Reduction of aqueous chromate by Fe(II)/Fe(III) carbonate green rust: kinetic and mechanistic studies

This work describes the heterogeneous reaction between FeII in carbonate green rust and aqueous chromate, in NaHCO3 solutions at 25 degrees C, and at pH values of 9.3-9.6. Evidence for reduction of CrVI to CrIII and concomitant solid-state oxidation of lattice FeII to FeIII was found from FeII titration and from structural analysis of the solids using FTIR, XRD, SEM, and XPS methods. Results indicate the formation of ferric oxyhydroxycarbonate and the concomitant precipitation of CrIII monolayers at the surface of the iron compound that induce passivation effects and progressive rate limitations. The number of CrIII monolayers formed at the completion of the reaction depends on [FeII]t=0, the molar concentration of FeII(solid) at t=0; on [n(o)]t=0, the molar concentration of reaction sites present at the surface of the solid phase at t=0; and on [CrVI]t=0, the molar concentration of CrVI at t=0. Kinetic data were modeled using a model based on the formation of successive CrIII monolayers, -(d[CrVI]/dt) = sigma(1)j k(i)[S] [CrVI]([n(i - 1)] - [n(i)]) with k(i)[S] (in s(-1) L mol(-1)), the rate coefficient of formation of CrIII monolayer i, and [n(i)] and [n(i - 1)], the molar concentration of CrIII precipitated in monolayer i and monolayer i - 1, respectively. Good matching curves were obtained with kinetic coefficients: k(1)[S] = 5-8 x 10(-4), k(2)[S] = 0.5-3 x 10(-5), and k(3)[S] about 1.7 x 10(-6) s(-1) m(-2) L. The CrVI removal efficiency progressively decreases along with the accumulation of CrIII monolayers at the surface of carbonate green rust particles. In the case of thick green rust particles resulting from the corrosion of iron in permeable reactive barriers, the quantity of FeII readily accessible for efficient CrVI removal should be rather low.     

Is Dimethyldecanal a Common Aggregation Pheromone of Tribolium Flour Beetles?

Flour beetles are cosmopolitan and common pests in grain stores and flour mills. Their ability to exploit a wide variety of stored products has contributed to their status as major pests of stored food. Although it was previously reported that the same aggregation pheromone, 4,8-dimethyldecanal (DMD), is shared by three flour beetles species (Tribolium castaneum, T. confusum, and T. freemani), the volatiles released by the other Tribolium species associated with stored products have not yet been examined. In the present study, the volatiles produced by males and females of eight Tribolium species were examined by solid phase microextraction (SPME). SPME samples were analyzed by gas chromatography coupled to mass spectrometry (GC-MS). Experiments were conducted to identify volatiles emitted by the adults of different Tribolium species and to determine whether DMD is a common aggregation pheromone. We observed that DMD is not a common pheromone of the eight species tested, but is common to T. castaneum, T. confusum, T. freemani, and T. madens. Two other volatiles were detected, 1-pentadecene, which is shown here to be a common semiochemical of flour beetles, and 1,6-pentadecadiene, which was detected in five species (T. audax, T. brevicornis, T. destructor, T. freemani, and T. madens).     

A general discontinuous Galerkin method for finite hyperelasticity. Formulation and numerical applications

A discontinuous Galerkin formulation of the boundary value problem of finite‐deformation elasticity is presented. The primary purpose is to establish a discontinuous Galerkin framework for large deformations of solids in the context of statics and simple material behaviour with a view toward further developments involving behaviour or models where the DG concept can show its superiority compared to the continuous formulation. The method is based on a general Hu–Washizu–de Veubeke functional allowing for displacement and stress discontinuities in the domain interior. It is shown that this approach naturally leads to the formulation of average stress fluxes at interelement boundaries in a finite element implementation. The consistency and linearized stability of the method in the non‐linear range as well as its convergence rate are proven. An implementation in three dimensions is developed, showing that the proposed method can be integrated into conventional finite element codes in a straightforward manner. In order to demonstrate the versatility, accuracy and robustness of the method examples of application and convergence studies in three dimensions are provided. Copyright © 2006 John Wiley & Sons, Ltd.     

Engine calibration: multi-objective constrained optimization of engine maps

We present two new approaches to address the optimization problem associated with engine calibration. In this area, the tuning parameters are traditionally determined in a local way, i.e., at each engine operating point, via a single-objective minimization problem. To overcome these restrictions, the first method we propose is able to cope with several objective functions simultaneously in the local formulation. The second method we put forward relies on a global formulation, which allows the whole driving cycle to be taken into account while remaining single-objective. At the practical level, the two methods are implemented by combining various existing techniques such as the LoLiMoT (Local Linear Model Tree) parameterization and the MO-CMA-ES (Multi-Objective Covariance Matrix Adaptation Evolution Strategy) algorithm. A better compromise appears to be achieved on real case applications.     

Long-term Uncertainty of Hydropower Revenue Due to Climate Change and Electricity Prices

Hydropower represents the world’s largest renewable energy source. As a flexible technology, it enhances reliability and security of the electricity system. However, climate change and market liberalization may hinder investment due to the evolution of water runoffs and electricity prices. Both alter expected revenue and bring uncertainty. It increases risk and deters investment. Our research assesses how climate change and market fluctuation affect annual revenue. But this paper focuses on the uncertainty, rather than on forecasting. This transdisciplinary topic is investigated by means of a mixed method, i.e. both quantitative and qualitative. The quantitative approach uses established models in natural sciences and economics. The uncertainty is accounted for by applying various scenarios and various datasets coming from different models. Based on those results, uncertainty is discussed through an analysis discerning three dimensions of uncertainty. Uncertainty analysis requires the assessment of a large panel of models and data sets. It is therefore rarely carried out. The originality of the paper also lies on the combination of quantitative established models with a qualitative analysis. The results surprisingly show that the greenhouse gas scenarios may in fact represent a low source of uncertainty, unlike electricity prices. Like forecasting, the main uncertainties are actually case study related and depend on the investigated variables. It is also shown that the nature of uncertainty evolves. Runoff uncertainty goes from variability, i.e. inherent randomness, to epistemic, i.e. limitation of science. The reverse situation occurs with the electricity price. The implications for scientists and policy makers are discussed.     

An enhanced Lemaitre model formulation for materials processing damage computation

The Lemaitre damage model is now widely used to deal with coupled damage analyses for various mechanical applications. In this article, different extensions of the model are presented and discussed to deal with complex multiaxial configurations—such as multi-stages bulk forming processes. A specific treatment is done to account for compressive damage growth, and a stress triaxiality cut-off value is considered to avoid any damage evolution below a critical negative triaxiality. The damage potential is also modified to deal with highly ductile materials, and the plastic strain is split into a negative part and a positive part to differentiate damage growth for compressive states of stress and for tensile states of stress. Finally, an anisotropic damage approach based on the comparison between grain flow orientation and principal loading directions is defined. A combination of these extensions is achieved within a single Lemaitre formulation. Application on different examples show the robustness and accuracy of the model defined in this paper.     

Hydraulic Modeling of a Mixed Water Level Control Hydromechanical Gate

This article describes the hydraulic behavior of a mixed water level control hydromechanical gate present in several irrigation canals. The automatic gate is termed “mixed” because it can hold either the upstream water level or the downstream water level constant according to the flow conditions. Such a complex behavior is obtained through a series of side tanks linked by orifices and weirs. No energy supply is needed in this regulation process. The mixed flow gate is analyzed and a mathematical model for its function is proposed, assuming the system is at equilibrium. The goal of the modeling was to better understand the mixed gate function and to help adjust their characteristics in the field or in a design process. The proposed model is analyzed and evaluated using real data collected on a canal in the south of France. The results show the ability of the model to reproduce the function of this complex hydromechanical system. The mathematical model is also implemented in software dedicated to hydraulic modeling of irrigation canals, which can be used to design and evaluate management strategies.     

Validation tests of the full-discontinuous Galerkin/extrinsic cohesive law framework of Kirchhoff-Love shells

Due to its ability to account for discontinuities, the discontinuous Galerkin (DG) method presents two main advantages for modeling crack initiations and propagation. On the one hand, it provides an easy way to insert the cohesive elements during the simulation and therefore avoids the drawbacks inherent to the use of an extrinsic cohesive law. On the other hand, the capture of complex crack path requires very thin meshes, and the recourse to a parallel implementation of DG formulations exhibits a high scalability of the resolution scheme. Recently, the authors developed such a DG-fracture framework for Kirchhoff-Love shells in the linear and non-linear ranges. They proved that this framework dissipates, during the fracture process, an amount of energy equal to the fracture energy of the material and that the model is able to propagate the crack with the right speed. In this paper, novel numerical benchmarks are presented to validate the method in various fracture conditions. The two first ones include an initial notch and study the fracture propagation under two different dynamic loadings (impact and blast). The two other ones focus on the fragmentation of initially unbroken specimens due to uniform expansion, in order to demonstrate the ability of the new framework to model crack initiations. Results are in all cases in agreement with the ones reported in the literature.     

A least‐squares coupling method between a finite element code and a discrete element code

This paper presents a coupling method between a discrete element code CeaMka3D and a finite element code Sem. The coupling is based on a least‐squares method, which adds terms of forces to finite element code and imposes the velocity at coupling particles. For each coupling face, a small linear system with a constant matrix is solved. This method remains conservative in energy and shows good results in applications. Copyright © 2014 John Wiley & Sons, Ltd.     

Influence of Cu off-stoichiometry on wide band gap CIGSe solar cells

The electric properties of solar cells based on co-evaporated Cu(In,Ga)Se₂ (CIGSe) thin film show a good tolerance regarding the absorber Cu content (y = [Cu]/([In] + [Ga])) for standard Ga concentration, i.e. x = [Ga] / ([In] + [Ga]) ~ 0.3. In the present contribution, we show that this tolerance is lost when the gallium content is increased. Wide bandgap CIGSe samples (x ~ 0.55) with a variation in y from 0.97 to 0.84 have been grown. The efficiency of the cells decreases from 12.6% to 6.5% for y = 0.97 and 0.84 respectively. For the lowest y, the efficiency is harmed because of a low short-circuit current density (J_sc), an increased voltage dependency in the current collection, which affects the fill factor (FF), and a decrease of the open-circuit voltage (V_oc). For y = 0.97 and 0.84 respectively, the decrease of the activation energy (E_a) from 1.36 to 1.24 eV indicates a shift of the area of the dominant recombination from the space charge region towards the interface. There seems to be evidence that reducing the Cu-content in the CIGSe thin film will cause a decrease in the width of the space charge region. Solar cells based on Cu-rich CIGSe (1.03 < y < 1.09) have also been fabricated and characterized. A strong deterioration of their electrical properties is observed despite the KCN etch of the segregated Cu_2 − xSe binary phases at the surface, suggesting the presence of residual Cu_2 − xSe precipitates within the layer.