Hydrogels are polymeric materials with chemically, physically or topologically crosslinked networks which have a capacity to absorb and retain water. They have been frequently used for many medical applications because of their useful physical properties such as oxygen permeability and excellent compatibility with living tissue and blood. The long term goal of this research is to develop a hydrogel system for potential use in reconstructive and plastic surgeries such as the closure of cleft palate defects and syndactyly (congenitally fused fingers or toes) repair. The medical requirements for such systems are not only a high degree of swelling, but also slow swelling rate, preferred direction of swelling (anisotropic swelling), appropriate mechanical strength, in addition to being biocompatible. A large degree of swelling would limit the number of surgical procedures required thereby reducing the cost and risk of surgery. A slow swelling rate can avoid tissue necrosis and help tissue growth during the tissue expansion process. Anisotropic swelling is required for specific surgical applications such as cleft palate repairs. Known to be biocompatible hydrogel systems, of a neutral gel system consisting of N-vinyl-2-pyrrolidinone (VP) and 2-hydroxyethyl methacrylate (HEMA) copolymers and an ionizable gel system of VP and acrylic acid (AA) copolymers were prepared using thermal and controlled UV-initiated polymerization. Using these VP/HEMA and VP/AA gel systems, various approaches to control their degree and rate of swelling were studied as a function of key controllable parameters. Their mechanical properties and structural characteristics determining their swelling behavior and mechanical properties also were investigated. Through these studies, how to control the key parameters that affect such swelling behavior was understood in addition to optimizing the gel systems for large degree of swelling, slow swelling rate, and mechanical integrity. Investigations into a number of methods to control the swelling rate were also undertaken for different VP/HEMA based gel systems. Multilayers of alternating gels and elastomer films (polybutadiene (PB) or polydimethylsiloxane (PDMS)) as well as gels encapsulated with the elastomer films were prepared. In addition, gels were prepared with inclusion of either silver nanoparticles or methacrylates with increasing the length of hydrophobic groups for the studies of swelling rate. In this work, two novel methods to control swelling direction (anisotropic swelling) of hydrogels were investigated. One method induces anisotropic swelling through structural gradients within the VP/HEMA gels synthesized by UV polymerization using gradient photomasks. A more promising method used stress induced anisotropic swelling for compressed VP/AA gels. The morphology-gradient VP/HEMA hydrogel system did not show large scale anisotropic swelling. However, the compressed VP/AA gels produced significant anisotropic swelling due to the controlled anisotropy of network morphology. A systematic study as a function of compression temperature, stain and strain rate was performed to derive an understanding of the anisotropic swelling behavior. These compressed gel systems produced not only a large degree of swelling and slow swelling rates but also high anisotropic swelling and proper mechanical stiffness of hydrogels. These materials are believed to be ideal candidates for tissue or skin expansion.

Hyaluronic acid (HA) is one of the primary chemical building blocks of the extracellular matrix and thus is an attractive material for biomedical applications. FDA approved HA-based materials are available as dermal fillers, joint viscosupplements, vitreous substitutes, and abdominal adhesion barriers. The engineering of new HA-based materials and applications is an active area of research. Here we develop several new types of HA-based hydrogels with unique and useful properties. To address the challenge of delivering hydrophobic drugs from hydrophilic hydrogel matrices we have grafted HA hydrogels with [Beta]-cyclodextrin to create hydrogels capable of binding poorly water soluble drugs. To create HA hydrogels with unique anisotropic swelling behavior we have developed a dual-crosslinking technique in which a super-swelling chemically crosslinked hydrogel is patterned with low-swelling photocrosslinked domains. When this dual-crosslinked hydrogel is swelled it contorts into a new shape because of differential swelling among photopatterned regions. To address the challenge of creating hydrogel scaffolds with biomimetic branched porosity we have invented a "crystal templating" technique. This technique grows dendritic crystals throughout a biopolymer solution, crosslinks the biopolymer around the crystals, and washes the crystals away to yield a hydrogel with a dendritic macroporous network. Lastly, we invented a method for patterning a substrate with a microarray of hydrogel compartments. A microarray of living cells is obtained when cells are seeded on the hydrogel patterned substrate. This method addresses the need for an inexpensive, simple method for obtaining living cell microarrays that does not require clean room labs and lithographic expertise. Each of these new materials were based on hyaluronic acid hydrogels but the methods are generalizable to hydrogels of other polymers too. In conclusion, the novel methods in this dissertation are a significant contribution to the engineering of HA-based materials. / text

De nombreux exemples de matériaux composites obtenus par l’association de fibres végétales et de polymères ont permis des allègements conséquents de structures dans divers domaines d’application. Cependant, la question demeure quant de la durabilité de ces pièces en service, essentiellement par manque de connaissances sur le vieillissement des fibres végétales, sur leurs interactions avec la matrice polymère et sur le comportement hydrothermique des composites biosourcés au cours du temps. Dans cette étude, nous avons étudié les cinétiques et mécanismes de sorption du matériau composite afin d’appréhender son comportement hydrique lors des vieillissements hydrothermiques par immersion dans l’eau à 23°C et 70°C. Cette étude a mis en évidence l’influence des fibres végétales sur les grandeurs caractéristiques de l’absorption en eau du matériau composite : forte prise en eau, gonflement anisotrope. Elle a également permis l’identification des mécanismes de dégradation des fibres de lin ; le rôle très nocif des résidus d’écorce rappelle l’importance du rouissage et du défibrage sur les performances de ces fibres. L’étude du comportement des constituants et du composite confrontés à des vieillissements hydrothermiques a ensuite été entreprise afin d’identifier et quantifier l’influence de chacun des matériaux constitutifs, ainsi que leur synergie. Il en ressort que la détérioration des fibres de lin est la principale cause de l’abattement des propriétés mécaniques du matériau composite. Si une immersion à 23°C pendant 70 jours n’a que peu d’effet sur les propriétés mécaniques, l’élévation de la température à 70°C induit des endommagements importants dès 14 jours d’immersion. La destruction des parois cellulaires et la dégradation des interfaces fibre/matrice sous l’effet de la présence d’eau détériorent le transfert de charge matrice/fibre. La corrélation entre les vieillissements accélérés et naturel a fait ressortir une similitude entre le maintien pendant 70 jours dans l’eau à 23°C et l’exposition aux conditions naturelles pendant 24 mois ; l’immersion à 70°C s’avère trop sévère. Une solution d’amélioration serait d’accentuer le rouissage des fibres afin de supprimer davantage les composés pectiques de la lamelle mitoyenne et de la paroi primaire. L’élimination de ces composés facilement hydrolysables par l’eau permettrait de prétendre à une meilleure qualité de l’interface fibres/matrice tout au long du vieillissement. / A great number of plant fiber – reinforced polymer composites allowed substantial lightening of structures in various fields of application. However, the question remains about the durability of these parts in service, mainly for lack of knowledge about the aging of plant fibers, their interactions with the polymer matrix and the hydrothermal behavior of biosourced composites over time. In this work, water absorption mechanisms and kinetics by the composite material are studied in order to understand the hydric behavior during hydrothermal aging by immersion in deionized water at 23°C or 70°C. The results show that water absorption by the composite is characterized by a high water uptake and an anisotropic swelling. It also allowed the identification of the degradation mechanisms of flax fibers; the very harmful role of bark residues recalls the importance of retting and decortication on the performance of these fibers.The investigation of the behaviors of the constituents and the composite under hydrothermal aging was then undertaken with the aim to identify and quantify the influence of each on the constituent materials, as well as their synergy. It shows that the deterioration of the flax fibers is the main cause of the reduction of the mechanical properties of the composite. If immersion at 23 ° C for 70 days has little effect on the mechanical properties, raising the temperature to 70 ° C induces significant damage from 14 days of immersion. The destruction of the cell walls and the degradation of the fiber/matrix interfaces due to water deteriorate the load transfer efficiency by the fiber/matrix interface. The correlation between accelerated and natural aging showed a similarity between holding for 70 days in water at 23 ° C and exposure to natural conditions for 24 months; immersion at 70 ° C is too severe. An improvement solution would be to increase the retting of the fibers in order to further remove the pectic compounds from the middle lamella and the primary wall. The elimination of these compounds easily hydrolysable by water would claim to a better quality of the fiber / matrix interface throughout aging.