Shadowing effects for continuum and discrete deposition models

We study the dynamical evolution of the deposition interface using both discrete and continuous models for which shadowing effects are important. We explain why continuous and discrete models implying both only shadowing deposition do not give the same result and propose a continuous model which allow to recover the result of the discrete one exhibiting a strong columnar morphology

Anomalous diffusion mediated by atom deposition into a porous substrate

Constant flux atom deposition into a porous medium is shown to generate a dense overlayer and a diffusion profile. Scaling analysis shows that the overlayer acts as a dynamic control for atomic diffusion in the porous substrate. This is modeled by generalizing the porous diffusion equation with a time-dependent diffusion coefficient equivalent to a nonlinear rescaling of timeComment: 4 page

Plasma based platinum nanoaggregates deposited on carbon nanofibers improve fuel cell efficiency

Improved platinum catalytic utilization has been achieved by creating an open support structure based on aligned carbon nanofibers (CNFs) attached to carbon loaded carbon cloth electrodes [known as gas diffusion layer (GDL)]. The nickel catalyst used to initiate the CNFs growth; the CNFs themselves and the 5nm Pt nanoaggregates were deposited sequentially in the same low pressure plasma reactor. This oriented catalyst structure was incorporated into a membraneelectrode assembly and tested with and without CNFs and on carbon paper or GDL. The performance of the fuel cells based on CNFs and GDL was better over the entire range of operating current.One of the authors A.C. gratefully acknowledges ARC Australian Research Network for Advanced Materials, CNRS GDR-I “Plasmas” and ANU for financial support

Do not forget the electrochemical characteristics of the membrane electrode assembly when designing a Proton Exchange Membrane Fuel Cell stack

International audienceThe membrane electrode assembly (MEA) is the key component of a PEMFC stack. Conventional MEAs are composed of catalyzed electrodes loaded with 0.1-0.4 mgPt cm−2 pressed against a Nafion® membrane, leading to cell performance close to 0.8 W cm−2 at 0.6 V. Due to their limited stability at high temperatures, the cost of platinum catalysts and that of proton exchange membranes, the recycling problems and material availability, the MEA components do not match the requirements for large scale development of PEMCFs at a low cost, particularly for automotive applications. Novel approaches to medium and high temperature membranes are described in this work, and a composite polybenzimidazole-poly(vinylphosphonic) acid membrane, stable up to 190 ◦C, led to a power density of 0.5 W cm−2 at 160 ◦C under 3 bar abs with hydrogen and air. Concerning the preparation of efficient electrocatalysts supported on a Vulcan XC72 carbon powder, the Bönnemann colloidal method and above all plasma sputtering allowed preparing bimetallic platinum-based electrocatalysts with a low Pt loading. In the case of plasma deposition of Pt nanoclusters, Pt loadings as low as 10 g cm−2 were achieved, leading to a very high mass power density of ca. 20 kW g−1 Pt . Finally characterization of the MEA electrical properties by Electrochemical Impedance Spectroscopy (EIS) based on a theoretical model of mass and charge transport inside the active and gas diffusion layers, together with the optimization of the operating parameters (cell temperature, humidity, flow rate and pressure) allowed obtaining electrical performance greater than 1.2 W cm−2 using an homemade MEA with a rather low Pt loading

High Power Impulse Magnetron Sputtering deposition of Pt inside fuel cell electrodes

International audienceHigh Power Impulse Magnetron Sputtering process is used to incorporate catalytic nanoclusters of platinum into microporous carbon. Such a process leads to an enhancement of the Pt species penetration into the porous media as evidenced by Rutherford backscattering spectroscopy analysis. Each catalyzed porous carbon is tested as a cathode of a proton exchange membrane fuel cell. An increase of 80 % at 0.65 V of the PEMFC power density for a low catalyst loading of 0.02 mg.cm-2 highlights the use of the HiPIMS process versus the conventional DC magnetron sputtering proces

X-μCT and DVC use for composite materials analysis

The complex mechanical behaviour of composite materials, due to internal heterogeneity and multi-layered composition imposes deeper studies. This paper presents an experimental protocol to perform volume kinematic measurements in composite materials. This work is centered on the transverse shear effects in relation with the composite materials mechanical behaviour. A lot of theories exist in literature to consider the existing warping section during high transverse shear stresses, but very few studies have been realized in the experimental way. The association of X-ray micro-computed tomography acquisitions and Digital Volume Correlation (DVC) technique allows the measurement of displacements and deformations in the whole volume of composite specimen. To elaborate the latter, composite fibres and epoxy resin are associated with metallic particles to make contrast in X-μCT acquisitions. A specific in-situ loading device is presented for three-point bending tests, which enables the visualization of transverse shear effects in composite structures

Far-and mid-infrared properties of carbon layers elaborated by plasma sputtering

International audienceThe far-and mid-infrared reflectivity spectra of two carbon layers deposited on pure (100) silicon substrates by DC magnetron sputtering were investigated at room temperature in the 10-5000 cm-1 wavenumber range. Their structural and textural features were also studied by combining Raman spectroscopy, Field Emission Scanning Electron Microscopy (FESEM), High Resolution Transmission Electron Microscopy (HRTEM), X-Ray Reflectivity (XRR) and Rutherford Backscattering Spectroscopy (RBS). The set of results was used to discuss afterwards the influence of the texture on the infrared properties at varying length scale. Thereby, the two layers were found to be heterogeneous as assessed by RBS, XRR and FESEM and their thicknesses had been measured by XRR and FESEM. The information on the structural organization and " crystallite " size was given by Raman spectroscopy. The influence of both the textural and structural parameters on the measured infrared reflectivity spectra was discussed. Finally, a methodology was proposed to recover the intrinsic index of refraction and the intrinsic index of absorption of each layer

Robust Trajectory Planning with Parametric Uncertainties

International audienceIn this paper we extend the previously introduced notion of closed-loop state sensitivity by introducing the concept of input sensitivity and by showing how to exploit it in a trajectory optimization framework. This allows to generate an optimal reference trajectory for a robot that minimizes the state and input sensitivities against uncertainties in the model parameters, thus producing inherently robust motion plans. We parametrize the reference trajectories with Béziers curves and discuss how to consider linear and nonlinear constraints in the optimization process (e.g., input saturations). The whole machinery is validated via an extensive statistical campaign that clearly shows the interest of the proposed methodology

Ballistic and molecular dynamics simulations of aluminum deposition in micro-trenches

Two different feature scale modeling frameworks are utilized for the study of aluminum (Al) deposition profiles inside micro-trenches. The first framework, which is applied in metal-organic chemical vapor deposition (MOCVD) of Al, couples a ballistic model for the local flux calculation, a surface chemistry model, and a profile evolution algorithm. The calculated conformity of the deposited film is compared with experimental results corresponding to Al MOCVD from dimethylethylamine alane (DMEAA). The outcome of the comparison is that the effective sticking coefficient of DMEAA is in the range of 0.1 - 1. There is also a strong indication that surface reaction kinetics follows Langmuir - Hinshelwood or Eley - Rideal mechanism. The second framework, which is applied in physical vapor deposition of Al, implements 2D molecular dynamics (MD) simulations. The simulations are performed in a "miniaturized" domain of some hundreds of Angstroms and are used to explore micro-trench filling during magnetron sputtering deposition of Al on a rotated substrate. Most of the experimental results are qualitatively reproduced by the MD simulations; the rotation, aspect ratio, and kinetic energy effects are correctly described despite the completely different length scales of simulation and experiment. The sticking probability of Al is calculated 0.6 for the conditions of the experiments

Membrane patterned by pulsed laser micromachining for proton exchange membrane fuel cell with sputtered ultra-low catalyst loadings

International audienceProton exchange membranes were nano-and micro-patterned on their cathode side by pressing them against stainless steel molds previously irradiated by a Ti:Sapphire femtosecond laser. The membranes were associated to ultra-low loaded thin catalytic layers (25 µgPt cm-2) prepared by plasma magnetron sputtering. The Pt catalyst was sputtered either on the membrane or on the porous electrode. The fuel cell performance in dry conditions were found to be highly dependent on the morphology of the membrane surface. When nanometric ripples covered by a Pt catalyst were introduced on the surface of the membrane, the fuel cell outperformed the conventional one with a flat membrane. By combining nano-and micro-patterns (nanometric ripples and 11-24 µm deep craters), the performance of the cells was clearly enhanced. The maximum power density achieved by the fuel cell was multiplied by a factor of 3.6 (at 50 °C and 3 bars): 438 mW cm-2 vs 122 mW cm-2. This improvement is due to high catalyst utilization with a high membrane conductivity. When Pt is sputtered on the porous electrode (and not on the membrane), the contribution of the patterned membrane to the fuel cell efficiency was less significant, except in the presence of nanometric ripples. This result suggests that the patterning of the membrane must be consistent with the way the catalyst is synthesized, on the membrane or on the porous electrode