Geometric modeling of homoepitaxial CVD diamond growth: I. The {1 0 0}{1 1 1}{1 1 0}{1 1 3} system

Plasma-assisted CVD homoepitaxial diamond growth is a process that must satisfy many stringent requirements to meet industrial applications, particularly in high-power electronics. Purity control and crystalline quality of the obtained samples are of paramount importance and their optimization is a subject of active research. In the process of such studies, we have obtained high purity CVD diamond monocrystals with unusual morphologies, namely with apparent {1 1 3} stable faces. This phenomenon has led us to examine the process of CVD diamond growth and build up a 3D geometrical model, presented here, describing the film growth as a function of time. The model has been able to successfully describe the morphology of our obtained crystals and can be used as a predictive tool to predetermine the shape and size of a diamond crystal grown in a given process configuration. This renders accessible control of desirable properties such as largest usable diamond surface area and/or film thickness, before the cutting and polishing manufacture steps take place. The two latter steps are more sensitive to the geometry of the growth sectors, which will be addressed in a companion paper.Our model, applicable to the growth of any cubic lattice material, establishes a complete mapping of the final morphology state of growing diamond, as a function of the growth rates of the crystalline planes considered, namely {1 0 0}, {1 1 1}, {1 1 0}, and {1 1 3} planes, all of which have been observed experimentally in diamond films. The model makes no claim as to the stability of the obtained faces, such as the occurrence of non-epitaxial crystallites or twinning. It is also possible to deduce transient behavior of the crystal morphology as growth time is increased. The model conclusions are presented in the form of a series of diagrams, which trace the existence (and dominance) boundaries of each face type, in presence of the others, and where each boundary crossing represent a topology change in terms of number of faces, edges and vertices. We validate the model by matching it against crystals published in the literature and illustrate its predictive value by suggesting ways to increase usable surface area of the diamond film.     

Modeling of H2 and H2/CH4 Moderate-Pressure Microwave Plasma Used for Diamond Deposition

One-dimensional transport models of moderate-pressure H ₂ and H ₂ /CH ₄ plasmas obtained in a diamond deposition microwave reactor are presented. These models describe the plasma as a thermochemically nonequilibrium flow with three different energy modes. The solution of the one-dimensional plasma transport equations enabled the estimation of plasma species concentrations and temperatures on the axis of the reactor. As far as pure H ₂ plasmas are concerned, results showed that the model predictions of gas and vibration temperatures are in good agreement with experimental measurements. The model also yields a relatively good qualitative prediction of the variations of H-atom mole fraction with the power density absorbed by the plasma. The results obtained for H ₂ /CH ₄ discharges showed that the model prediction on the variations of H-atom mole fraction with methane percentage in the discharge is in good qualitative agreement with experimental results. They also showed that methane is rapidly converted to acetylene before reaching the discharge zone. The concentrations of neutral hydrocarbon species in the reactor are mainly governed by thermal chemistry. The addition of methane strongly affects the ionization kinetics of the plasma. Three major ions are generally obtained in H ₂ /CH ₄ plasmas: C ₂ H ₂ ⁺ , C ₂ H ₃ ⁺ , and C ₂ H ₅ ⁺ . The relative predominance of these ions depends on the considered plasma region and on the discharge conditions. The ionic species concentrations are also mainly governed by chemistry, except very near the substrate surface. Finally the use of this transport model along with the surface chemistry model of Goodwin ⁽¹⁾ enabled us to estimate the diamond growth rate for several discharge conditions.     

The oxime bond formation as an efficient tool for the conjugation of ruthenium complexes to oligonucleotides and peptides

A convenient method for the conjugation of ruthenium complex on oligonucleotides and peptides through chemoselective oxime linkage is reported. Novel Ru(II) complexes sustaining an aminooxy containing ligand were prepared and efficiently coupled with the oligonucleotides and peptides functionalized with the complementary reactive aldehyde group. The method described herein could be a useful tool for preparing a broad range of metal complex-oligonucleotide and peptide conjugates.     

An evaluation of semidefinite programming based approaches for discrete lot-sizing problems

The present work is intended as a first step towards applying semidefinite programming models and tools to discrete lot-sizing problems including sequence-dependent changeover costs and times. Such problems can be formulated as quadratically constrained quadratic binary programs. We investigate several semidefinite relaxations by combining known reformulation techniques recently proposed for generic quadratic binary problems with problem-specific strengthening procedures developed for lot-sizing problems. Our computational results show that the semidefinite relaxations consistently provide lower bounds of significantly improved quality as compared with those provided by the best previously published linear relaxations. In particular, the gap between the semidefinite relaxation and the optimal integer solution value can be closed for a significant proportion of the small-size instances, thus avoiding to resort to a tree search procedure. The reported computation times are significant. However improvements in SDP technology can still be expected in the future, making SDP based approaches to discrete lot-sizing more competitive.     

Brain MRI lesion load quantification in multiple sclerosis: a comparison between automated multispectral and semi-automated thresholding computer-assisted techniques

Brain magnetic resonance imaging (MRI) lesion volume measurement is an advantageous tool for assessing disease burden in multiple sclerosis (MS). We have evaluated two computer-assisted techniques: MSA multispectral automatic technique that is based on bayesian classification of brain tissue and NIH image analysis technique that is based on local (lesion by lesion) thresholding, to establish reliability and repeatability values for each technique. Brain MRIs were obtained for 30 clinically definite relapsing-remitting MS patients using a 2.0 Tesla MR scanner with contiguous, 3 mm thick axial, T1, T2 and PD weighted modalities. Digital (Dicom 3) images were analyzed independently by three observers; each analyzed the images twice, using the two different techniques (Total 360 analyses). Accuracy of lesion load measurements using phantom images of known volumes showed significantly better results for the MSA multispectral technique (p < 0.001). The mean intra-and inter-observer variances were, respectively, 0.04 ± 0.4 (range 0.04–0.13), and 0.09 ± 0.6 (range 0.01–0.26) for the multispectral MSA analysis technique, 0.24 ± 2.27 (range 0.23–0.72) and 0.33 ± 3.8 (range 0.47–1.36) for the NIH threshold technique. These data show that the MSA multispectral technique is significantly more accurate in lesion volume measurements, with better results of within and between observers’ assessments, and the lesion load measurements are not influenced by increased disease burden. Measurements by the MSA multispectral technique were also faster and decreased analysis time by 43%. The MSA multispectral technique is a promising tool for evaluating MS patients. Non-biased recognition and delineation algorithms enable high accuracy, low intra-and inter-observer variances and fast assessment of MS related lesion load.     

Massively parallel LES of azimuthal thermo-acoustic instabilities in annular gas turbines

Increasingly stringent regulations and the need to tackle rising fuel prices have placed great emphasis on the design of aeronautical gas turbines, which are unfortunately more and more prone to combustion instabilities. In the particular field of annular combustion chambers, these instabilities often take the form of azimuthal modes. To predict these modes, one must compute the full combustion chamber, which remained out of reach until very recently and the development of massively parallel computers. In this article, full annular Large Eddy Simulations (LES) of two helicopter combustors, which differ only on the swirlers' design, are performed. In both computations, LES captures self-established rotating azimuthal modes. However, the two cases exhibit different thermo-acoustic responses and the resulting limit-cycles are different. With the first design, a self-excited strong instability develops, leading to pulsating flames and local flashback. In the second case, the flames are much less affected by the azimuthal mode and remain stable, allowing an acceptable operation. Hence, this study highlights the potential of LES for discriminating injection system designs. To cite this article: P. Wolf et al., C. R. Mecanique 337 (2009).     

On the origin of the cation templated self-assembly of uranyl-peroxide nanoclusters

Uranyl-peroxide nanoclusters display different topologies based on square, pentagonal and hexagonal building blocks. Computed complexation energies of different cations (Li(+), Na(+), K(+), Rb(+), and Cs(+)) with [UO(2)(O(2))(H(2)O)](n) (n = 4, 5, and 6) macrocycles suggest a strong cation templating effect. The inherent bent structure of a U-O(2)-U model dimer is demonstrated and justified through the analysis of its electronic structure, as well as of the inherent curvature of the four-, five-, and six-uranyl macrocyles. The curvature is enhaced by cation coordination, which is suggested to be the driving force for the self-assembly of the nanocapsules.     

High performance parallel computing of flows in complex geometries

Efficient numerical tools taking advantage of the ever increasing power of high-performance computers, become key elements in the fields of energy supply and transportation, not only from a purely scientific point of view, but also at the design stage in industry. Indeed, flow phenomena that occur in or around the industrial applications such as gas turbines or aircraft are still not mastered. In fact, most Computational Fluid Dynamics (CFD) predictions produced today focus on reduced or simplified versions of the real systems and are usually solved with a steady state assumption. This article shows how recent developments of CFD codes and parallel computer architectures can help overcoming this barrier. With this new environment, new scientific and technological challenges can be addressed provided that thousands of computing cores are efficiently used in parallel. Strategies of modern flow solvers are discussed with particular emphases on mesh-partitioning, load balancing and communication. These concepts are used in two CFD codes developed by CERFACS: a multi-block structured code dedicated to aircrafts and turbo-machinery as well as an unstructured code for gas turbine flow predictions. Leading edge computations obtained with these high-end massively parallel CFD codes are illustrated and discussed in the context of aircrafts, turbo-machinery and gas turbine applications. Finally, future developments of CFD and high-end computers are proposed to provide leading edge tools and end applications with strong industrial implications at the design stage of the next generation of aircraft and gas turbines.     

Premixed turbulent combustion modeling using tabulated detailed chemistry and PDF

Tabulated chemistry and presumed probability density function (PDF) approaches are combined to perform RANS modeling of premixed turbulent combustion. The chemistry is tabulated from premixed flamelets with three independent parameters: the equivalence ratio of the mixture, the progress of reaction, and the specific enthalpy, to account for heat losses at walls. Mean quantities are estimated from presumed PDFs. This approach is used to numerically predict a turbulent premixed flame diluted by hot burnt products at an equivalence ratio that differs from the main stream of reactants. The investigated flame, subjected to high velocity fluctuations, has a thickened-wrinkled structure. A recently proposed closure for scalar dissipation rate that includes an estimation of the coupling between flame wrinkling and micromixing is retained. Comparisons of simulations with experimental measurements of mean velocity, temperature, and reactants are performed.