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.     

Selective saturation and inversion of multiple resonances in high-resolution solid-state 13C experiments using slow spinning CP/MAS and tailored DANTE pulse sequences.

Taking advantage of the long 13C T1 values generally encountered in solids, selective saturation and inversion of more than one resonance in 13C CP/MAS experiments can be achieved by sequentially applying several DANTE pulse sequences centered at different transmitter frequency offsets. A new selective saturation pulse sequence is introduced composed of a series of 90 degrees DANTE sequences separated by interrupted decoupling periods during which the selected resonance is destroyed. Applications of this method, including the simplification of the measurement of the principal values of the 13C chemical shift tensor under slow MAS conditions, are described. The determination of the aromaticity of coal using a relatively slow MAS rate is also described.     

Microstructural evolution of decagonal quasicrystal in the undercooled Al72Ni12Co16 alloy melts

The microstructure evolution of decagonal quasicrystals in Al₇₂Ni₁₂Co₁₆ alloy was investigated by the electromagnetic melting and cyclic superheating method. Single-phase decagonal quasicrystals have been obtained when the undercoolings were larger than 60 K. The decagonal quasicrystals formed at various undercoolings show different microstructural morphologies. Furthermore, grain refinement was found near the undercooling of 120 K. Based on current thermodynamic and dendrite growth theories, a dimensionless superheating parameter was adopted to explain the effect of processing conditions on the microstructure of Al₇₂Ni₁₂Co₁₆ alloy. The result indicate that the fine equiaxied microstructure of decagonal quasicrystal (D-phase) formed near on undercooling of 120 K originates from the break-up of dendrites.     

The study of lithium fast ion conductors of Li3xLa0.67−xScyTi1−2yNbyO3 system

Perovskite-type lithium fast ion conductors of Li_3xLa_0.67−xSc_yTi_1−2yNb_yO₃ system were prepared by solid state reaction. X-Ray powder diffraction shows that perovskite solid solution form in the ranges of x=0.10, y≤0.10. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of the order of 10⁻⁴ S·cm⁻¹ and 10⁻⁵ S·cm⁻¹ at 25 °C respectively. The compositions have low bulk activation energies of about 17 kJ/mol in the temperature ranges of 298 – 523 K and total activation energies of about 37 kJ/mol in the temperature ranges of 298 – 523 K.     

Effect of end groups on complexation kinetics between cyclodextrins and guest polymers

α‐Cyclodextrin (α‐CD) has been complexed with various poly(ethylene glycol) (PEG) derivatives in aqueous solution. It has been found that the end groups of PEG derivatives affect the complexation kinetics greatly, but have only a little influence on the thermodynamic behavior. By increasing the hydrophobicity of end groups, the complexation speeds up rapidly. On the other hand, the bulky end groups slow down the threading of polymeric guests into the cavity of CD. By changing the hydrophobicity and the size of end groups, the complexation rate can be adjusted in the range of several orders of magnitudes, which should be quite useful in the design of new supramolecular systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2050–2057, 2006     

Determination of carbamazepine by chemiluminescence detection using chemically prepared tris(2,2'-bipyridine)ruthenium(III) as oxidant.

A new chemiluminescence method for the determination of carbamazepine (CBZ) has been developed. The method is based on the chemiluminescence produced in the reaction of tris(2,2'-bipyridine)ruthenium(III) and CBZ in an acidic medium. The chemiluminescence intensity was enhanced by organic solvents in the reaction system. Under the optimum experimental conditions, the calibration curve was linear over the range 4.0 x 10(-3)-8.6 x 10(-7) mol/L for CBZ. The detection limit (S/N = 3) was 2.5 x 10(-7) mol/L and the relative standard deviation of six replicate measurements was 2.6% for 4.0 x 10(-4) mol/L of CBZ. The possible reaction mechanism were also discussed. The chemiluminescence method was successfully applied to assay the CBZ contents in pharmaceutical tablets.     

Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003     

Crystallographic report: Bis(norfloxacin)dilead(II) tetranitrate, [Pb2(H‐Norf)2(ONO2)4]

The centrosymmetric binuclear structure of [Pb₂(H‐Norf)₂(ONO₂)₄]shows the geometry around each lead(II) atom to be distorted trigonal bipyramidal with Pb–O distances ranging from 2.357(3) to 2.769(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.     

核内核子－核子非弹散射截面（Ⅰ）

在与平均场、核内核子－核子弹性散射截面以及输运方程相统一的理论框架内推导了核内核子－核子非弹散射截面的解析表达式．其数值结果能很好地重现自由非弹截面的实验值，所计算的有效非弹截面与Ｄｉｒａｃ－Ｂｒｕｅｃｋｎｅｒ的计算结果相一致．     

Meromorphic functions connected with polylogarithms

M. V. Lomonosov Moscow State University. Translated from Funktsional'nyi Analiz i Ego Prilozheniya, Vol. 25, No. 1, pp. 88–91, January–March, 1991.