Romain Rodrigues

Ce travail de thèse est axé sur le développement d'une technique de traitement chimique par déchloration réductrice de l'hexachlorobutadiène (HCBD) et de l'hexachloroéthane (HCA). La première partie a consisté en l'acquisition de données expérimentales de solubilité des deux composés (i) à différentes températures et (ii) en présence de surfactants. Les essais en température ont notamment permis de proposer, par le calcul des variations des grandeurs thermodynamiques de dissolution, une explication physique à la présence d'un minimum de solubilité entre 12 et 45 °C. La seconde partie, basée sur une étude préalable de sélection d'un réactif pour son efficacité, a consisté principalement en l'étude du mécanisme de déchloration réductrice par les microparticules de Pd/Fe en suspension dans l'acide polylactique, un polymère biodégradable. Différentes conditions expérimentales ont permis de démontrer que l'hydrogène atomique est le principal réducteur du système. Plusieurs lois cinétiques ont ensuite été utilisées pour la modélisation de la disparition de HCBD et HCA en études individuelles et en mélange.

The use of indirect electrical techniques is gaining interest for monitoring the corrosion of steel in concrete as they do not require any connection to the rebar. In this paper, we provide insights into the physical aspects of the indirect galvanostatic pulse (GP) method in the Wenner configuration. Considering uniform corrosion, the instantaneous ohmic drop is decreased due to the presence of the rebar, which acts as a short-circuit. However, we observed that this phenomenon is independent of the electrochemical parameters of the Butler–Volmer equation. They are, however, responsible for the nonlinear decrease of the current that polarizes the rebar over time, especially for a passive rebar due to its high polarization resistance. This evolution of the resulting potential difference with time is explained by the increase of the potential difference related to concrete resistance and the global decrease of the potential difference related to the polarization resistance of the rebar. The indirect GP technique is then fundamentally different than the conventional one in three-electrode configuration, as here the steady-state potential is not only representative of polarization resistance but also of concrete resistance. Considering non-uniform corrosion, the presence of a small anodic area disturbs the current distribution in the material. This is essentially due to the different capability of anodic and cathodic areas to consume the impressed current, resulting in slowing down the evolution of the transient potential as compared to uniform corrosion. Hence, highly corroding areas have a greater effect on the transient potential than on the steady-state one. The use of this temporal evolution is thus recommended to qualitatively detect anodic areas. For the estimation of their length and position, which is one of the main current problematic issue when performing any measurement on reinforced concrete (RC) structures with conventional techniques, we suggest adjusting the probe spacing to modulate the sensitivity of the technique.

The degradation mechanism of the pollutant hexachloroethane (HCA) by a suspension of Pd-doped zerovalent iron microparticles (Pd-mZVI) in dissolved lactic acid polymers and oligomers (referred to as PLA) was investigated using gas chromatography and the indirect monitoring of iron corrosion by continuous measurements of pH, oxidation-reduction potential (ORP), and conductivity. The first experiments took place in the absence of HCA, to understand the evolution of the Pd-mZVI/PLA/H₂O system. This showed that the evolution of pH, ORP, and conductivity is related to changes in solution chemistry due to iron corrosion and that the system is initially cathodically controlled by H⁺ mass transport to Pd surfaces because of the presence of an extensive PLA layer. We then investigated the effects of Pd-mZVI particles, temperature, initial HCA concentration, and PLA content on the Pd-mZVI/PLA/HCA/H₂O system, to obtain a better understanding of the degradation mechanism. In all cases, HCA dechlorination first requires the production of atomic hydrogen H^*—involving the accumulation of tetrachloroethylene (PCE) as an intermediate—before its subsequent reduction to non-chlorinated C₂ and C₄ compounds. The ratio between Pd-mZVI dosage, initial HCA concentration, and PLA content affects the rate of H^* generation as well as the rate-determining step of the process. A pseudo-first-order equation can be applied when Pd-mZVI dosage is much higher than the theoretical stoichiometry (600 mg for [HCA]₀ = 5–20 mg L⁻¹). Our results indicate that the HCA degradation mechanism includes mass transfer, sorption, surface reaction with H^*, and desorption of the product.