A comparison of spin relaxation and local motion between symmetrically and asymmetrically ring-substituted bisphenol units in dissolved polycarbonates

Carbon-13 and proton spin-lattice relaxation times were measured at two field strengths on solutions 10% by weight of two polycarbonates in C₂D₂Cl₄ from ?20 to +120°C. The first polycarbonate is an asymmetrically substituted form with one chlorine on one of the two phenylene aromatic rings of the bisphenol unit, whereas the second polycarbonate is symmetrically substituted with two chlorines on each of the two rings. The nuclear spin relaxation data are interpreted in terms of several local motions likely in these polymers. Segmental motion was described by the Hall–Helfand correlation function. Segmental motion in the monosubstituted polycarbonate is somewhat slower than in unsubstituted polycarbonate, whereas segmental motion in the tetrasubstituted polycarbonate is considerably slower. Phenylene ring rotation is observed in unsubstituted polycarbonate and in the monosubstituted polycarbonate above 40°C. Below 40°C in the monosubstituted species, and at all temperatures in the tetrasubstituted species, ring rotation is replaced by ring libration as the predominant motion contributing to spin lattice relaxation. In addition, the rotational motion of the two types of rings in the asymmetric monosubstituted form are very similar although not identical. The substituted ring is slightly less mobile than the rings of unsubstituted polycarbonate. This indicates a strong coupling of ring motion, although the coupling leads to less than synchronous motion. Methyl group rotation is present in both polymers and is little affected by the various structural modifications.     

Nonlinear Theory of the Plasma Wave Excitation in a Bounded Beam-Plasma System

The excitation of symmetric and antisymmetric plasma waves by a beam layer that moves within a homogeneous plasma enclosed by a metallic wall was dealt with theoretically. Investigations were carried out for the magnetic field free case and for a magnetized electron beam. In the latter case, the beam electrons are assumed to be unable to move in the perpendicular direction. The theoretical model bases upon an extension of the well known single wave theory to a two-dimensional beam-plasma system. Special emphasis should be paid to the fact that the perpendicular wave profile of the excited waves was determined self-consistently. Energy and momentum balance equations are derived for this system. The theoretical method outlined in this paper which is based on a Green's-function technique can be extended easily to three-dimensional systems or to beam-plasma systems with other boundary conditions. The main features of the saturation process of the basic unstable wave types are discussed. Several interesting effects were found in the magnetic field free case: (i) numerical solutions describe an increasing steepening of the wave amplitudes in perpendicular direction near the center of the system for the symmetric potential wave; (ii) for the antisymmetric wave, a smoothing tendency was found in the development of the perpendicular wave potential profile; (iii) spatial separation of the slow and fast beam electrons was observed; (iv) it is shown for the antisymmetric potential wave type that, under certain conditions, a very efficient beam particle retardation mechanism occurs which is connected with a strong reduction of the formation of a fast particle group; (v) generally it was shown that the conversion of the kinetic energy of the beam electrons into the plasma wave energy may be more effective as compared with the case of the magnetized beam.     

X-ray scattering studies of the structure of aqueous hydroxy-propylcellulose solutions

X-ray diffraction studies have been undertaken on aqueous solutions of hydroxy propylcellulose (HPC) over a wide range of the scattering vector Q. The experiments revealed only modest differences in local structure on a distance scale ca. 5–300 Å despite the fact that they covered concentrations generally interpreted as ranging from the isotropic (35.1 wt %) to the anisotropic liquid crystalline (LC) phase (53.5 wt %). Several models were used to interpret the small-angle scattering data, and each gave similar structural parameters and extrapolated intensities ( Q → 0) for both solutions. Peaks were observed with d-spacings ca. 12–17 Å in both materials. Wide-angle x-ray scattering (WAXS) showed slightly increased local order over a size range ca. 5–20 Å for the anisotropic solution, and this is consistent with a greater intensity of the 13 Å peak in this material. It is difficult to reconcile these findings with an interpretation of the LC state involving major differences with the isotropic phase and a high degree of orientational order extending over long length scales.     

Mean-value theorems and the nonoscillatory nature of solutions of partial differential equations in the spaces En and Pn

Analogs of the mean-value theorem are obtained for the Poisson equation with the Laplace-Beltrami operator in Euclidean and spherical spaces.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 44, No. 11, pp. 1477–1483, November, 1992.     

PERFORMANCE CHARACTERIZATION AND MODELING OF A COMPOSITE HIP PROSTHESIS

Hip prostheses made from thick laminated composite material were cyclically tested under biaxial compressive loading. Fatigue damage was studied using X-ray radiography, a surface replication, and sectioning of the specimens. It has been shown that damage in the neck region occurred predominantly in form of matrix cracking along fiber directions in the major load-carrying plies. These matrix cracks initiated from the surface of the medial-posterior corner, as a result of local high compressive stress, extended to the lateral side, and distributed toward the anterior side, with an increase of applied cycles. We also briefly outlined a life-prediction model for predicting the remaining life and strength of the composite prosthesis based on a "critical element" concept, as well as how laboratory test results can be used in the model.     

Identification of peroxyacetic acid uroporphyrin I in the urine of patients with congenital erythropoietic porphyria by liquid chromatography and mass spectrometry

A new porphyrin, peroxyacetic acid uroporphyrin I, has been isolated from the urine of patients with congenital erythropoietic porphyria by reversed phase high performance liquid chromatography. The porphyrin was characterized by high resolution mass spectrometry and by typical chemical reactions of a peroxyacid.     

Fluorescence anisotropy of acridinedione dyes in glycerol: Prolate model of ellipsoid

Time-dependent reorientations of resorcinol-based acridinidione (ADR) dyes in glycerol were studied using steady-state and time-resolved fluorescence studies. The difference between fluorescence anisotropy decays recorded at 460 nm when exciting at 250 nm and those obtained when exciting at 394 nm are reported. When exciting at 394 nm, the fluorescence anisotropy decay is bi-exponential, while on exciting at 250 nm a mono-exponential fluorescence anisotropy decay is observed. We interpret this in terms of different directions of the absorption dipole at 394 and 250 nm with the emission dipole respectively, which is experimentally validated and further analysed as a prolate model of ellipsoid.     

Static polarizabilities for the ne-isoelectronic series using Harbola–Sahni potential

The recently proposed Harbola–Sahni local potential in its exchange-only version [Phys. Rev. Lett. 62 , 689 (1989)] is found to give the static dipole and quadrupole polarizabilities for the Neisoelectronic series in excellent agreement with the corresponding Hartree–Fock estimates. © 1992 John Wiley & Sons, Inc.