The mid-infrared is a promising region for detection different materials. Many vibrational modes, including bending and stretching, are located in this regime. Photothermal spectroscopy and imaging in the mid-infrared region is an emerging new method for non-contact detection of molecular groups. Our approach to photothermal spectroscopy and imaging utilizes a near-infrared erbium doped fiber laser (EDFL) to detect the photothermal induced changes in the refractive index. These changes are excited by a mid-infrared quantum cascade laser (QCL) pump beam. The probe beam is detected by a commercially available near-infrared photodetector. This method has advantages of high sensitivity, label-free detection, high spatial resolution and high signal-to-noise ratio (SNR). Hydrogels such as pHEMA are polymers that are of interest for contact lens, drug delivery and soft tissue replacement. The pHEMA hydrogel can retain water content, causing the material to swell. Additionally, pHEMA has a critical temperature at which the hydrogel undergoes a glass transition. Photothermal spectroscopy of pHEMA is demonstrated in this thesis where the presence of this glass transition temperature can be revealed. Additionally, photothermal imaging of a PMMA USAF target sample is shown and ideal parameters for high-resolution photothermal imaging are determined. In this thesis, we report a spatial resolution much smaller than the diffraction limited spot size of the mid-infrared beam. / 2018-07-09T00:00:00Z

This thesis explores a new technique for investigating the photochemical mechanisms of femtosecond laser inscription of permanent photonic structures in Poly(methylmethacrylate) (PMMA). The refractive index (RI) structures were fabricated with a direct writing method without ablation, and analysed using a non-invasive method - namely: Raman mapping spectrometry. The writing conditions for the photonic structures under investigation are mainly represented by 800nm and 400nm wavelength with 44fs and 100fs pulse length and a low repetition rate in the kHz domain. The mass percentage of the induced monomer and end groups modification (MMA) as a measure of the modification of the ratio of C=C and C=O Raman transition varies linearly with the total fluence (total). The mass percentage of the induced monomer and end groups change is defined by the modification of normalised ratio of the Raman intensity of C=C bond (I(C=C)) and the Raman intensity of C=O bond (I(C=O)) which is denoted by I(C=C/C=O)n. The modification of this ratio is denoted by I (C=C/C=O)n and also by MMA. MMA varies linearly with total with a positive slope for both writing conditions due to the induced main chain scission and unzipping. If total increases by 1J/cm2, it is predicted an increase in MMA, by (1.550±0.11)x10-2 (cntsxcm2)/J, for the near infrared (NIR) irradiated samples that is higher than the increase of MMA for the ultraviolet (UV) irradiated sample that show a value of (1.9200.274)x10-3 ( (cntsxcm2)/J). The same trend was found for the variation of MMA with diffraction efficiency () for NIR irradiated structures and also for UV irradiated structures. If  increases by 1cnt, it is predicted that there will be an increase in MMA, by (4.233±0.383) cnts for NIR irradiated samples that is lower than the increase of MMA for the UV irradiated sample that shows a value of (14.3922.477) cnts. The variation of MMA with  is higher for UV irradiated samples than for NIR irradiated samples, and this indicates that the nonlinear absorption of two photons produces a larger percentage of the monomer and end groups than the nonlinear absorption of three photons. Gel Permeation Chromatography (GPC), which is a destructive analytical method, was applied only for the investigation of the time dependent behaviour of the molecular weight of the photonics structures which were written with the parallel writing technique using 775nm wavelength and 160fs pulse length that shows an increase of 66 in  after seven days from the laser irradiation. Twenty-four hours after laser irradiation, the GPC results show that the weighted average molecular weight (Mw) of the exposed sample of 28,610,000 Daltons is about thirty times higher than the MW of the unexposed sample of 963,425 Daltons. This is an indication of the photo-cross-linking reaction. As a result of this reaction, the polymer chains link together through intermolecular forces to form a 3D network which produces an increase of molecular weight. It was also observed that there was a further decrease of molecular weight after three days to 437,441 Daltons due to main chain scission and unzipping. The main chain scission is actually the breaking of C-C bonds between structural units and the formation of radicals which further produce the monomer and end groups (MMA) through the unzipping reaction which leads to a decrease of the molecular weight. The main chain scission occurred with the greatest efficiency after three days following the end of irradiation, when the number of the main chain scissions (Ns) reached the maximum value of 1.193. An increase of molecular weight signifies an increase of the refractive index since the optical density has increased. The mechanical properties of PMMA optical fibres (e.g., Young's modulus) and of bulk PMMA (e.g., glass transition temperature) were investigated using Dynamical Mechanical Analysis (DMA) tests (e.g., stress-strain test and temperature ramp/frequency sweep test). These measurements were performed to study the effect of the manufacturing process that involves stretching and heating or cooling on the mechanical properties of PMMA optical fibres and unmodified PMMA material. T he ultimate aim of this section was to see the effect of the laser irradiation on the strain properties of an optical fibre sensor with gratings. The stress strain results show an increase of Young's modulus of the PMMA optical fibre of 5%, and this is an indication of decreased elasticity which is induced during the fabrication process. For a femtosecond laser irradiated region with UV wavelength, it is expected that there will be an increase of Young's modulus to 65%. This variation was obtained inthe research group from The Photon Science Institute by measuring Young's modulus for a diffraction grating which was written in PMMA with 180fs pulse length and 387nm wavelength and which was subjected to a strain. The elasticity was measured using the displacement of the first order diffracted beams as a result of a modification due to the applied strain [ ]. The temperature ramp/frequency sweep test shows an increase of glass transition temperature of the bulk PMMA of 54.12% which is also an indication of decreased elasticity induced during the fabrication process. A further increase in this temperature is expected for UV irradiated samples.

Les diodes électroluminescentes hybrides organiques-inorganiques ou Quantum Dot- Light-Emitting Diodes (QD-LED) sont le parangon de dispositifs qui associeraient les propriétés semi-conductrices des matériaux organiques conjugués, ainsi que leur facilité de mise en oeuvre en couche mince, aux propriétés exceptionnelles (couleur accordable par la taille, bon rendement quantique de photoluminescence) des nanoparticules nanométriques de semi-conducteurs inorganiques, telles que CdSe/ZnS (TOPO). Diverses approches ont été explorées pour optimiser les QD-LEDs ; elles reposent sur la réalisation d'architectures diverses (uni, bi, tri couches) combinant matériaux organiques et QDs (en couche compacte ou dispersés dans une matrice), obtenues par diverses méthodes de dépôt (spin coating, tampon, impression jet d'encre). Dans ce travail de thèse, nous avons d'abord réalisé une structure originale sous forme de diodes comportant une couche hybride nanocomposite, obtenue en incorporant les QDs dans une matrice diélectrique de PMMA. Le but était de contrôler les flux de porteurs pour maximiser leur recombinaison sur les QDs. Les mesures des caractéristiques électriques, d'électro- et photoluminescence sont discutées, conjointement à des études de la morphologie des dépôts par AFM qui ont montré comment la microstructure dépendait des caractéristiques du, ou des, solvant(s) utilisé(s) pour le spin coating. D'une façon générale, les nanoparticules sont agrégées et la couche apparait inhomogène et rugueuse, ce qui permet des contacts entre les couches de transport. La faible électroluminescence résulterait de transferts d'excitation à partir d'états excités produits par les recombinaisons à ces endroits. Dans une seconde partie, nous avons déposé les QDs par spin coating à partir de solutions dans l'heptane, un solvant qui ne perturbe pas les couches organiques préalablement déposées. Les morphologies observées sont celles d'ilots compacts, avec des taux de couverture allant de 0 à 100%. La diminution, puis la disparition, de l'électroluminescence aux fortes couvertures confirme que l'émission des QDs provient exclusivement de transferts d'excitation à partir d'espèces excitées générées à l'interface organique-organique, en fonction de la nature des matériaux organiques. Les mécanismes d'injection des porteurs à la cathode, dépendant de la nature de celle-ci et de la couche de transport d'électrons, sont variables eux-aussi.

Ce travail s'inscrit dans la problématique de la dégradation des prothèses de hanche cimentées par fretting corrosion. L'endommagement de l'acier inoxydable 316L, alliage constituant la tige fémorale, par frottement contre du polyméthacrylate de méthyle (PMMA), composé modèle du ciment chirurgical, a été particulièrement étudié. Deux types d'expériences ont été envisagées : à sec et en solution de Ringer voisine, par sa teneur en chlorures, de la composition du liquide physiologique. Dans un premier temps, à partir des conditions expérimentales choisies de déplacement et de force normale, la carte de fretting a été tracée pour le contact 316L/PMMA permettant de fixer des conditions reproductibles de glissement total pour un déplacement sinusoïdal de demi-amplitude égale à 40 μm et des forces normales comprises entre 42,5 N et 170 N. Ensuite, l'étude, à sec, du fretting entre l'acier inoxydable et du PMMA a permis de quantifier le volume d'usure du PMMA, seul matériau à se dégrader, en fonction de l'énergie dissipée. Le phénomène de stick-slip a été nettement mis en évidence lors du glissement et augmente en fonction de la force normale de contact. Grâce à la transparence du PMMA, la production et l'évolution des débris ont pu être isolées et commentées en cours de fretting. De plus, les analyses infrarouges des débris de PMMA, à la surface de l'acier inoxydable, ont amené des informations sur le changement de configuration au cours du processus de dégradation. En solution de Ringer, milieu corrosif, l'acier inoxydable se dégrade d'une manière très significative pendant le fretting contre du PMMA et du ciment chirurgical. Au cours du processus de dissolution à potentiel libre, la réaction de réduction des ions oxoniums semble s'ajouter à la réduction du dioxygène. L'acier inoxydable 316L présente une forme particulière d'usure en ‘W'. Un effet de crevasse permet de proposer un mécanisme d'endommagement assisté par le fretting. De plus, l'énergie dissipée varie en fonction du potentiel imposé. Une analyse des courants a montré l'existence d'une réaction cathodique supplémentaire. Enfin, les expériences effectuées à l'air ambiant et en solution de Ringer ont fourni des données quantitatives d'usure du PMMA et du 316L.

Ce travail concerne l'étude du comportement rhéologique de nanocomposites modèles à base de Laponite dans du polyoxyde d'éthylène ou des mélanges polyoxyde d'éthylène avec du polyméthacrylate de méthyle. L'influence des paramètres moléculaires, masse molaire de la matrice et mode de protection des particules sur les propriétés rhéologiques a été étudiée. La meilleure dispersion est obtenue à partir d'une solution, la dilution d'un mélange maître conduisant à des matériaux hétérogènes. Les mélanges POE/PMMA sont compatibles à l'état fondu dans toute la gamme de concentrations mais hétérogènes à température ambiante au-dessus de 30% en poids de particules. En diluant un mélange Laponite/PEO dans le PMMA, nous avons montré que ces domaines se concentrent en particules en dessous de 30% de PEO et qu'une cocontinuité de phases PEO contenant les particules et PMMA essentiellement pur est formée au-dessus de 30% de PEO. La présence des particules diminue fortement la cristallinité.

THE CHARACTERIZATION OF SOME METHACRYLATE AND ACRYLATE HOMOPOLYMERS, COPOLYMERS AND FIBERS VIA DIRECT PYROLYSIS MASS SPECTROSCOPY &Ouml / zlem G&uuml / ndogdu, Suriye Ph.D., Department of Polymer Science and Technology Supervisor: Prof. Dr. Jale Hacaloglu December 2012, 177 pages Poly(methyl methacrylate) possesses many desirable properties and is used in various areas. However, the relatively low glass transition temperature limits its applications in textile and optical-electronic industries. Monomers containing isobornyl, benzyl and butyl groups as the side chain are chosen to copolymerize with MMA to increase Tg and to obtain fibers with PMMA. In this work, thermal degradation characteristics, degradation products and mechanisms of methacrylate homopolymers, poly(methyl methacrylate), poly(butyl methacrylate), poly(isobornyl methacrylate) and poly(benzyl methacrylate), acrylate homopolymers, poly(n-butyl acrylate), poly(t-butyl acrylate), poly(isobornyl acrylate), two, three and four component copolymers of MMA and fibers are analyzed via direct pyrolysis mass spectrometry. The effects of substituents on the main and side chains, the components present in the copolymers and fiber formation on thermal stability, degradation characteristics and degradation mechanisms are investigated. According to the results obtained, the depolymerization mechanism yielding mainly the monomer is the main thermal decomposition route for the methacrylate polymers, acrylate polymers degradation occurs by H-transfer reactions from the main chain to the carbonyl groups. However, when the alkoxy group involves

Biomaterials used for stabilization of compressed vertebraes due to osteoporosis, have mainly been based on resin materials, like PMMA (polymethyl methacrylate), but have recently expanded to consist of injectable ceramics, such as calcium-aluminate. In this in vitro study human osteoblast-like cells, MG-63, were cultured on three different injectable biomaterials based on: Ca-aluminate, Bis-GMA (bisphenol A-glycidylmethacrylate) and PMMA, to investigate the cellular response elicited by these materials. Cell proliferation was measured by the NucleoCounter® system, cell viability was investigated by LDH (lactate dehydrogenase) analysis, cell differentiation and mineralization was evaluated by mRNA gene expression of the osteoblastic markers: ALP (alkaline phosphatase), OC (osteocalcin) and COLL-I (collagen type I) by qPCR (quantitative polymerase chain reaction) analysis. Two control materials were used: TCP (tissue culture polystyrene, negative control) and PVC (polyvinyl chloride, positive control). The results showed that all the bone cement materials were non-toxic and biocompatible, i.e. they provided good cell viability and proliferation of the MG-63 cells. They are specific for bone cells, since they expressed high values of the osteoblast-specific differentiation markers, and are thus promising as injectable bone cement materials. Among the bone cements, Xeraspine appears to be the most biocompatible material for bone cells. It is followed by Cortoss and then Vertebroplastic.

Metal coordinated polymer nanocomposites have gained great attention due to their superior characteristics. Polymethylmethacyrlate (PMMA) is the most commonly used polymer since it is easily processed. In this study, modified TiO2 nanoparticles prepared by insitu and exsitu methods were embedded into PMMA in order to improve its thermal stability and the effects of TiO2 nanoparticles on thermal characteristics of PMMA were investigated by direct pyrolysis mass spectrometry. The insitu method which is a sol gel method, TiO2/SiO2 nanoparticles were synthesized by mixing titanium(IV) tetraisopropoxide, TTIP, with silane coupling agent, 3-(3-methoxysilyl)methylmetacrylate, MSMA in absolute ethanol. In exsitu method, TiO2 powder was directly mixed with silane coupling reagent. TiO2/SiO2 nanoparticles were embedded into the PMMA by direct mixing resulting in exsitu and insitu TiO2/SiO2/PMMA nanocomposites. The synthesized TiO2/SiO2/PMMA nanocomposites were characterized by TEM, ATR-FT-IR and analyzed for the investigation of their reaction mechanism and thermal characteristics by pyrolysis mass spectroscopy. iv TEM images confirmed the formation of TiO2/SiO2 nanoparticles and TiO2/SiO2/PMMA nanocomposites and indicated that the average particle size of TiO2/SiO2 nanoparticles was around 6 nm whereas average particle size of SiO2/TiO2/PMMA nanocomposites were around 25 nm. The increase in the size of nanoparticles is associated with incorporation of TiO2/SiO2 nanoparticles into PMMA matrix. ATR-FTIR spectrum of 5% TiO2/SiO2/PMMA nanocomposites showed the formation of TiO2/SiO2 nanopartciles clearly. Pyrolysis mass spectrometry analysis revealed that incorporation of TiO2/SiO2 nano- particles into PMMA resulted in higher thermal stability only for low weight percentage insitu TiO2/SiO2/PMMA. At high weight percentages a decrease in thermal stability was detected. On the other hand, in case of exsitu TiO2/SiO2/PMMA, contrary to our expectations a decrease in thermal stability was detected. The decrease in thermal stability was attributed to evolution of methacrylic acid during thermal degradation of silane groups.

Four denture base materials of poly(methyl methacrylate) (QC-20, Pladent-20, Hygenic, and Optilon-399) were prepared by convention water bath and microwave-energy cured methods. While the resin was in the dough stage, it was packed into two molds (65 mm ¡¦15 mm ¡¦10 mm) in the fiber reinforced plastic flask. The variation of temperature with time was recorded by two thermocouples during the microwave heating at 80, 160, and 240 watts, respectively. Microwave polymerization was carried out in the same equipment. The microwave flask containing the same size of resin blocks were processed at 80, 160, 240, and 560 watts for 15, 10, 7, and 2 min, separately. Then each flask was turned over, and cured an additional 2 min at 560 watts. In the case of water-bath method, the resin in the dough stage was packed in the Brass flask, and then cured at 70¢J for 9 hours. Ten specimens were prepared for each condition studied. The surface hardness, porosity, flexural properties and solubility of both process conditions were evaluated. The samples were sectioned by microtome and stained 2 % Osmiun tetroxide, then the morphology of Optilon-399 was observed by using TEM (Transmission electron microscopy) at 160 KV. The result indicate that the flexural strength for Optilon-399 specimens prepared by water-bath method was 20 MPa higher than that prepared in microwave oven, however, there were no obvious difference between the samples cured at different power. Phase separation in two different sizes was observed in all of the Optilon-399 specimens. The larger domain was with 0.18 mm~0.67 mm diameter has dispersed rubber phase surrounded by a rubber periphery. The smaller domain with 0.1 mm diameter is rich with rubber phase. The size and distribution of the larger domain were correlated with the microwave power and curing time. The sample cured by water-bath has the largest average domain diameter (0.395¡Ó0.068 mm). In the specimens prepared by microwave method, the domain size decreased with increasing power. In additions, the domain size varied across the specimen. The size difference between the largest and the smallest domain for specimens cured at 80W was 0.03 mm, and that for specimens cured at 560W was 0.05 mm. This indicated that the larger the power watt was, the higher the morphology difference was.

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