of the scattering profiles of SBS/PS blends in the disordered state, was found to be a function of temperature and composition. Composition fluctuations were found to exist in SBS/PS blends, increasing with increasing addition of PS but diminishing with increasing molecular weight of the added PS.

Phase behavior in mixtures of a homopolymer and a block copolymer .4. SALS and SAXS studies

Phase behavior of blends of poly(vinyl methyl ether) (PVME) with four styrene-butadienestyrene (SBS) triblock copolymers, being of various molecular weights, architecture, and compositions, was investigated by small-angle light scattering. Small-angle X-ray scattering investigation was accomplished for one blend. Low critical solution temperature (LCST) and a unique phase behavior, resembling upper critical solution temperature (UCST), were observed. It was found that the architecture of the copolymer greatly influenced the phase behavior of the blends. Random phase approximation theory was used to calculate the spinodal phase transition curves of the ABA/C and BAB/C systems; LCST and resembling UCST phase behavior were observed as the parameters of the system changed. Qualitatively, the experimental and the theoretical results are consistent with each other. (C) 1996 John Wiley & Sons, Inc.

AN INFRARED SPECTROSCOPIC STUDY ON THE STRUCTURAL PHASE-TRANSITIONS OF LAURYLAMMONIUM CHLORIDE

Infrared spectroscopy was used to study the structural phase, transitions of laurylammonium chloride in the temperature range from 290 to 365K. It was shown that there is a solid-solid phase transition at 339 K with a pre-transition at 327 K. The infrared spectra indicated that virgin crystals at room temperature form a well-ordered phase with all-trans hydrocarbon chains, and the lengths of N-H...Cl hydrogen bonds are different. The spectra suggested that the gauche conformers begin to appear at temperature above 327 K. The spectra at high temperature over 339 K demonstrated that the interaction between the chains decreases, the partial ''melting'' of the chains is obvious, and the hydrogen bonds (N-H...Cl) have the same lengths. The main transition and pre-transition are mainly assigned to the intramolecular and intermolecular order-disorder changes, respectively.

AN INFRARED SPECTROSCOPIC CHARACTERIZATION OF THE SOLID SOLID BEHAVIOR OF DODECYLAMMONIUM CHLORIDE

The infrared spectra of the bilayer system dodecylammonium chloride has been studied as a function of temperature. Unusual splitting of some vibrational modes helps us to characterize the structure of different solid states. This study provided the evidence for the occurrence of an order-disorder phase transition whose onset occurs at 327 K and its completion ends at 339 K. In the low temperature phase below 327 K, the virgin crystals form a well-ordered phase with all-transhydrocarbon chains. In the intermediate state between 327 and 339 K, the data demonstrate the introduction of intramolecular as well as intermolecular disorder. The coexistence of solid and liquid-crystal-like states is shown by the persistence of factor group splittings together with the existence of defect bands in the wide intermediate temperature range. In the high temperature phase over 339 K the crystals convert to a liquid-crystal-like system with extensive motional and conformational disorder, but still show characteristics in their infrared spectra which indicate the presence of ordered segments in the hexagonal solid phase.

AN INFRARED SPECTROSCOPIC STUDY OF THE STRUCTURAL PHASE-TRANSITION IN THE PEROVSKITE-TYPE LAYER COMPOUND [N-C16H33NH3]2COCL4

The solid-solid phase transitions in the perovskite-type layer compound [n- C16H33NH3]2CoCl4 have been studied by infrared spectroscopy. A new phase transition at 340 K was found by comparison with differential scanning calorimetry results. A temperature dependence study of the infrared spectra provides evidence of the occurrence of structural phase transitions related to the dynamics of the alkylammonium ions and hydrogen bonds. The main transition at 374 K corresponds to the conformational order-disorder change in the chain, which probably couples with reorientational motions of the NH3 polar heads. GTG or GTG' defects appear in the high temperature disordered phase.

THERMAL ANALYSIS AND INFRARED SPECTRA OF DIALKYLAMMONIUM TETRAC HLOROCUPRATE

The thermal stability and the solid solid phase transitions in Ills compounds with n = 7-12 have been studied by DSC and TG methods. Comparision with CnZn compounds want made. The nature of three phases of CnCu has been discussed in terms of infrared spectroscopy and the assignment of the phase transitions has been given. The thermal stability of CnCu is lower than that of CnZn and presents an obvious odd even effect. All of these compounds exhibit two solid solid phase transitions in the temperature range of 248-337 K. The peak tempe nature of phase transitions changes regularly. The peak temperature or the main phase transition increases with the chain length. The total transition enthalpies and entropies increase with increasing chain length. When n <= 9, the high temperature phase exists in a partial disorder state. When n >= 10, the high temperature phase exists in a conformational disorder state. The main phase transition and the phase transition at 307.7 K of CnCu may mainly are from the change of the packing structure and the change of the partial conformational order-disorder of alkyl chain, respectively.

Statistical analysis of synthetic earthquake catalogs generated by models with various levels of fault zone disorder

The stress release model, a stochastic version of the elastic rebound theory, is applied to the large events from four synthetic earthquake catalogs generated by models with various levels of disorder in distribution of fault zone strength (Ben-Zion, 1996) They include models with uniform properties (U), a Parkfield-type asperity (A), fractal brittle properties (F), and multi-size-scale heterogeneities (M). The results show that the degree of regularity or predictability in the assumed fault properties, based on both the Akaike information criterion and simulations, follows the order U, F, A, and M, which is in good agreement with that obtained by pattern recognition techniques applied to the full set of synthetic data. Data simulated from the best fitting stress release models reproduce, both visually and in distributional terms, the main features of the original catalogs. The differences in character and the quality of prediction between the four cases are shown to be dependent on two main aspects: the parameter controlling the sensitivity to departures from the mean stress level and the frequency-magnitude distribution, which differs substantially between the four cases. In particular, it is shown that the predictability of the data is strongly affected by the form of frequency-magnitude distribution, being greatly reduced if a pure Gutenburg-Richter form is assumed to hold out to high magnitudes.

Fourth order accurate compact scheme with group velocity control (GVC)

For solving complex flow field with multi-scale structure higher order accurate schemes are preferred. Among high order schemes the compact schemes have higher resolving efficiency. When the compact and upwind compact schemes are used to solve aerodynamic problems there are numerical oscillations near the shocks. The reason of oscillation production is because of non-uniform group velocity of wave packets in numerical solutions. For improvement of resolution of the shock a parameter function is introduced in compact scheme to control the group velocity. The newly developed method is simple. It has higher accuracy and less stencil of grid points.

Weak Zone Related Seismic Cycles in Progressive Failure Leading to Collapse in Brittle Crust

Until quite recently our understanding of the basic mechanical process responsible for earthquakes and faulting was not well known. It can be argued that this was partly a consequence of the complex nature of fracture in crust and in part because evidence of brittle phenomena in the natural laboratory of the earth is often obliterated or obscured by other geological processes. While it is well understood that the spatial and temporal complexity of earthquakes and the fault structures emerge from geometrical and material built-in heterogeneities, one important open question is how the shearing becomes localized into a band of intense fractures. Here the authors address these questions through a numerical approach of a tectonic plate by considering rockmass heterogeneity both in microscopic scale and in mesoscopic scale. Numerical simulations of the progressive failure leading to collapse under long-range slow driving forces in the far-field show earthquake-like rupture behavior. $En Echelon$ crack-arrays are reproduced in the numerical simulation. It is demonstrated that the underlying fracturing induced acoustic emissions (or seismic events) display self-organized criticality------from disorder to order. The seismic cycles and the geometric structures of the fracture faces, which are found greatly depending on the material heterogeneity (especially on the macroscopic scale), agree with that observed experimentally in real brittle materials. It is concluded that in order to predict a main shock, one must have extremely detailed knowledge on very minor features of the earth's crust far from the place where the earthquake originated. If correct, the model proposed here seemingly provides an explanation as to why earthquakes to date are not predicted so successfully. The reason is not that the authors do not understand earthquake mechanisms very well but that they still know little about our earth's crust.

A second-order dynamic subgrid-scale stress model

A second-order dynamic model based on the general relation between the subgrid-scale stress and the velocity gradient tensors was proposed. A priori test of the second-order model was made using moderate resolution direct numerical simulation date at high Reynolds number ( Taylor microscale Reynolds number R-lambda = 102 similar to 216) for homogeneous, isotropic forced flow, decaying flow, and homogeneous rotating flow. Numerical testing shows that the second-order dynamic model significantly improves the correlation coefficient when compared to the first-order dynamic models.

A high order accurate difference scheme for complex flow fields

A high order accurate finite difference method for direct numerical simulation of coherent structure in the mixing layers is presented. The reason for oscillation production in numerical solutions is analyzed, It is caused by a nonuniform group velocity of wavepackets. A method of group velocity control for the improvement of the shock resolution is presented. In numerical simulation the fifth-order accurate upwind compact difference relation is used to approximate the derivatives in the convection terms of the compressible N-S equations, a sixth-order accurate symmetric compact difference relation is used to approximate the viscous terms, and a three-stage R-K method is used to advance in time. In order to improve the shock resolution the scheme is reconstructed with the method of diffusion analogy which is used to control the group velocity of wavepackets. (C) 1997 Academic Press.

Fracture criterion based on the higher-order asymptotic fields

A complete development for the higher-order asymptotic solutions of the crack tip fields and finite element calculations for mode I loading of hardening materials in plane strain are performed. The results show that in the higher-order asymptotic solution (to the twentieth order), only three coefficients are independent. These coefficients are determined by matching with the finite element solutions carried out in the present paper (our attention is focused on the first five terms of the higher-order asymptotic solution). We obtain an analytic characterization of crack tip fields, which conform very well to the finite element solutions over wide range. A modified two parameter criterion based on the asymptotic solution of five terms is presented. The upper bound and lower bound fracture toughness curves predicted by modified two parameter criterion are given. These two curves agree with most of the experimental data and fully capture the proper trend.

Bending solution of high-order refined shear deformation-theory for rectangular composite plates

A new high-order refined shear deformation theory based on Reissner's mixed variational principle in conjunction with the state- space concept is used to determine the deflections and stresses for rectangular cross-ply composite plates. A zig-zag shaped function and Legendre polynomials are introduced to approximate the in-plane displacement distributions across the plate thickness. Numerical results are presented with different edge conditions, aspect ratios, lamination schemes and loadings. A comparison with the exact solutions obtained by Pagano and the results by Khdeir indicates that the present theory accurately estimates the in-plane responses.

Higher-order analysis of crack-tip fields in power-law hardening materials

In this paper, we present an exact higher-order asymptotic analysis on the near-crack-tip fields in elastic-plastic materials under plane strain, Mode I. A four- or five-term asymptotic series of the solutions is derived. It is found that when 1.6 < n less-than-or-equal-to 2.8 (here, n is the hardening exponent), the elastic effect enters the third-order stress field; but when 2.8< n less-than-or-equal-to 3.7 this effect turns to enter the fourth-order field, with the fifth-order field independent. Moreover, if n>3.7, the elasticity only affects the fields whose order is higher than 4. In this case, the fourth-order field remains independent. Our investigation also shows that as long as n is larger than 1.6, the third-order field is always not independent, whose amplitude coefficient K3 depends either on K1 or on both K1 and K2 (K1 and K2 arc the amplitude coefficients of the first- and second-order fields, respectively). Firmly, good agreement is found between our results and O'Dowd and Shih's numerical ones[8] by comparison.

High order asymptotic field for plane stress crack problem

This paper presents an exact analysis for high order asymptotic field of the plane stress crack problem. It has been shown that the second order asymptotic field is not an independent eigen field and should be matched with the elastic strain term of the first order asymptotic field. The second order stress field ahead of the crack tip is quite small compared with the first order stress field. The stress field ahead of crack tip is characterized by the HRR field. Hence the J integral can be used as a criterion for crack initiation.