Metastable Phase Selection and Partitioning for Zr(1−x)AlxO(2−x/2) Materials Synthesized with Liquid Precursors

Aqueous solutions of zirconium acetate and aluminum nitrate were spray pyrolyzed at 250°C and upquenched to different temperatures to yield metastable solid solutions of composition Zr_{(1− x )}Al_xO_{(2− x /2)}. An amorphous oxide forms first during pyrolysis which subsequently crystallizes as a single phase for x ≤ 0.57 (≤40 mol% Al₂O₃). The crystallization temperature increased with Al₂O₃ content. Electron diffraction, supported by Raman spectroscopy, indicates that the initial phase is tetragonal. At higher temperatures, the initial solid solation partitions to other metastable phases, viz., t -ZrO₂+γ-Al₂O₃, prior to achieving their equilibrium phase assemblage, m -ZrO₂+α-Al₂O₃. Partitioning yields a nanocomposite microstructure with grain sizes of 20–100 nm, compared to the 3 to 5 nm in the initial, single phase. Compositions containing 45 to 50 mol% Al₂O₃ concurrently crystallize and partition. The structure selected during crystallization and the partitioning phenomena are discussed in terms of diffusional constraints during crystallization, which are conceptually similar to those operating during rapid solidification.     

Acceleration or retardation to crystallization if liquid-liquid phase separation occurs: Studies on a polyolefin blend by SAXS/WAXD, DSC and TEM

Blends of statistical copolymers containing ethylene/hexene (PEH) and ethylene/butene (PEB) exhibited the behavior of upper critical solution temperature (UCST). The interplay between the early and intermediate stage liquid-liquid phase separation (LLPS) and crystallization of the PEH/PEB 50/50 blend was studied by time-resolved simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques. Samples were treated by two different quench procedures: in single quench, the sample was directly quenched from 160 °C to isothermal crystallization temperature of 114 °C; while in double quench, the sample was firstly quenched to 130 °C for 20 min annealing, where LLPS occurred, and then to 114 °C. It was found that in the early stage of crystallization, the integrated values of Iq² and crystallinity, X_c, in the double quench procedure were consistently higher than those in the single quench procedure, which could be attributed to accelerated nucleation induced by enhanced concentration fluctuations and interfacial tension. In the late stage of crystallization, some morphological parameters were found to crossover and then reverse, which could be explained by retardation of lamellar growth due to phase separation formed during the double quench procedure. This phenomenon was also confirmed by DSC measurements in blends of different compositions at varying isothermal crystallization temperatures. The crystal lamellar thickness determined by SAXS showed a good agreement with TEM observation. Results indicated that the early stage LLPS in the PEH/PEB blend prior to crystallization indeed dictated the resulting lamellar structures, including the average size of lamellar stack and the stack distribution. There seemed to be little variation of lamellar thickness and long period between the two quenching procedures (i.e., single quench versus double quench).     

Non-newtonian flow through open channels

A general method is proposed for prediction of the flow rate and maximum velocity in the isothermal, steady, uniform, laminar flow of any incompressible, time-independent non-Newtonian fluid in straight open channels of arbitrary cross section. The method requires only a knowledge of two geometric coefficients and a function of shear stress, used to characterize the behavior of the fluid model. The slip effect at the solid boundary has been taken into consideration. Numerical values of the geometric parameters have been determined for flow through an inclined plane of infinite width, semi-circular, semi-elliptical, rectangular, and 90° and 60° symmetric triangular open channels. Applications have been made to various non-Newtonian fluid models such as the power-law, Bingham, Ellis, Meter and the Reiner-Rivlin general model. Numerical examples are presented. A generalization of the Fanning friction factor — Reynolds number is also presented. The problem of determining the point of transition from laminar to turbulent flow in the general case is examined, as is the problem of prediction of the friction factor in turbulent flow.     

Thermodynamic Modeling of Alkali Metal Oxide-Silica Binary Melts

The evaluation of the thermodynamic properties as well as the phase diagrams for the binary Na₂O–SiO₂, K₂O–SiO₂, and Li₂O–SiO₂ systems are carried out with a structural model for silicate melts and glasses. This thermodynamic model is based on the assumption that each metallic oxide produces the depolymerization reaction of silica network with a characteristic free-energy change. A least squares optimization program permits all available thermodynamic and phase diagram data to be optimized simultaneously. In this manner, data for these binary systems have been analyzed and represented with a small number of parameters. The resulting equations represent the thermodynamic and phase diagram data for these alkali metal oxide–silica systems within experimental error limits. In particular, the measured limiting liquidus slope at     is well reproduced.     

High molecular weight methyl ester of microbial poly(β,l-malic acid): Synthesis and crystallization

High molecular weight poly(α-methyl β,l-malate) (M_n ∼ 25,000, PD ∼ 1.7) was prepared from microbial poly(β,l-malic acid) (M_n ∼ 29,000, PD ∼ 1.3) by methylation with diazomethane in dry acetone without substantial cleavage of the polyester main chain. The thermal properties of this poly(malate) were assessed and its crystal structure was preliminary examined. Two crystal forms were identified by X-ray diffraction, their occurrence being dependent on crystallization conditions. The kinetics of nonisothermal and isothermal crystallizations from the melt were studied and modelled using the Avrami approach. Results were compared to those recently reported by us for low molecular weight poly(α-methyl β,l-malate) (M_n ∼ 3000, PD ∼ 1.3).     

Frontline robots in tourism and hospitality: service enhancement or cost reduction?

Electronic Markets - Robots are being implemented in many frontline services, from waiter robots in restaurants to robotic concierges in hotels. A growing number of firms in hospitality and tourism...     

A New Geometric Subproblem to Extend Solvability of Inverse Kinematics Based on Screw Theory for 6R Robot Manipulators

Geometric inverse kinematics procedures that divide the whole problem into several subproblems with known solutions, and make use of screw motion operators have been developed in the past for 6R robot manipulators. These geometric procedures are widely used because the solutions of the subproblems are geometrically meaningful and numerically stable. Nonetheless, the existing subproblems limit the types of 6R robot structural configurations for which the inverse kinematics can be solved. This work presents the solution of a novel geometric subproblem that solves the joint angles of a general anthropomorphic arm. Using this new subproblem, an inverse kinematics procedure is derived which is applicable to a wider range of 6R robot manipulators. The inverse kinematics of a closed curve were carried out, in both simulations and experiments, to validate computational cost and realizability of the proposed approach. Multiple 6R robot manipulators with different structural configurations were used to validate the generality of the method. The results are compared with those of other methods in the screw theory framework. The obtained results show that our approach is the most general and the most efficient.

     

Analytic expressions for the isosteric heat of adsorption from adsorption isotherm models and two-dimensional SAFT-VR equation of state

The isosteric heat of adsorption is an important thermodynamic property used to characterize and optimize adsorption processes. In this work, analytic expressions for isosteric heats of adsorption are derived for a collection of commonly used isotherm models and a two-dimensional molecular equation of state based on the SAFT-VR approach. The use of these expressions is presented with an example of adsorption of nitrous oxide, N₂O, on biochar, which is a waste biomass charcoal that exhibits high adsorption potential. The results show that accurate fitting of the adsorption isotherms leads to consistent results obtained with different approaches; however, the predicted isosteric heat of adsorption exhibits strong variations in the regions where experimental data is insufficient such in the region of low pressure/low coverage. Convergence on the prediction of the isosteric heat of adsorption by the different models is only observed in the region where no extrapolation of experimental data is needed.     

An investigation of the synergistic effect between magnetite nanoparticles and polypyrrole in nanostructured layer-by-layer films

In this paper, we report the controlled fabrication of layer-by-layer (LbL) films deposited on gold substrates with three different supramolecular architectures using polypyrrole (Ppy) and magnetite nanoparticles (Fe₃O₄-np), besides conventional poly(allylamine hydrochloride) (PAH) e poly(vinyl sulfonic acid) (PVS) polyelectrolytes, demonstrating the synergistic effect between Ppy and Fe₃O₄-np such as a result of their interaction. Modified gold electrodes were analyzed by contact angle (wettability), surface plasmon resonance (SPR), raman spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The (Fe₃O₄-np/Ppy)₃ architecture was also evaluated by scanning electron microscopy. The modified gold electrodes present more homogeneous covering, higher electron transfer and a decrease of resistance with the incorporation of the nanostructured materials such as Ppy and Fe₃O₄-np forming (Fe₃O₄-np/Ppy)₃ LbL film. The results carried out in this study suggest that the (Fe₃O₄-np/Ppy)₃ LbL film can be applied as a possible electrochemical or optical non-enzymatic sensor for analytical detection.     

Modulating drug release from poly(lactic-co-glycolic) acid microparticles by the addition of alginate and pectin

The aim of the present work is the characterization of PLGA microparticles including biopolymers for the controlled release of tilmicosin, a broad-spectrum antibiotic. Microparticles were prepared using the double-emulsion solvent evaporation technique. The effect of alginate and pectin incorporation over particle size and porosity, encapsulation efficiency (EE) and pH-responsive drug release was evaluated. Formulations presented a mean particle size of 5.5 μm approximately and a drug EE ranged from 22%–57%. PLGA-Alginate particles showed an increased porosity. Tilmicosin release profiles from PLGA and PLGA-biopolymer microparticles were affected by the particular combination of polymers and the pH of the release medium. The experimental data was simulated using a mathematical model, which takes into account the autocatalytic polymer degradation and the different mechanisms of drug transport. The combination of PLGA and biopolymers strongly influenced the morphology of the particles, offering the possibility of controlling the drug release profiles according to the therapy.