The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Rheological and physical properties of aliphatic hyperbranched polyesters

The effects of the size (pseudo‐generation number) and nature of end groups on physical and rheological properties were investigated for a series of hyperbranched polyesters based on an ethoxylated pentaerythritol core and 2,2‐bis‐(hydroxymethyl)propionic acid repeat units. The observed linear dependence of the melt viscosity on the molar mass in the high pseudo‐generation‐number limit indicated that entanglement effects were substantially absent. Moreover, the marked influence of end capping of the end groups on the physical and rheological properties suggested that intermolecular interactions were dominated by contacts between the outer shells of the molecules, in which the end groups were assumed to be concentrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1218–1225, 2004     

Random oscillations in the Van der Pol system under the action of a broadband random process

We construct the second approximation for random oscillations described by the Van der Pol equation which are under the action of a broadband random process. Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 50, No. 11, pp. 1517–1521, November, 1998.     

Surface and interfacial properties of PVDF/acrylic copolymer blends before and after UV exposure

Morphological and chemical properties of both the surface and interface of poly(vinylidene fluoride)/poly(methyl methacrylate)-co-poly(ethyl acrylate) (PVDF/PMMA-co-PEA) blend films have been investigated before and after the samples were exposed to ultraviolet (UV) irradiation using a xenon arc lamp at 50 °C and 9% relative humidity (RH) for 7 months. Surface and interfacial morphologies were studied by atomic force microscopy (AFM). Chemical composition information was obtained by confocal Raman microscopy, attenuated total reflection-FTIR spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Results show an enrichment of the PVDF material at the air surface, while the acrylic copolymer enriches the interface. Blends having greater than 50% mass fraction of PVDF show little change in the surface morphology after UV exposure for 7 months. However, for a lower PVDF content, blends exhibit significant degradation of PMMA-co-PEA copolymer and a much rougher surface after UV exposure. Microstructural changes in the PVDF spherulites are also observed after UV degradation. It is found that the surface and interfacial morphologies are correlated with the chemical properties.     

Direct measurement of fluid velocity gradients at a wall by PIV image processing with stereo reconstruction

Velocity gradient is typically estimated in Particle Image Velocimetry (PIV) by differentiating a measured velocity field, which amplifies noise in the measured velocities. If gradients near a boundary are sought, such noise is usually greater than in bulk fluid, because of small tracer displacement, uncertainty in the effective positions of velocity vectors, intense deformation of tracer patterns, and laser reflection. We consider here a modified form of the Particle Image Distortion (PID) method todirectly calculate velocity gradients at a fixed wall, and refer it as “PIV/IG” (“Interface Gradiometry”). Results from synthetic 2D PIV images suggest our method achieves higher SNR and accuracy than velocity differentiation. Also, we have developed a procedure to reconstruct three-dimensional velocity gradient at a fixed wall the two non-zero components from PIV/IG data obtained in stereo views; these equations simplify considerably thanks to the no-slip condition. Experimental data from the bottom wall of turbulent open channel flow appear to suffer from a form of pixel locking. As with standard PIV, this underlines the importance of adequate tracer diameter in the images, sufficient seeding density, and of dynamic range of the camera sensor.     

A Higher-Dimensional Version of the Brody Reparametrization Lemma

We prove a generalization of the Brody reparametrization lemma.__________Published in Ukrains’kyi Matematychnyi Zhurnal, Vol. 56, No. 10, pp. 1369 – 1377, October, 2004.     

Convergence estimates of Galerkin-wavelet solutions to a Cauchy problem for a class of periodic pseudodifferential equations

A class of Cauchy problems for interesting complicated periodic pseudodifferential equations is considered. By the Galerkin-wavelet method and with weak solutions one can find sufficient conditions to establish convergence estimates of weak Galerkin-wavelet solutions to a Cauchy problem for this class of equations.

     

Graphitic nanofillers in PMMA nanocomposites—An investigation of particle size and dispersion and their influence on nanocomposite properties

Mechanical, thermal, and electrical properties of graphite/PMMA composites have been evaluated as functions of particle size and dispersion of the graphitic nanofiller components via the use of three different graphitic nanofillers: “as received graphite” (ARG), “expanded graphite,” (EG) and “graphite nanoplatelets” (GNPs) EG, a graphitic materials with much lower density than ARG, was prepared from ARG flakes via an acid intercalation and thermal expansion. Subsequent sonication of EG in a liquid yielded GNPs as thin stacks of graphitic platelets with thicknesses of ～10 nm. Solution‐based processing was used to prepare PMMA composites with these three fillers. Dynamic mechanical analysis, thermal analysis, and electrical impedance measurements were carried out on the resulting composites, demonstrating that reduced particle size, high surface area, and increased surface roughness can significantly alter the graphite/polymer interface and enhance the mechanical, thermal, and electrical properties of the polymer matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2097–2112, 2007