Solution Polymerization of N-vinylcaprolactam in 1,4-dioxane. Kinetic Dependence on Temperature, Monomer, and Initiator Concentrations

The kinetics of the solution free radical polymerization of N-vinylcaprolactam, in 1,4-dioxane and under various polymerization conditions was studied. Azobisisobutyronitrile and 3-mercaptopropionic acid were used as initiator and as chain transfer agent (CTA), respectively. The influence of monomer and initiator concentrations and polymerization temperature on the rate of polymerizations (R(p)) was investigated. In general, high conversions were obtained. The order with respect to initiator was consistent with the classical kinetic rate equation, while the order with respect to the monomer was greater than unity. The overall activation energy of 53.6 kJ mol(-1) was obtained in the temperature range 60-80 degrees C. The decreasing of the absolute molecular weights when increasing the CIA concentration was confirmed by GPC/SEC/LALS analyses. It was confirmed by UV-visible analyses the effect of molecular weights on the lower critical solution temperature of the polymers. It was also verified that the addition of the CTA influenced the kinetic of the polymerizations. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 229-240, 2010

Corrosion behavior of Ti-xNb-13Zr alloys in Ringer`s solution

Ti-6Al-4V alloy has been widely used in restorative surgery due to its high corrosion resistance and biocompatibility. Nevertheless, some studies showed that V and Al release in the organism might induce cytotoxic effects and neurological disorders, which led to the development of V-free alloys and both V- and Al-free alloys containing Nb, Zr, Ta, or Mo. Among these alloys, Ti-13Nb-13Zr alloy is promising due to its better biomechanical compatibility than Ti-6Al-4V. In this work, the corrosion behavior of Ti, Ti-6Al-4V, and Ti-xNb-13Zr alloys (x=5, 13, and 20) was evaluated in Ringer`s solution (pH 7.5) at 37 degrees C through open-circuit potential measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy. Spontaneous passivity was observed for all materials in this medium. Low corrosion current densities (in the order of 10(-7) A/cm(2)) and high impedance values (in the order of 10(5) Omega cm(2) at low frequencies) indicated their high corrosion resistance. EIS results showed that the passivating films were constituted of an outer porous layer (very low resistance) and an inner compact layer (high resistance), the latter providing the corrosion resistance of the materials. There was evidence that the Ti-xNb-13Zr alloys were more corrosion resistant than both Ti and Ti-6Al-4V in Ringer`s solution.

Combined solution for fault location in three-terminal lines based on wavelet transforms

This work presents the study and development of a combined fault location scheme for three-terminal transmission lines using wavelet transforms (WTs). The methodology is based on the low- and high-frequency components of the transient signals originated from fault situations registered in the terminals of a system. By processing these signals and using the WT, it is possible to determine the time of travelling waves of voltages and/or currents from the fault point to the terminals, as well as estimate the fundamental frequency components. A new approach presents a reliable and accurate fault location scheme combining some different solutions. The main idea is to have a decision routine in order to select which method should be used in each situation presented to the algorithm. The combined algorithm was tested for different fault conditions by simulations using the ATP (Alternative Transients Program) software. The results obtained are promising and demonstrate a highly satisfactory degree of accuracy and reliability of the proposed method.

On the accuracy of two-fluid model predictions for a particular gas-solid riser flow

Literature presents a huge number of different simulations of gas-solid flows in risers applying two-fluid modeling. In spite of that, the related quantitative accuracy issue remains mostly untouched. This state of affairs seems to be mainly a consequence of modeling shortcomings, notably regarding the lack of realistic closures. In this article predictions from a two-fluid model are compared to other published two-fluid model predictions applying the same Closures, and to experimental data. A particular matter of concern is whether the predictions are generated or not inside the statistical steady state regime that characterizes the riser flows. The present simulation was performed inside the statistical steady state regime. Time-averaged results are presented for different time-averaging intervals of 5, 10, 15 and 20 s inside the statistical steady state regime. The independence of the averaged results regarding the time-averaging interval is addressed and the results averaged over the intervals of 10 and 20 s are compared to both experiment and other two-fluid predictions. It is concluded that the two-fluid model used is still very crude, and cannot provide quantitative accurate results, at least for the particular case that was considered. (C) 2009 Elsevier Inc. All rights reserved.

Chaos-Galerkin solution of stochastic Timoshenko bending problems

This paper presents an accurate and efficient solution for the random transverse and angular displacement fields of uncertain Timoshenko beams. Approximate, numerical solutions are obtained using the Galerkin method and chaos polynomials. The Chaos-Galerkin scheme is constructed by respecting the theoretical conditions for existence and uniqueness of the solution. Numerical results show fast convergence to the exact solution, at excellent accuracies. The developed Chaos-Galerkin scheme accurately approximates the complete cumulative distribution function of the displacement responses. The Chaos-Galerkin scheme developed herein is a theoretically sound and efficient method for the solution of stochastic problems in engineering. (C) 2011 Elsevier Ltd. All rights reserved.

A solid-like FEM for geometrically non-linear 3D frames

This study presents a solid-like finite element formulation to solve geometric non-linear three-dimensional inhomogeneous frames. To achieve the desired representation, unconstrained vectors are used instead of the classic rigid director triad; as a consequence, the resulting formulation does not use finite rotation schemes. High order curved elements with any cross section are developed using a full three-dimensional constitutive elastic relation. Warping and variable thickness strain modes are introduced to avoid locking. The warping mode is solved numerically in FEM pre-processing computational code, which is coupled to the main program. The extra calculations are relatively small when the number of finite elements. with the same cross section, increases. The warping mode is based on a 2D free torsion (Saint-Venant) problem that considers inhomogeneous material. A scheme that automatically generates shape functions and its derivatives allow the use of any degree of approximation for the developed frame element. General examples are solved to check the objectivity, path independence, locking free behavior, generality and accuracy of the proposed formulation. (C) 2009 Elsevier B.V. All rights reserved.

Consolidation of elastic-plastic saturated porous media by the boundary element method

This paper presents a domain boundary element formulation for inelastic saturated porous media with rate-independent behavior for the solid skeleton. The formulation is then applied to elastic-plastic behavior for the solid. Biot`s consolidation theory, extended to include irreversible phenomena is considered and the direct boundary element technique is used for the numerical solution after time discretization by the implicit Euler backward algorithm. The associated nonlinear algebraic problem is solved by the Newton-Raphson procedure whereby the loading/unloading conditions are fully taken into account and the consistent tangent operator defined. Only domain nodes (nodes defined inside the domain) are used to represent all domain values and the corresponding integrals are computed by using an accurate sub-elementation scheme. The developments are illustrated through the Drucker-Prager elastic-plastic model for the solid skeleton and various examples are analyzed with the proposed algorithms. (c) 2008 Elsevier B.V. All rights reserved.

Constitutive model for long term municipal solid waste mechanical behavior

This paper presents some improvements in the model proposed by Machado et al. [Machado SL, Carvalho MF, Vilar OM. Constitutive model for municipal solid waste. J Geotech Geoenviron Eng ASCE 2002; 128(11):940-51] now considering the influence of biodegradation of organic matter in the mechanical behavior of municipal solid waste. The original framework considers waste as composed of two component groups; fibers and organic paste. The particular laws of behavior are assessed for each component group and then coupled to represent waste behavior. The improvements introduced in this paper take into account the changes in the properties of fibers and mass loss due to organic matter depletion over time. Mass loss is indirectly calculated considering the MSW gas generation potential through a first order decay model. It is shown that as the biodegradation process occurs the proportion of fibers increases, however, they also undergo a degradation process which tends to reduce their ultimate tensile stress and Young modulus. The way these changes influence the behavior of MSW is incorporated in the final framework which captures the main features of the MSW stress-strain behavior under different loading conditions. (C) 2007 Elsevier Ltd. All rights reserved.

Identification of new ozonation disinfection byproducts of 17 beta-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L(-1) range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17 beta-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L(-1) and 100 mu g L(-1)) and at varying ozone dosages (0-30 mg L(-1)). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and El have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of El, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages. (C) 2011 Elsevier Ltd. All rights reserved.

Kinetic studies of urban solid residues and leachate from sanitary landfill

Urban solid residues are constituted of food remaining, grass leaves, fruit peelings, paper, cardboard, rubber, plastic, etc. The organic fraction formed represents about 50% during the decomposition yields biogas and leachate, which are sources of pollution. Residue samples were collected from the landfill in different and cells from several ages and the corresponding leachate, both after treatments, were submitted to thermal analysis. Kinetic parameters were determined using Flynn-Wall-Ozawa method. The linear relation between the two kinetic parameters (ln A and E) was verified for organic residue urban`s samples, but not for leachate`s sample. The occurred difference can be attributed to the constituents present in leachate.

Influence of the Solvent Evaporation Rate on the Crystalline Phases of Solution-Cast Poly(Vinylidene Fluoride) Films

The influence of the solvent-evaporation rate on the formation of of. and P crystalline phases in solution-cast poly(vinylidene fluoride) (PVDF) films was systematically investigated. Films were crystallized from PVDF/N,N-dimethylformamide solutions with concentrations of 2.5, 5.0, 10, and 20 wt % at different temperatures. During crystallization, the solvent evaporation rate was monitored in situ by means of a semianalytic balance. With this system, it was possible to determine the evaporation rate for different concentrations and temperatures of the solution under specific ambient conditions (pressure, temperature, and humidity). Fourier-Transform InfraRed spectroscopy with Attenuated Total Reflectance revealed the P-phase content in the PVDF films and its dependence on previous evaporation rates. Based on the relation between the evaporation rate and the PVDF phase composition, a consistent explanation for the different amounts of P phase observed at the upper and lower sample surfaces is achieved. Furthermore, the role of the sample thickness has also been studied. The experimental results show that not only the temperature but also the evaporation rate have to be controlled to obtain the desired crystalline phases in solution-cast PVDF films. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 785-791, 2010

Buckling and post-buckling of extensible rods revisited: A multiple-scale solution

An exact non-linear formulation of the equilibrium of elastic prismatic rods subjected to compression and planar bending is presented, electing as primary displacement variable the cross-section rotations and taking into account the axis extensibility. Such a formulation proves to be sufficiently general to encompass any boundary condition. The evaluation of critical loads for the five classical Euler buckling cases is pursued, allowing for the assessment of the axis extensibility effect. From the quantitative viewpoint, it is seen that such an influence is negligible for very slender bars, but it dramatically increases as the slenderness ratio decreases. From the qualitative viewpoint, its effect is that there are not infinite critical loads, as foreseen by the classical inextensible theory. The method of multiple (spatial) scales is used to survey the post-buckling regime for the five classical Euler buckling cases, with remarkable success, since very small deviations were observed with respect to results obtained via numerical integration of the exact equation of equilibrium, even when loads much higher than the critical ones were considered. Although known beforehand that such classical Euler buckling cases are imperfection insensitive, the effect of load offsets were also looked at, thus showing that the formulation is sufficiently general to accommodate this sort of analysis. (c) 2008 Elsevier Ltd. All rights reserved.

Numerical solution of the two-phase expansion of a metastable flashing liquid jet using the dispersion-controlled dissipative scheme

This paper presents a study of the stationary phenomenon of superheated or metastable liquid jets, flashing into a two-dimensional axisymmetric domain, while in the two-phase region. In general, the phenomenon starts off when a high-pressure, high-temperature liquid jet emerges from a small nozzle or orifice expanding into a low-pressure chamber, below its saturation pressure taken at the injection temperature. As the process evolves, crossing the saturation curve, one observes that the fluid remains in the liquid phase reaching a superheated condition. Then, the liquid undergoes an abrupt phase change by means of an oblique evaporation wave. Across this phase change the superheated liquid becomes a two-phase high-speed mixture in various directions, expanding to supersonic velocities. In order to reach the downstream pressure, the supersonic fluid continues to expand, crossing a complex bow shock wave. The balance equations that govern the phenomenon are mass conservation, momentum conservation, and energy conservation, plus an equation-of-state for the substance. A false-transient model is implemented using the shock capturing scheme: dispersion-controlled dissipative (DCD), which was used to calculate the flow conditions as the steady-state condition is reached. Numerical results with computational code DCD-2D vI have been analyzed. Copyright (C) 2009 John Wiley & Sons, Ltd.

Surface tension of flotation solution and its influence on the selectivity of the separation between apatite and gangue minerals

This work presents and discusses the influence of the surface tension (gamma(LV)) of methanol/water mixtures on the flotation response of apatite versus gangue minerals conditioned with flotation reagents (75 g/t cornstarch and 100 g/t Berol 867) at pH 10.6. Berol 867 is a collector composed of sodium alkyl sarcosinate plus nonionic surfactant. The highest Schulz efficiency of separation (recovery of apatite minus recovery of gangue) was achieved at approximate to 51.0 mN/m. The critical surface tension of wettability (gamma(C)) of apatite was found to occur at 34.7 mN/m when determined by means of gamma flotation experiments, , and it was 33.9 mN/m when determined by Zisman`s approach.

A contribution to the exact modal solution of in-plane beam structures

The exact vibration modes and natural frequencies of planar structures and mechanisms, comprised Euler-Bernoulli beams, are obtained by solving a transcendental. nonlinear, eigenvalue problem stated by the dynamic stiffness matrix (DSM). To solve this kind of problem, the most employed technique is the Wittrick-Williams algorithm, developed in the early seventies. By formulating a new type of eigenvalue problem, which preserves the internal degrees-of-freedom for all members in the model, the present study offers an alternative to the use of this algorithm. The new proposed eigenvalue problem presents no poles, so the roots of the problem can be found by any suitable iterative numerical method. By avoiding a standard formulation for the DSM, the local mode shapes are directly calculated and any extension to the beam theory can be easily incorporated. It is shown that the method here adopted leads to exact solutions, as confirmed by various examples. Extensions of the formulation are also given, where rotary inertia, end release, skewed edges and rigid offsets are all included. (C) 2008 Elsevier Ltd. All rights reserved.