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.     

液相添加剂对PTCR陶瓷电性能的影响

液相添加剂ＡＳＴ（Ａｌ２Ｏ３＋ＳｉＯ２＋ＴｉＯ２）对ＢａＴｉＯ３陶瓷材料电性能的影响很大，随着Ａｌ２Ｏ３含量的增加，材料的电性能降低；ＳｉＯ２、ＴｉＯ２的物理特性对材料电性能影响较大；过量ＴｉＯ２对材料ＰＴＣ效应有重要影响，适当过量ＴｉＯ２含量，可得到性能优良的ＰＴＣＲ陶瓷。     

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.     

激光冲击诱发相变的实验研究

本对激光冲击是否可以诱发相变进行了试验研究。用功率密度为１．０６×１０＾８Ｗ／ｃｍ＾２的激光器冲击Ｔ８钢表面。实验结果表明激光冲击处理使Ｔ８钢的表面显微硬度有所提高并可以发生马氏体相变。冲击处理后材料表面硬度提高了两倍，认为相变是Ｔ８钢表面硬度提高的原因之一。     

Growth of high-quality GaSb by metalorganic vapor phase epitaxy

The growth of nominally undoped GaSb layers by atmospheric pressure metalorganic vapor phase epitaxy on GaSb and GaAs substrates is studied. Trimethylgallium and trimethylantimony are used as precursors for the growth at 600°C in a horizontal reactor. The effect of carrier gas flow, V/III-ratio, and trimethylgallium partial pressure on surface morphology, electrical properties and photoluminescence is investigated. The optimum values for the growth parameters are established. The carrier gas flow is shown to have a significant effect on the surface morphology. The optimum growth rate is found to be 3–8 μm/ h, which is higher than previously reported. The 2.5 μm thick GaSb layers on GaAs are p-type, having at optimized growth conditions room-temperature hole mobility and hole concentration of 800 cm² V⁻¹ s⁻¹ and 3·10¹⁶ cm^-3, respectively. The homoepitaxial GaSb layer grown with the same parameters has mirror-like surface and the photoluminescence spectrum is dominated by strong excitonic lines.     

InSb,GaSb, and GaInSb grown using trisdimethylaminoantimony

GalnSb alloys as well as the constituent binaries InSb and GaSb have been grown by organometallic vapor phase epitaxy using the new antimony precursor trisdimethylaminoantimony (TDMASb) combined with conventional group III precursors trimethylindium (TMIn) and trimethylgallium (TMGa). InSb layers were grown at temperatures between 275 and 425°C. The low values of V/III ratio required to obtain good morphologies at the lowest temperatures indicate that the pyrolysis temperature is low for TDMASb. In fact, at the lowest temperatures, the InSb growth efficiency is higher than for other antimony precursors, indicating the TDMASb pyrolysis products assist with TMIn pyrolysis. A similar, but less pronounced trend is observed for GaSb growth at temperatures of less than 500°C. No excess carbon contamination is observed for either the InSb or GaSb layers. Ga_1-xIn_xSb layers with excellent morphologies with values of x between 0 and 0.5 were grown on GaSb substrates without the use of graded layers. The growth temperature was 525°C and the values of V/III ratio, optimized for each value of x, ranged between 1.25 and 1.38. Strong photoluminescence (PL) was observed for values of x of less than 0.3, with values of halfwidth ranging from 13 to 16 meV, somewhat smaller than previous reports for layers grown using conventional precursors without the use of graded layers at the interface. The PL intensity was observed to decrease significantly for higher values of x. The PL peak energies were found to track the band gap energy; thus, the luminescence is due to band edge processes. The layers were all p-type with carrier concentrations of approximately 10¹⁷ cm³. Transmission electron diffraction studies indicate that the Ga_0.5In_0.5 Sb layers are ordered. Two variants of the Cu-Pt structure are observed with nearly the same diffracted intensities. This is the first report of ordering in GalnSb alloys.     

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