My research has focussed on the development of a technique to tailor photochromic switching rates by creating a customised local environment for the dye within an otherwise rigid host matrix. Living radical polymerisation offers the potential to design such a system. A living radical initiator based on a spirooxazine compound was used to polymerise a polymer chain of well controlled molecular weight and polydispersity. This technique facilitated the construction of a conjugate with every photochromic moiety convalently attached to a polymer chain with uniform characteristics. The photochromic behaviour of these new polymer-spirooxazine conjugates were investigated in a cross-linked polymer matrix with a Tg of approximately 120??C. It is well known that photochromic switching is susceptible to local environment effects such as rigidity, free volume and polarity.1, 2 The goal of these systems was to create a uniform local environment which would facilitate controlled changes in the photochromic switching rates. The photophysical investigation of these systems demonstrated the success of this technique. The photochromic rates were directly related to the characteristics of the polymer conjugate. It was postulated the conjugates acted as a customised local environment for the photochromic moiety, encapsulating it from the host matrix. Consequently systematic tailoring of the photochromic switching rates was achieved by changes in the characteristics of the attached polymer. To our knowledge this is the first technique to control local environment of a photochromic compound and thus the first example of systematic tuning of photochromic switching rates. Throughout this research, several characteristics of the attached polymer were modified to give a series of rules for the tuning of photochromic switching rates using this technique. The largest variation in switching speed is achieved through variation of Tg. A range of photochromic rates from extremely slow to near solution-like can be easily achieved. The necessary variations in Tg can be achieved easily using living radical polymerisation techniques. The use of different homopolymers, block and random copolymers were all demonstrated successfully in this work. For finer tuning of the photochromic rates, changes in chain length can be used. It was also found the best living radical polymerisation method for this work was ATRP due to the bulky or incompatible halogen which contributed to efficient encapsulation. However this endgroup effect is only important in systems which do not have a low Tg component. The incorporation of such a component overrides all other contributions to the overall behaviour.

Thesis (Honors)--College of William and Mary, 2009. / Includes bibliographical references (leaf 12). Also available via the World Wide Web.

My research has focussed on the development of a technique to tailor photochromic switching rates by creating a customised local environment for the dye within an otherwise rigid host matrix. Living radical polymerisation offers the potential to design such a system. A living radical initiator based on a spirooxazine compound was used to polymerise a polymer chain of well controlled molecular weight and polydispersity. This technique facilitated the construction of a conjugate with every photochromic moiety convalently attached to a polymer chain with uniform characteristics. The photochromic behaviour of these new polymer-spirooxazine conjugates were investigated in a cross-linked polymer matrix with a Tg of approximately 120??C. It is well known that photochromic switching is susceptible to local environment effects such as rigidity, free volume and polarity.1, 2 The goal of these systems was to create a uniform local environment which would facilitate controlled changes in the photochromic switching rates. The photophysical investigation of these systems demonstrated the success of this technique. The photochromic rates were directly related to the characteristics of the polymer conjugate. It was postulated the conjugates acted as a customised local environment for the photochromic moiety, encapsulating it from the host matrix. Consequently systematic tailoring of the photochromic switching rates was achieved by changes in the characteristics of the attached polymer. To our knowledge this is the first technique to control local environment of a photochromic compound and thus the first example of systematic tuning of photochromic switching rates. Throughout this research, several characteristics of the attached polymer were modified to give a series of rules for the tuning of photochromic switching rates using this technique. The largest variation in switching speed is achieved through variation of Tg. A range of photochromic rates from extremely slow to near solution-like can be easily achieved. The necessary variations in Tg can be achieved easily using living radical polymerisation techniques. The use of different homopolymers, block and random copolymers were all demonstrated successfully in this work. For finer tuning of the photochromic rates, changes in chain length can be used. It was also found the best living radical polymerisation method for this work was ATRP due to the bulky or incompatible halogen which contributed to efficient encapsulation. However this endgroup effect is only important in systems which do not have a low Tg component. The incorporation of such a component overrides all other contributions to the overall behaviour.

Thesis (Ph.D.)--Ohio University, November, 2007. / Title from PDF t.p. Includes bibliographical references.

De nos jours, des fibres et films photochromiques sont tournés vers le développement des matériaux intelligent qui sont appliqués pour évaluer, signaliser et réagir à un changement de couleur et de spectre d’absorbance. Dans ce travail, l’activité photochromique de six différents types commerciaux de polyuréthane contenant de petites quantités de spiropyrane [1-hexyle-3,3-diméthyle-6'-nitrospiro (indoline-2',2'-benzopyrane)] a été étudiée. Les effets d'épaisseur du film, du temps d'irradiation, et de la concentration en SP sur la réponse photochromique des films de PU/SP ont été étudiés et également leurs interactions. En outre, le comportement photochromique de ces films sous étirement et leurs cinétiques de décoloration ont été abordés. La cinétique et la caractérisation des systèmes photochromiques de spiropyrane incorporé dans le polyuréthane et irradié avec la lumière monochromatique ont été modélisées. Les modèles obtenus peuvent être correctement appliqués dans tous les cas (avec et sans irradiation, avec et sans étirement), en particulier pour tous les rapports massique de SP et pour toute l’épaisseur de film. Le comportement mécanique des polyuréthanes et sa relation avec leurs propriétés photochromiques ont été étudiés et modélisées. Ce modèle est capable de déterminer le taux d’étirement qui peut être traduit en compression locale à partir de quatre mesures photochromiques, et ceci ouvre la porte à des applications potentielles. Un intérêt particulier dans ce contexte, peut être porté aux textiles utilisés pour des applications biomédicales, y compris les bas de contention destinés à empêcher ou traiter la thrombose profonde des veines. Une autre application possible est le développement récent de l'habillement sportif pour améliorer la récupération après des efforts violents / Nowadays, photochromic fibers and films are turned towards the development of intelligent “smart” materials which are applied to evaluate, signalize and react to a change in color and absorbance spectra. In this work, the photochromic activity of six commercial grades of polyurethane that contains small quantities of spiropyran [1-hexyle-3,3-diméthyle-6'-nitrospiro (indoline-2',2'-benzopyran)] has been studied. The effects of film thickness, irradiation time, and SP concentration on the photochromic response of PU/SP films have been studied and also their couplings. Furthermore, the photochromic behaviors of these films under stretching and their decoloration kinetics have been investigated. The kinetics and characterization of the photochromic system of spiropyran incorporated into polyurethane and irradiated with monochromatic light was modeled. The obtained models can be correctly applied in all cases (with and without irradiation, with and without stretching), in particular for all SP mass ratios and for all film thickness. The mechanical behavior of polyurethanes and its relation with the photochromic properties is studied and modeled. This model has the capability to determine the stretching ratio which can be translate to the local compression by employing only four photochromic measurements and this open the way for a wide range of potential applications. Of particular interest in this context are the textiles used for biomedical applications, including graduated compression stockings for preventing or treating deep vein thrombosis. Another related application is the recent development of special sport clothing for improving recovery after strong efforts