Effect of molybdenum on the kinetics of phase transformation of undercooled austenite in high-speed steels under continuous cooling

The aim of these investigations was to determine the effect of the ratio % Mo to % W in the austenite of high-speed steels on the kinetics of its transformation under continuous cooling. The investigations were carried out on model alloys. Three CCT curves were drawn. Also the influence of cooling velocity on the volume fraction of retained austenite in high-speed steels was evaluated. It was determined that with the increase of the Mo content in the high-speed steel matrix the M_S temperature decreases and the fraction of retained austenite increases, the development of the bainite transformation decreases and the stability of austenite increases in the range of diffusion transformations. With an increased cooling rate, the volume fraction of retained austenite decreases at first and then it increases. These changes are caused by the precipitation of carbides from undercooled austenite and can give rise to the differences in the content of retained austenite on the cross-section of quenched tools.     

Direct <Emphasis Type="SmallCaps">d</Emphasis>-Glucose Oxidation over Noble Metal Nanoparticles Introduced on Polymer and Inorganic Supports

In the present work, nanocatalysts prepared on inorganic supports (zeolites) were investigated in d-glucose oxidation and compared to systems supported on polymer (hypercrosslinked polystyrene (HPS)) previously described. Catalytic activities and selectivities were measured under various reaction conditions. The selectivity of d-glucose oxidation and activity of both Pd-containing zeolites and HPS-Ru were similar (99.7% and TOF 0.013–0.014 mol/(mol Me s)). Physicochemical analysis X-ray photoelectron spectroscopy, liquid nitrogen physisorption, diffuse reflectance infrared Fourier transform spectroscopy of adsorbed CO for metal sites evaluation, CD₃CN for acid sites evaluation showed that Pd species were in oxidic form, while Ru species were in oxidic and reduced form. The catalytic activity decreased when acidic sites were present in Pd-containing zeolites.     

New Indenylidene‐Schiff Base‐Ruthenium Complexes for Cross‐Metathesis and Ring‐Closing Metathesis

We here report on the stability and catalytic activity of new indenylidene‐Schiff base‐ruthenium complexes 3a – f through representative cross‐metathesis (CM) and ring‐closing metathesis (RCM) reactions. Excellent activity of the new complexes was found for the two selected RCM reactions; prominent conversion was obtained compared to the commercial Hoveyda–Grubbs catalyst 2 . Moreover, excellent results were obtained for a standard CM reaction. Higher conversions were achieved with one of the indenylidene catalysts compared with Hoveyda–Grubbs catalyst. Unexpectedly, an isomerization reaction was observed during the CM reaction of allylbenzene. To the best of our knowledge, isomerization reactions in this model CM reaction in closed systems have never been described using first generation catalysts, including the Hoveyda–Grubbs catalyst. The first model CM reactions as well as the RCM reactions have been monitored using ¹H NMR. The course of the CM reaction of 3‐phenylprop‐1‐ene ( 8 ) and cis‐1,4‐diacetoxybut‐2‐ene ( 9 ) was monitored by GC. The isomerization reaction was studied by means of GC‐mass spectrometry and in situ IR spectroscopy. All catalysts were structurally characterized by means of ¹H, ¹³C, and ³¹P NMR spectroscopy.     

Anti-Inflammatory Effect of Very High Dose Local Vessel Wall Statin Administration: Poly(L,L-Lactide) Biodegradable Microspheres with Simvastatin for Drug Delivery System (DDS)

Atherosclerosis involves an ongoing inflammatory response of the vascular endothelium and vessel wall of the aorta and vein. The pleiotropic effects of statins have been well described in many in vitro and in vivo studies, but these effects are difficult to achieve in clinical practice due to the low bioavailability of statins and their first-pass metabolism in the liver. The aim of this study was to test a vessel wall local drug delivery system (DDS) using PLA microstructures loaded with simvastatin. Wistar rats were fed high cholesterol chow as a model. The rat vessels were chemically injured by repeated injections of perivascular paclitaxel and 5-fluorouracil. The vessels were then cultured and treated by the injection of several concentrations of poly(L,L-lactide) microparticles loaded with the high local HMG-CoA inhibitor simvastatin (0.58 mg/kg) concentration (SVPLA). Histopathological examinations of the harvested vessels and vital organs after 24 h, 7 days and 4 weeks were performed. Microcirculation in mice as an additional test was performed to demonstrate the safety of this approach. A single dose of SVPLA microspheres with an average diameter of 6.4 μm and a drug concentration equal to 8.1% of particles limited the inflammatory reaction of the endothelium and vessel wall and had no influence on microcirculation in vivo or in vitro. A potent pleiotropic (anti-inflammatory) effect of simvastatin after local SVPLA administration was observed. Moreover, significant concentrations of free simvastatin were observed in the vessel wall (compared to the maximum serum level). In addition, it appeared that simvastatin, once locally administered as SVPLA particles, exerted potent pleiotropic effects on chemically injured vessels and presented anti-inflammatory action. Presumably, this effect was due to the high local concentrations of simvastatin. No local or systemic side effects were observed. This approach could be useful for local simvastatin DDSs when high, local drug concentrations are difficult to obtain, or systemic side effects are present.     

Higher‐order differentiation of network functions using signal flow graphs

This paper presents the application of signal flow graphs (SFG) in the calculation of higher‐order derivatives (sensitivities) of the linear circuit functions. The idea of exact differentiation of the circuit functions is based on the adjoint networks, translated into SFG language. Thanks to its application, it is possible to calculate the exact value of any order derivative of circuit function without knowing this function in explicit form. Moreover, these derivatives can be determined on the basis of analysis of only two graphs (circuits): the original and adjoint one. We show that the SFG approach to the sensitivity calculation allows to reduce greatly the complexity of calculations. Copyright © 2011 John Wiley & Sons, Ltd.     

Catalytic graphene formation in coal tar pitch- derived carbon structure in the presence of SiO2 nanoparticles

A simple and effective way to manufacture graphene from a coal tar pitch (CTP) is demonstrated. Silica (SiO₂) nanoparticles were used to modify the CTP as carbon precursor. A silica nanofiller introduced into the CTP matrix underwent carboreduction during heat treatment to 2000 °C, resulting in the formation of silicon carbide. Surfaces of SiC grains were sites for graphene formation. The influence of SiO₂ on the structure and microstructure of CTP- based carbon matrix, after annealing up to 2800 °C, was studied. Carbon samples were analyzed using X- ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and Raman Spectroscopy. Crystallite sizes (L_a, L_c) and interplanar distance (d₀₀₂) were determined. The presence of SiO₂ in CTP carbon precursor favored the crystallites’ growth in the ‘a′ crystallographic graphite direction, and inhibited their growth on the ‘c′ axis. The crystallites composing of graphene layers, were characterized by an elongated dimension in the ‘a′ axis direction. Above 2000 °C silicon carbide decomposed, followed by the sublimation of silicon from the carbon matrix.     

Extension of the node‐to‐segment contact element for surface‐expansion‐dependent contact laws

A class of friction laws depending on the measure of contact surface expansion is defined in the paper within the continuum contact mechanics framework. The nominal and spatial forms of constitutive relations are discussed, including incremental penalty relations. Further, an extended node‐to‐segment element is derived which is capable of treating surface‐expansion‐dependent contact laws in a consistent way. The approach is suitable for any kind of node‐to‐segment contact elements. Finally, the computational efficiency of the extended element as well as other possible approaches are illustrated by numerical examples relevant to metal forming applications. Copyright © 2001 John Wiley & Sons, Ltd.     

Learning in dynamic neural networks using signal flow graphs

The paper presents the universal approach to the determination of the sensitivity functions for dynamic neural networks and its application in learning algorithms of adaptive networks. The method is based on the application of signal flow graph and specially defined graph adjoint to it. The method is equally applied to either feed‐forward or recurrent network structures. This paper is mainly concerned with neural network applications of the approach. Different kinds of dynamic neural networks are considered and discussed in the paper: the FIR dynamic multilayer perceptron (MLP), the cascade connection of dynamic MLPs as well as two non‐linear recurrent systems: the dynamic recurrent MLP network and ARMA recurrent network. The rule of sensitivity determination has been applied in practical learning of neural networks. Chosen results of numerical experiments concerning the application of this approach to the learning processes of recurrent neural networks are also given and discussed. Copyright © 1999 John Wiley & Sons, Ltd.     

Low-frequency dielectric properties for diagnosis of aging in polymeric cables

The results of thermally stimulated discharging currents and isothermal direct currents measurements, performed on crosslinked polyethylene cable models aged under different thermal and electrothermal stresses, are presented and discussed. It is shown that aging affects the low-frequency behavior of the polymer. The changes observed in the relaxation processes are related to those of other properties, e.g., density, melting enthalpy, electric strength, electrical conductivity, and microstructure, as well as to the degradation phenomena caused in the insulation by the applied stresses. The proposed techniques, therefore, prove to be an effective diagnostic tool for investigating the aging of polymeric insulating materials. © 1996 John Wiley & Sons, Inc.     

Nanoparticles from polylactide and polyether block copolymers: formation, properties, encapsulation, and release of pyrene--fluorescent model of hydrophobic drug

Polylactide-b-polyglycidol-b-poly(ethylene oxide) terpolymers and their derivatives with carboxyl and 4-(phenylazo)phenyl labels in polyglycidol blocks were used for formation of nanoparticles. Nanoparticles were produced by self assembly of terpolymer macromolecules in water above the critical aggregation concentration and by dialysis of terpolymer solutions in 1,4-dioxane against water. For terpolymers with 4-(phenylazo)phenyl labels critical aggregation concentrations increased after irradiation with UV light (300 < lambda < 400 nm) inducing conformational change of the label from trans- to cis-conformation. Diameters of nanoparticles obtained by self-assembly of macromolecules ranged from 20 to 44 nm. Dialysis yielded nanoparticles with bimodal diameter distribution. One fraction had diameters below 35 nm and diameters of the second fraction were in a range from 350 to 2300 nm, depending on terpolymer structure. Mixtures of terpolymers with poly(L,L-lactide) and poly(D,D-lactide) blocks yielded nanoparticles with diameters from 350 to 440 nm. Pyrene was incorporated into nanoparticles by partition between solution and nanoparticles or directly during particle formation by dialysis. Monitoring of pyrene release from nanoparticles suggests that a fraction of this compound was entrapped into the polylactide core whereas the remaining one was located in the polyether rich shell. The release from shells is faster for nanoparticles made from copolymers with carboxyl labels in polyglycidol blocks.