A modern approach to the treatment of localized disease involves the use of advanced polymeric or ceramic implant materials for controlled-rate drug delivery. These implants are dynamic systems that maintain drug concentrations within the optimal therapeutic window via complex hydration, swelling, and degradation processes. To optimize the performance of these materials, however, requires a fundamental understanding of the mechanisms that govern drug release. Magnetic resonance imaging (MRI) provides a means of non-invasively characterizing the microstructure and transport properties in this type of material, and has proven to be an invaluable tool for their advancement. Calcium polyphosphate (CPP) is a biomaterial that has shown promise as a degradable matrix for drug delivery and bone defect repair. Release rates are potentially governed by hydrogelation, swelling, and polymer chain scission. CPP bioceramics have previously been studied using models for drug elution, but these tend to be simplistic and unable to explain the many interrelated mechanisms. Structural analysis techniques have also been applied, but these tend to be inherently destructive and unable to characterize the material in situ. With the aim of characterizing degradation/drug release mechanisms, a non-invasive approach based on MRI was developed and optimized for imaging two existing types of CPP device. Techniques included mapping of the T1 and T2 relaxation times and the apparent diffusion coefficient (ADC), which together provide sensitivity to local fluid transport parameters. The non-destructive nature of MRI permitted longitudinal observation, and structural degradation effects were investigated by correlation with concurrent drug elution measurements. Temporal variation in the release mechanisms was treated by analyzing elution in stages. Large variation between samples was found, but on average, drug elution that was controlled by a structural-relaxation mechanism appeared correlated with the gradual formation of a highly-mobile ``free'' water component within the disk. Other characteristics, such as swelling rate, did not appear to correlate with drug release at all. While the data did not implicate a singular, governing scheme for drug release from CPP bioceramics, the approach did yield an assessment of the relative importance of the various contributing mechanisms.

Les différents processus de dégradation des structures de génie civil induisent une micro, puis macro- fissuration du béton. Celle-ci génère alors une réduction des propriétés mécaniques de l'ouvrage et, à terme, sa perte d'étanchéité. Il est donc nécessaire de fournir des informations quant à la présence et à la taille de fissures pour procéder aux réparations nécessaires et conserver l'intégrité de l'ouvrage. Dans un premier temps, le contrôle du béton ainsi que la morphologie de la fissure réelle sont présentés. La notion de contacts entre ses lèvres est introduite pour définir la problématique de sa caractérisation. La bibliographie montre que les méthodes acoustiques standards ne sont pas adaptées à la caractérisation d'une fissure dans le béton. Deux pistes sont alors identifiées : les ultrasons diffus et l'acoustique non linéaire. Nous présentons dans un second temps la caractérisation de la fissure par analyse du transport de l'énergie suivant une équation de diffusion. Les paramètres associés (diffusivité et dissipation) sont déterminés expérimentalement sur des éprouvettes fissurées sur différentes profondeurs. Nous introduisons et définissons le temps d'arrivée du maximum de l'énergie (ATME) qui s'avère être le paramètre le plus sensible à la partie ouverte d'une fissure. Son évolution au regard des incertitudes de mesure ne permet toutefois pas de caractériser totalement la partie fermée. Une simulation numérique en différences finies est réalisée. Elle met en évidence le rôle des contacts au sein de la partie fermée de la fissure et confirme les observations expérimentales. / The various processes of deterioration of the building structures lead to a micro and macro-cracking of the concrete. Consequently, the mechanical properties of the structure are reduced and, eventually, the building is no longer airtight. It is therefore necessary to supply information regarding the presence and size of cracks to carry out the necessary repairs and keep the integrity of the structure. First, the control of concrete as well as the morphology of the actual crack are presented. The notion of contacts between its lips is introduced to define the problem of its characterization. The bibliography shows that the standard acoustic methods are not adapted for characterizing of a crack in concrete. Two tracks are then identified: the diffuse ultrasound and the nonlinear acoustics. Subsequently, we present the characterization of the crack by analyzing the transport of the energy with a diffusion equation. The associated parameters (diffusivity and dissipation) are experimentally determined on test tubes cracked at different depths. We introduce and define the arrival time of the maximum energy (ATME), which turns out to be the most sensitive parameter to the open part of a crack. Its evolution with regard to the measurement uncertainties does not allow a full characterization of the closed part. A digital modeling in finite differences is performed. It highlights the role of the contacts within the closed part of the crack and confirms the experimental observations. Then, we present the nonlinear acoustics and the associated methods applied to concrete.

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