Interaction Mechanisms Between Ar–O<Subscript>2</Subscript> Post-Discharge and Stearic Acid II: Behaviour of Thick Films

We study the interaction of thick films (~4 mm) of stearic acid (SA), a C₁₈ alkane skeleton with an acid function, with late Ar–O₂ post-discharge. Contrary to what is observed with thin films of SA (~2–3 μm) which are efficiently etched (part I), only functionalization is observed over the first 2 h of treatment with a plasma source operated in the continuous mode, whatever the temperature. The heat released by surface reactions affects non-linearly the temperature of the substrate. Pulsing the source at a frequency ranging from 0.1 to 1 kHz slows down the functionalization process but does not allow any etching of the material. On the contrary, the SA can be etched as thick films by pulsing the oxygen flow rate at a frequency below 50 mHz. By pulsing the reactive gas, the time averaged value of the [O]/[O₂] ratio is decreased, limiting the functionalization processes due to oxygen atoms, and the mean temperature is lowered, decreasing the diffusion length of O₂ (and/or possibly O₂*) species in the SA which are responsible for the scission of C–C bonds of radicals.     

Mathematical Analysis of a Transport Model with Unbounded Heat Capacities

We consider a problem of nuclear waste contamination in the basement. We derive a detailed model describing the simultaneous transport of brine, radionuclides and heat in a compressible flow through a porous medium. It leads to a nonlinear system of fully coupled partial differential equations. Using a fixed point approach, we prove existence of physically relevant weak solutions.      

Importance of Outer‐Sphere and Aggregation Phenomena in the Relaxation Properties of Phosphonated Gadolinium Complexes with Potential Applications as MRI Contrast Agents

A series composed of a tetra‐, a tris‐ and a bisphosphonated ligand based on a pyridine scaffold ( L⁴ , L³ and L² , respectively) was studied within the frame of lanthanide (Ln) coordination. The stability constants of the complexes formed with lanthanide cations (Ln=La, Nd, Eu, Gd, Tb, Er and Lu) were determined by potentiometry in aqueous solutions (25.0 °C, 0.1 M NaClO₄), showing that the tetraphosphonated complexes are among the most stable Ln^III complexes reported in the literature. The complexation of L⁴ was further studied by different titration experiments using mass spectrometry and various spectroscopic techniques including UV/Vis absorption, and steady state and time‐resolved luminescence (Ln=Eu and Tb). Titration experiments confirmed the formation of highly stable [Ln L⁴ ] complexes. ³¹P NMR experiments of the Lu L⁴ complex revealed an intramolecular interconversion process which was studied at different temperatures and was rationalized by DFT modelling. The relaxivity properties of the Gd^III complexes were studied by recording their ¹H NMRD profiles at various temperatures, by temperature dependent ¹⁷O NMR experiments (Gd L⁴ ) and by pH dependent relaxivity measurements at 0.47 T (Gd L³ and Gd L² ). In addition to the high relaxivity values observed for all complexes, the results showed an important second‐sphere contribution to relaxivity and pH dependent variations associated with the formation of aggregates for Gd L² and Gd L³ . Finally, intravenous injection of Gd L⁴ to a mouse was followed by dynamic MRI imaging at 1.5 T, which showed that the complex can be immediately found in the blood stream and rapidly eliminated through the liver and in large part through the kidneys.     

Hydrodynamic Limit for an Arc Discharge at Atmospheric Pressure

In this paper we study a partially ionized plasma that corresponds to an arc discharge at atmospheric pressure. We derive an inviscid hydrodynamic/diffusion limit, characterized by two temperatures, from a system of Boltzmann type transport equations modelling that plasma problem. The original property of this system is that impact ionization is a leading order collisional process. As a consequence, the density of electrons is given in terms of the density of the other species (and its temperature) via a Saha law.     

Interaction of (3-Aminopropyl)triethoxysilane with Pulsed Ar–O<Subscript>2</Subscript> Afterglow: Application to Nanoparticles Synthesis

The interaction of (3-Aminopropyl)triethoxysilane (APTES) with pulsed late Ar–O₂ afterglow is characterized by the synthesis of OH, CO and CO₂ in the gas phase as main by-products. Other minor species like CH, CN and C₂H are also produced. We suggest that OH radicals are produced in a first step by dehydrogenation of APTES after interaction with oxygen atoms. In a second step, the molecule is oxidized by any O₂ state, to form peroxides that transform into by-products, break thus the precursor C–C bonds. If oxidation is limited, i.e. a low duty cycle, fragmentation of the precursor is limited and produced nanoparticles keep the backbone structure of the precursor, but contain amide groups produced from the amine groups initially available in APTES. At high duty cycle, silicon-containing fragments contain some carbon and react together and produce nanoparticles with a non-silica-like structure.     

Asymptotic Analysis of a Nonlinear Parabolic Problem Modelling Miscible Compressible Displacement in Porous Media

We study the asymptotic behavior, with respect to high Peclet numbers, of a model describing a compressible and miscible displacement in a porous medium. The transport of mass is then described by a nonlinear, fully coupled and degenerate parabolic system. Using non-classical estimates and renormalization tools, we prove existence of relevant weak solutions for the limit problem.      

Cut cell strategy for 3-D blast waves numerical simulations

   Abstract. This paper presents the results obtained by a generalized cut cells strategy on 3-D blast waves problems. The mesh is cartesian except when it is intersected by the surface of the solids inserted in the computational domain. The improvement, relatively to a classical cut-cells method, is the treatment of the cut which preserves the real geometry of the surface instead of approximating it by a plane. This approach avoids a loss of precision of the numerical scheme at the boundaries and allows future extension to higher order schemes (). Moreover it is useful for any kind of geometry with a high efficiency in computation time. The drawback is the complexity of the geometrical problems which can rise because of the diversity of situations in the treatment of the cuts. The performance of the approach is tested on a few examples allowing comparisons with experiments or other techniques and physical discussions. Received 15 November 1999 / Accepted 11 July 2000     

Derivation of the Double Porosity Model of a Compressible Miscible Displacement in Naturally Fractured Reservoirs

We derive a double porosity model for a displacement of one compressible miscible fluid by another in a naturally fractured reservoir. The microscopic model consists of the usual equations describing Darcy flow in a reservoir except that the porosity and the permeability coefficients are highly discontinuous. The viscosity is assumed to be constant. Over the matrix domain, the coefficients are scaled by a parameter ? representing the size of the matrix blocks. This scaling preserves the physics of the flow in the matrix as ? tends to zero. Using homogenization theory, we derive rigorously the corresponding double porosity model. To this purpose, we mainly use the concept of two-scale convergence. The less permeable part of the rock then contributes as nonlinear memory terms. To specify them in spite of the strong nonlinearities and of the coupling, we then use some appropriate dilation operator.