Preparation of rhodium–phyllosilicate catalysts without leaching in liquid-phase 1-hexene hydrogenation

Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.     

Shear banding in strained semicrystalline polyamide 6 films as revealed by atomic force microscopy: Role of the amorphous phase

Atomic force microscopy (AFM) has been used to visualize the plastic deformation mechanisms that are responsible for the yielding of semicrystalline polymers of low degree of crystallinity (<50%). Indeed, AFM, if operated in suitable conditions, is able to image both the amorphous and the crystalline phases. Polyamide 6 films have been drawn at temperatures T < 160 °C. Postmortem AFM observations show that, at yield, shear bands nucleate and propagate in the amorphous phase. They cross the crystalline lamellae and run over the whole surface of the sample. By crossing the lamellae, they form nanoblocks of uniform size. Neither the size of the nanoblocks nor the angle between the tensile axis and the shear bands can be explained in terms of crystal plasticity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 687–701, 2004     

Time-resolved synchrotron X-ray study of crystalline phase transition in poly(aryl ether ketone ketone) containing alternated terephthalic/isophthalic moieties

Unique crystallization and melting behavior in poly(aryl ether ketone ketone) containing alternated terephthalic and isophthalic moieties were studied by time-resolved synchrotron x-ray methods. Recently, this material has been shown to exhibit three polymorphs (forms I, II, and III). In this work, we further investigated their distinctive thermal properties and found that form I is the dominating and the most thermally stable phase while form II is favored by fast nucleation conditions and is the least stable phase. On the other hand, form III represents a minor intermediate phase that usually coexists with form I and can be transferred from form II and to form I. Structural and morphological changes in form I have been followed by simultaneous wide-angle x-ray diffraction (WAXD)/small-angle x-ray scattering (SAXS) measurements during cold- or melt-crystallization and subsequent melting. In all cases, a larger dimensional change was found in the crystallographic a-axis than the b-axis during heating and cooling. This may be due to the greater lateral stress variation with respect to temperature along the a direction of the primary lamellae which is induced by either the formation of secondary lamellae or the preferential chain-folding direction in poly(aryl ether ketone ketone)s. During the phase transitions of form II ← III in the cold-crystallized specimen and form III ← I in the melt-crystallized samples, lamellar variables (long period, lamellar thickness, and invariant) obtained from SAXS remain almost constant. This indicates that the density distribution in the long spacing is independent of the melting in form II or III. For melt-crystallization, the corresponding changes in unit-cell dimensions and lamellar morphology during the annealing-induced low endotherm are most consistent with the argument that these changes are due to the melting of thin lamellar population. © 1995 John Wiley & Sons, Inc.     

The epitaxial growth of gaas using alkylarsine: Part 2. molecular orbital calculation

Semi-empirical molecular orbital calculations were carried out for the compounds (C₂H₅)₃As, (C₂H₅)₃Ga and RAsH₂ (R = C₂H₅, i-C₃H₇, i-C₄H₉, and t-C₄H₉) by using the CNDO/2-U program, and their capability of β-elimination reaction is compared on the basis of the torsion energy to the transition state, electrostatic interactions and orbital overlapping between the central atom and the β-hydrogen, and bond order of the metal-carbon, and carbon-hydrogen bond. In the comparison of (C₂H₅)₃As with (C₂H₅)₃Ga, we found that the β-elimination of (C₂H₅)₃As could hardly be expected to take place in the thermal decomposition. The capability of β-elimination would be smaller in C₂H₅AsH₂ than that in (C₂H₅)₃As. Moreover when the ethyl group is replaced by a t-butyl group in RAsH₂, the β-elimination reaction appears to become more difficult and a large possibility for a radical process is suggested.     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

Discontinuous travelling wave solutions for certain hyperbolic systems

In an earlier paper on a malignant cell invasion model (Marchantet al., SIAM J. Appl. Math, 60, 2000) we introduced a novelform of discontinuous travelling wave solution. These solutionscould be studied easily by combining behaviour within a phaseplane with the Rankine–Hugoniot shock conditions, whichdescribe properties (such as the ratio of the jump discontinuitiesto the speed of propagation) that solutions may possess. Theseresults were new for several reasons. The shock conditions relateto hyperbolic equations (which the model is) but were appliedin a travelling wave ordinary differential equation phase planeusing techniques that usually apply to parabolic reaction–diffusionsystems. In addition the solutions possess singular behaviournear several points in the phase plane but in spite of thisthere exists a robust and stable family of physically interestingsolutions. In this paper we discuss two previously studied models, oneof detonation theory and one of angiogenesis. We show that eachof these models also possesses a family of discontinuous travellingwave solutions which was not previously discovered. Of particularinterest is the solution which has a blunt interface at thefront of the invading profile. In all three models it is thissolution that is seen to stably evolve from physically relevantinitial data, and for physically relevant parameter values. This work confirms the robustness of these novel travellingwave solutions and their applicability to a wider range of mathematicalmodelling situations.     

A microspectroscopic study of the electronic homogeneity of ordered and disordered Sr2FeMoO6

Disordered Sr₂FeMoO₆ shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish that e_xtensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with composition fluctuations of the type Sr₂Fe_1+x Mo_1-x O₆ with Fe-rich (x > 0) and Mo-rich (x < 0) regions. Dedicated to Prof J Gopalakrishnan on his 62nd birthday.     

A RAPID APPROXIMATION FOR PREDICTING THE HYDROCARBON DISCOVERY RATE: PART 1. ASSESSING THE ACCURACY

The hydrocarbon discovery prediction problem is important to firms having to make decisions about the deployment of scarce exploration resources. Traditional methods for estimating the discovery rate rely on the completion of time consuming simulation experiments. A rapid approximation that does not require the completion of simulation exists and has been shown to have some promise as a prediction tool. This paper investigates the accuracy of the approximation method under a wide variety of distributional and drilling efficiency assumptions. The results indicate that the approximation produces predictions close to those of simulation under most of the tested conditions. This suggests that resource exploration firms could conveniently use the method for a wide variety of planning purposes without incurring the same costs in time and personnel required for simulation.     

On the retrograde condensation of one or two liquids

This contribution discusses the phenomena of retrograde condensation of one or two liquids. It w1 be shown that both phenomena can be well understood. Also the relation of retrograde condensation of one liquid phase with the condensation behavior of natural gas will be discussed. Similarly that of two liquid phases with multiple phase behavior occurring in low temperature reservoir fluids will be pointed out.     

Gelation of poly(n-butylisocyanate) in benzene

Poly (n-butylisocyanate)-benzene solutions prepared by solubilization at 45°C, followed by aging at room temperature were found to be metastable for months, although, eventually, they separated into a birefringent polymer-rich phase and an isotropic solution. These metastable solutions, as well as isothermally phase-separated biphasic samples, flowed and exhibited dynamic moduli indicative of low polymer connectivity. By contrast samples prepared by a freeze-thaw cycle were uniformly and highly birefringent and showed network (gel) behavior at room temperature. The mechanism of gel formation is most likely the exclusion of the polymer from the benzene crystal during crystallization, forcing the polymer to align and exist at grain boundaries. Films formed from solutions have different moduli than those formed from gels, and are consistent with the proposed mechanism.