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.     

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.     

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.     

Quantitative theory of living free‐radical polymerization. III. Calculation of copolymerization products' spinodal

The problem of finding conditions of the loss of thermodynamic stability by the reaction system was solved on the basis of the developed theory of living free‐radical copolymerization. The spinodal's calculations were carried out for a significant number of systems differing in the values of kinetic, stoichiometric, and thermodynamic parameters. Analysis of the results of such calculations revealed some regularities in the spinodal curves' behavior and permitted us to classify their possible topological types. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 892–902, 2003     

Insight into chain dimensions in PEO/water solutions

Small‐Angle Neutron Scattering has been performed from poly(ethylene oxide) in deuterated water at temperature ranging from 10 to 80 °C. A simple fitting model was used to obtain a correlation length and a Porod exponent. The correlation length L characterizes the average distance between entanglements in the semidilute region and is proportional to the individual coil sizes in the dilute region. L was found to increase with temperature in the semidilute region but it decreases with temperature in the dilute region. This decrease is the precursor to the single‐chain collapse which applies to very dilute polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2196–2200, 2007     

Solvothermal synthesis of TiO2: anatase nanocrystals and rutile nanofibres from TiCl4 in acetone

This work reports a new synthetic approach for single‐phase TiO₂ nanomaterials by solvothermal treatment of titanium tetrachloride in acetone at 80–110 °C. Small, uniform, and yet size‐tunable (5–10 nm) anatase titania nanocrystallites were obtained using a low concentration of TiCl₄ in acetone (i.e., at molar ratios of TiCl₄/acetone ≤ 1:15) in the temperature range of 80–110 °C, while rutile nanofibers were synthesized using a high concentration of TiCl₄ (e.g., TiCl₄/acetone = 1:10) at 110 °C. Copyright © 2007 John Wiley & Sons, Ltd.     

Some geometrical aspects of semidefinite linear complementarity problems

This article studies some geometrical aspects of the semidefinite linear complementarity problem (SDLCP), which can be viewed as a generalization of the well-known linear complementarity problem (LCP). SDLCP is a special case of a complementarity problem over a closed convex cone, where the cone considered is the closed convex cone of positive semidefinite matrices. It arises naturally in the unified formulation of a pair of primal-dual semidefinite programming problems. In this article, we introduce the notion of complementary cones in the semidefinite setting using the faces of the cone of positive semidefinite matrices and show that unlike complementary cones induced by an LCP, semidefinite complementary cones need not be closed. However, under R₀-property of the linear transformation, closedness of all the semidefinite complementary cones induced by L is ensured. We also introduce the notion of a principal subtransformation with respect to a face of the cone of positive semidefinite matrices and show that for a self-adjoint linear transformation, strict copositivity is equivalent to strict semimonotonicity of each principal subtransformation. Besides the above, various other solution properties of SDLCP will be interpreted and studied geometrically.     

Restorations of punctured languages and similarity of languages

Punctured languages are languages whose words are partial words in the sense that the letters at some positions are unknown. We investigate to which extent restoration of punctured languages is possible if the number of unknown positions or the proportion of unknown positions per word, respectively, is bounded, and we study their relationships for different boundings. The considered restoration classes coincide with similarity classes according to some kind of similarity for languages. Thus all results we can also formulate in the language of similarity. We show some hierarchies of similarity classes for each class from the Chomsky hierarchy and prove the existence of linear languages which are not δ ‐similar to any regular language for any δ < ½. For δ ≥ ½ this is unknown but it could only be possible in the case of non‐slender linear languages. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)