<p>In this work, a gradient of interpenetrating polymer networks, consisting of anionic</p><p>and cationic polymers, has been investigated with respect to protein resistant</p><p>properties and swelling characteristics at different pH and ionic strength</p><p>conditions.</p><p> </p><p>The swelling and protein adsorption have been studied using <em>in situ </em>spectroscopic</p><p>ellipsometry(SE) and imaging surface plasmon resonance(iSPR) respectively.</p><p>It has been shown that, by altering the buffer pH, the region of lowest</p><p>protein adsorption on the surface could be moved laterally. The swelling has</p><p>similarly been shown to respond to both changes in pH and ionic strength. Additionally,</p><p>the arise of surface charge and the polymer swelling in solution, both a</p><p>consequence of the ionisation of fixed charges on the polymer, have been indicated</p><p>to occur at different buffer pH.</p><p> </p><p>The studied polymer systems show promising properties for future applications</p><p>in, for example, the biosensor area, where the surface chemistry can be</p><p>tailor-made to work optimally in a given environment.</p>

abstract: Droplet-structure interactions play a pivotal role in many engineering applications as droplet-based solutions are evolving. This work explores the physical understanding of these interactions through systematic research leading to improvements in thermal management via dropwise condensation (DWC), and breathable protective wearables against chemical aerosols for better thermoregulation. In DWC, the heat transfer rate can be further increased by increasing the nucleation and by optimally ‘refreshing’ the surface via droplet shedding. Softening of surfaces favor the former while having an adverse effect on the latter. This optimization problem is addressed by investigating how mechanical properties of a substrate impact relevant droplet-surface interactions and DWC heat transfer rate. The results obtained by combining droplet induced surface deformation with finite element model show that softening of the substrates below a shear modulus of 500 kPa results in a significant reduction in the condensation heat transfer rate. On the other hand, interactions between droplet and polymer leading to polymer swelling can be used to develop breathable wearables for use in chemically harsh environments. Chemical aerosols are hazardous and conventional protective measures include impermeable barriers which limit the thermoregulation. To solve this, a solution is proposed consisting of a superabsorbent polymer developed to selectively absorb these chemicals and closing the pores in the fabric. Starting from understanding and modeling the droplet induced swelling in elastomers, the extent and topological characteristic of swelling is shown to depend on the relative comparison of the polymer and aerosol geometries. Then, this modeling is extended to a customized polymer, through a simplified characterization paradigm. In that, a new method is proposed to measure the swelling parameters of the polymer-solvent pair and develop a validated model for swelling. Through this study, it is shown that for this polymer, the concentration-dependent diffusion coefficient can be measured through gravimetry and Poroelastic Relaxation Indentation, simplifying the characterization effort. Finally, this model is used to design composite fabric. Specifically, using model results, the SAP geometry, base fabric design, method of composition is optimized, and the effectiveness of the composite fabric highlighted in moderate-to-high concentrations over short durations. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2019

In this work, a gradient of interpenetrating polymer networks, consisting of anionic and cationic polymers, has been investigated with respect to protein resistant properties and swelling characteristics at different pH and ionic strength conditions. The swelling and protein adsorption have been studied using \emph{in situ} spectroscopic ellipsometry(SE) and imaging surface plasmon resonance(iSPR) respectively. It has been shown that, by altering the buffer pH, the region of lowest protein adsorption on the surface could be moved laterally. The swelling has similarly been shown to respond to both changes in pH and ionic strength. Additionally, the arise of surface charge and the polymer swelling in solution, both a consequence of the ionisation of fixed charges on the polymer, have been indicated to occur at different buffer pH. The studied polymer systems show promising properties for future applications in, for example, the biosensor area, where the surface chemistry can be tailor-made to work optimally in a given environment.

No description available.

In the current study, SAPs of cationic monomer [2 - (Methacryloyloxy) ethyl] trimethylammonium chloride have been prepared by free radical solution polymerisation with different crosslinkers. They were subjected to repeated cycles of swelling and de-swelling in DI water and NaCl solution. The conductivity of the swelling medium was measured and related to the swelling/de-swelling characteristics of the SAPs. The swelling capacity was also determined in saline solution. The swelling and de-swelling processes were described by first-order kinetics. The SAPs exhibited varied swelling capacity for crosslinkers of the same functionality as well as different functionality. The SAPs were used to adsorb, the dye Orange G at different initial concentrations of the dye. The equilibrium adsorption data followed the Langmuir adsorption isotherms. The SAPs were also used to adsorb three other dyes, Congo red, Amido black and Alizarin cyanine green. They exhibited different adsorption capacity for different dyes. The adsorption phenomenon was found to follow first order kinetics. In the later part of the study, the co-monomers of [2 - (Methacryloyloxy) ethyl] trimethylammonium chloride with zwitter-ionic monomers [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide and [3-(Methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide inner salt were prepared in turns at two different concentrations. The effect of the addition of the zwitter-ionic monomers and their concentration of the swelling capacity and dye adsorption capacity was studied. There was no effect on the swelling capacity of the polymers due to either the species of the zwitter-ionic monomer or their concentration. However, there was a reduction in soluble content of the polymers. The dye adsorption capacity decreased at the higher concentration of the zwitter-ionic monomer.

No description available.

Le procédé d’imprégnation par voie CO2 supercritique est une solution prometteuse pour préparer des implants polymère à libération contrôlée de médicaments.Ce travail a permis de comprendre l’influence des paramètres gouvernant ce procédé et de préciser dans quelle mesure ce procédé peut être utilisé pour préparer des implants polymères chargés en médicament. Pour ce faire, nous avons combiné les informations obtenues grâce aux techniques classiques de caractérisation de polymères et à un dispositif que nous avons développé basé sur la micro-spectroscopie FTIR haute pression in situ.Dans cette étude, des fils de suture de PLLA, PP and PET ont été imprégné avec deux anti-inflammatoires (aspirine et kétoprofène).Tout d’abord, l’évolution du comportement des systèmes binaires médicament/CO2 (solubilité et spéciation) et polymère/CO2 (quantité de CO2 adsorbé, gonflement de la matrice, évolution de la microstructure et des propriétés de tension du polymère) a été déterminé en fonction de la pression et de la température. Ensuite, le procédé d’imprégnation a été étudié. L’influence des conditions expérimentales sur le taux d’imprégnation a été déterminée et expliquée par la quantité de CO2 adsorbé, le gonflement de la matrice, la solubilité du médicament, l’évolution de la microstructure du polymère et aussi l’affinité médicament/polymère. La matrice de PLLA a pu être plus largement imprégnée (jusqu’à 32%) que celles de PP et PET (5% max). Enfin, l’influence des conditions d’imprégnation et de dépressurisation sur le relargage a été démontrée sur le système PLLA/Kétoprofène, la durée de relargage variant de 3jours à 3mois. / The scCO2 impregnation process is a promising alternative to other manufacturing process to prepare drug-eluting polymer implants.This work enabled to rationalize the influence of the key parameters governing this process and to determine in which extent this process can be used to prepare drug-eluting implants. We have combined the information obtained with traditional polymer characterization techniques and a newly characterization set-up we have developed that is based on in situ FTIR micro-spectroscopy. We have worked on the impregnation of sutures made of PLLA, PP and PET with two anti-inflammatory drugs namely ketoprofen and aspirin.Firstly, the thermodynamic behaviors of the systems drug/CO2 (solubility and speciation of the drug) and polymer/CO2 (CO2 sorption, polymer swelling, evolution of the polymer microstructure and of the tensile properties) were studied as a function of pressure and temperature. Then, the scCO2 impregnation process was investigated. The impact of the operational conditions on the drug loading (contact time, pressure, temperature and depressurization conditions) was explored and accounted regarding to the CO2 sorption, the2swelling, the drug solubility as well as the changes in the polymer microstructure with the experimental conditions and the presence of the drug. The drug/polymer affinity was also explored. The tensile properties of the impregnated fibers were also evaluated. PLLA was more impregnated (up to 32%) than PP and PET (up to 5%) in the investigated conditions. Finally, we have shown that the drug release can be tuned from 3 days to 3 months by varying the impregnation and depressurization conditions on the system PLLA/Ketoprofen.

<p></p><p>This doctoral dissertation takes the reader through a journey where applied shear rheology and flow-velocimetry are used to understand the mesoscopic factors that control the flow behavior of three microstructured fluids. Three individual protocols that measure relative physical and mechanical properties of the flow are developed. Each protocol aims to advance the particular transformation of novel soft materials into a commercial product converging in the demonstration of the real the chemical, physical and thermodynamical factors that could potentially drive their successful transformation. </p> <p> </p> <p>First, this dissertation introduces the use of rotational and oscillatory shear rheometry to quantify the solvent evaporation effect on the flow behavior of polymer solutions used to fabricate isoporous asymmetric membranes. Three different A-B-C triblock copolymer were evaluated: polyisoprene-<i>b</i>-polystyrene-<i>b</i>-poly(4-vinylpyridine) (ISV); polyisoprene-<i>b</i>-polystyrene-<i>b</i>-poly(<i>N</i>,<i>N</i>-dimethylacrylamide) (ISD); and polyisoprene-<i>b</i>-polystyrene-<i>b</i>-poly(<i>tert</i>-butyl methacrylate) (ISB). The resulting evaporation-induced microstructure showed a solution viscosity and film viscoelasticity strongly dependent on the chemical structure of the triblock copolymer molecules. </p> <p> </p> <p>Furthermore, basic shear rheometry, flow birefringence, and advanced flow-velocimetry are used to deconvolute the flow-microstructure relationships of concentrated surfactant solutions. Sodium laureth sulfate in water (SLE₁S) was used to replicate spherical, worm-like, and hexagonally packed micelles and lamellar structures. Interesting findings demonstrated that regular features of flow curves, such as power-law shear thinning behavior, resulted from a wide variety of experimental artifacts that appeared when measuring microstructured fluids with shear rheometry.</p> <p> </p> <p>Finally, the successful integration of shear rheometry to calculate essential parameters to be used in a cost-effective visualization technique (still in development) used to calculate the dissolution time of polymers is addressed. The use of oscillatory rheometry successfully quantify the viscoelastic response of polyvinyl alcohol (PVA) solutions and identify formulations changes such as additive addition. The flow behavior of PVA solutions was correlated to dissolution behavior proving that the developed protocol has a high potential as a first screening tool.</p><br><p></p>