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This dissertation details the development and applications of two innovative types of optical filament-based impulsive Raman spectroscopy: filament-assisted Raman spectroscopy (FAIRS) and spectral-to-temporal amplitude mapping polarization spectroscopy (STAMPS). These techniques provide complimentary vibrational and rotational information on molecular systems of interest. Both are powerful due to their impulsive nature which allows for rapid measurement of entire Raman spectra. However, each type of spectroscopy utilizes the filament in a different manner. The recently reported vibrational technique, referred to as filament-assisted impulsive Raman spectroscopy, employs the pulse shortening and continuum generation of filamentation to impulsively excite a massive vibrational coherence in a molecular system for simultaneous measurement of all the Raman-active modes. In the first half of this dissertation, FAIRS is further developed and applied to a plethora of signature molecules. Radioactive decay signature molecules, including nitrogen oxides, ozone, and ions are detected via FAIR spectroscopy. Concurrent generation and detection of ozone, ionic, and excited-state molecules through filamentation is reported for the first time. Production of these species through the strong field chemistry of filamentation and their subsequent filament-driven excitation is a mark of sensitivity of FAIRS. Spatial studies of combustion species in a natural gas flame are also presented. FAIRS monitors the Raman signal intensities of known reactants and products as a function of vertical flame position. The appearance of combustion products as a function of flame height is also tracked. Spectral fringes overlapping the Raman-active modes are present in all measurements and enable more sensitive detection of low signal intensity species. The results described illustrate the potential of FAIRS for threat sensing applications. The rotational technique, referred to as spectral-to-temporal amplitude mapping polarization spectroscopy, temporally chirps the spectral content of the white-light continuum generated during filamentation to map the transient rotational rivals that are impulsively excited by a short pump pulse. In the second half of this dissertation, the initial development and testing, followed by the applications of STAMPS are described. STAMPS proves successful in mapping the rotational wavepacket rephasing of simple linear molecules, including nitrogen, oxygen, and carbon dioxide, as well as the more complicated asymmetric top molecules, ethylene and methanol. The application of STAMPS to the detection of nitrogen oxides and nitrous oxide, which are considered signatures of multiple threat substances and events, is demonstrated. A pressure study of nitrous oxide reveals dephasing effects as a function of time and pressure. These preliminary results also indicate the potential of STAMPS for hazard sensing applications. / Chemistry

Novel, highly functional rod-like copolymers have been synthesized by alternating copolymerization of N, N, Nâ , Nâ -tetraalkyl-4, 4â -diaminostilbenes (TDAS) with maleic anhydride. Dynamic light scattering, 2H solid state NMR and persistence length measurement reveal high chain rigidity of the polymer backbone. Double quantum heteronuclear local field solid state NMR spectroscopy (2Q-HLF Solid State NMR) has been employed to investigate the chain structure of ¹³C labelled copolymer. The torsional angle of the H-13C-13C-H part of the anhydride ring was zero degrees, indicating an all cis configuration of the H-13C-13C-H moiety of the anhydride ring. Rod-coil block copolymers containing rigid polyampholyte blocks were designed and synthesized by addition-fragmentation chain transfer (RAFT) copolymerization. The rigid polyampholytes blocks were formed by hydrolysis of alternating copolymers and the flexible coil block consists of poly(oligo(ethylene glycol) methacrylate). The rod-coil block copolymers form polyion complex (PIC) aggregates even when the polyampholyte blocks are charge imbalanced. The aggregates did not dissociate upon the addition of high concentrations of NaCl unlike the dissociation of flexible polyampholytes in NaCl solution. These unique solution properties are induced by 'like-charge attractions' of the rigid polyampholytic alternating copolymer chains. An example, of what is birefringent to be a novel class of material, has been prepared which enables the control of the birefringence of a polymer film by controlling the rotation of aromatic groups pendant to the polymer backbone. A linear rigid bisphenol monomer, 4,4′-dihydroxyterphenyl (DHTP), has been incorporated into poly(aryl ether sulfone)s (PAES) in a study to impart crystallization to these amorphous polymers. Three bisphenols, 4, 4′-isopropylidenediphenol, 4, 4′-(hexafluoroisopropylidene)diphenol and 4,4′-dihydroxybiphenyl have been copolymerized with DHTP and dichlorodiphenylsulfone. Only the segmented polysulfone containing 50% BP and 50% DHTP was semi-crystalline. This PAES had a melting temperature (Tm) 320°C in the first heating cycle of a DSC measurement and the presence of crystallites was confirmed by wide angle X-ray diffraction (WAXS). / Ph. D.

No / An experimental configuration that combines the powerful capabilities of a short-term shearing apparatus with simultaneous optical and X-ray scattering techniques is demonstrated, connecting the earliest events that occur during shear-induced crystallization of a polymer melt with the subsequent kinetics and morphology development. Oriented precursors are at the heart of the great effects that flow can produce on polymer crystallization (strongly enhanced kinetics and formation of highly oriented crystallites), and their creation is highly dependent on material properties and the level of stress applied. The sensitivity of rheo-optics enables the detection of these dilute shear-induced precursors as they form during flow, before X-ray techniques are able to reveal them. Then, as crystallization occurs from these precursors, X-ray scattering allows detailed quantification of the characteristics and kinetics of growth of the crystallites nucleated by the flow-induced precursors. This simultaneous combination of techniques allows unambiguous correlation between the early events that occur during shear and the evolution of crystallization after flow has stopped, eliminating uncertainties that result from the extreme sensitivity of flow-induced crystallization to small changes in the imposed stress and the material. Experimental data on a bimodal blend of isotactic polypropylenes are presented.

L’optique non linéaire qui convertit la gamme de fréquences des sources lasers vers l’ultraviolet, le visible, l’infrarouge ou le térahertz par exemple, joue un rôle crucial pour la médicine, l’industrie, les applications militaires, la recherche etc. L’accord de phase par biréfringence (BPM) ou le quasi-accord de phase (QPM) à partir de processus non linéaires quadratiques, peuvent être utilisés pour la conversion de fréquence dans le domaine de transparence de cristaux non linéaires. Dans ce travail de thèse, un cristal uniaxe de La3Ga5.5Nb0.5O14 (LGN) a été élaboré en utilisant une méthode de Czochralski, puis il a été étudié pour le BPM. Nous avons aussi validé la théorie du QPM angulaire (AQPM), qui correspond à la généralisation du QPM à n’importe quel angle par rapport au vecteur du réseau. Pour cela, nous avons étudié un cristal biaxe de Rb: KTiOPO4 à domaines ferroélectriques alternés périodiquement (PPRKTP) usiné en forme de sphère. Tous ces résultats constituent une base fiable for les études avenir consacrées à la conception de dispositifs pour la conversion de fréquence. / Nonlinear optics converting the frequency range of laser sources to ultraviolet, visible, infrared or terahertz ranges for example, plays a crucial role in medicine, industry, military applications, research and so on. Birefringence phase-matching (BPM) or quasi-phase-matching (QPM) from quadratic nonlinear processes, can be used for frequency conversion in the transparency range of nonlinear crystals. In this PhD work, a La3Ga5.5Nb0.5O14 (LGN) uniaxial crystal was grown using a Czochralski method and then studied for BPM. We also validated the theory of angular-QPM (AQPM), corresponding to a generalization of QPM achieved at any angle with respect to the grating vector. For that purpose, we studied a periodically-poled large-aperture Rb:KTiOPO4 (PPRKTP) biaxial crystal cut a sphere. All the results provide a reliable basis for further studies devoted to the design of frequency conversion devices.

Ce travail se place dans le cadre de la mesure ultrasensible d’anisotropie de phase optique que permet l’emploi adapté des cavités de très haute finesse. Pour stabiliser la fréquence laser sur une résonance de la cavité, un schéma d’asservissement reposant sur la rétroaction optique est utilisé.Une première partie décrit le couplage optique entre le laser et la cavité à travers l’analyse du comportement de la fréquence d’émission du laser auto-réinjecté. Une comparaison analytique théorie expérience a permis d’identifier les signaux d’erreur nécessaires au maintien durable de la fréquence du laser à l’exacte résonance d’un mode de la cavité. Après une description détaillée du dispositif d’asservissement, sa réalisation expérimentale sur une cavité de finesse de quelques milliers (F = 3 000)a démontré la possibilité de stabiliser la fréquence laser sur plus de dix heures avec une excursion résiduelle à la seconde de 375 Hz.Dans la deuxième partie, le développement précédent a été mis en œuvre sur une cavité de très haute finesse (F = 250 000) et a permis la mesure ultrasensible de biréfringence induite dans des gaz par effet Kerr. L’originalité du dispositif repose sur la mise à profit de la biréfringence résiduelle des miroirs de haute réflectivité.Elle est utilisée d’une part comme source à la rétroaction optique, et d’autre part comme biais optique à la mesure de la biréfringence du gaz. Une étude théorique et expérimentale détaillée des sources de bruit présent dans la chaîne de détection en fonction de la valeur du biais optique a permis de réaliser la mesure de déphasage au niveau du bruit de photons avec quelques mW de puissance laser. Ainsi, une sensibilité référence sur la mesure de déphasage Kerr de 3.10−13 rad a été démontrée pour un temps de mesure de 800 sec. Cette valeur record améliore de trois ordres de grandeur les déphasages Kerr précédemment mesurés. Le dispositif a été de plus mis à profit pour la mesure à faible champ électrique (< 40 V /mm) et à pression atmosphérique, des constantes de Kerr de différents gaz moléculaires et atomiques jusqu’à l’He. / The context of the work is the ultra-sensitive measurement of phase anisotropy permits by well-used of very high finesse cavity. To stabilize the laser frequency at the exact resonance of one cavity mode, a servo control based on optical feedback is used.In the first part, the optical coupling between laser and cavity is described through the comportment of the frequency of the self-locked laser. A comparison between experience and theory has permitted to identify the error signals in order to keep enduringly the laser frequency at the exact resonance. The experimental realization of the servo control into a 3 000 finesse cavity had demonstrated the stabilization of the laser frequency during more than ten hours with a residual one second excursion of 375 Hz.In the second part, the previous development has been used with a very high finesse cavity (F=250 000) to measure static Kerr birefringence in gases. The originality of the set-up is the use of the residual high reflectivity mirrors birefringence, firstly as the source of the optical feedback and secondly as an optical bias to measure the weak gas birefringence. An experimental and theoretical study of the noise according to the value of the optical bias has permitted a photon noise limited measurement (laser intensity of few mW). A record sensitivity of the phase shift induced by Kerr effect has been demonstrated at 3.10-13 rad with 800 s integration time. The scheme has been used to measure, in weak electric field (<40 V/mm) and in standard condition of pressure and temperature, the Kerr constant of molecular and atomic gases, even He gas

Les liquides diffèrent des solides par une réponse retardée à la sollicitation en cisaillement; c’est-à-dire une absence d’élasticité de cisaillement et un comportement d'écoulement à basses fréquences (<1 Hz). Ce postulat pourrait ne pas être vrai à toutes échelles. A l’échelle submillimétrique, les mesures viscoélastiques (VE) réalisées en améliorant l'interaction entre le liquide et le substrat, montrent qu’une élasticité basses-fréquences existe dans des liquides aussi variés que les polymères, les surfondus, les liquides à liaison H, ioniques ou van der Waals. Ce résultat implique que les molécules à l'état liquide ne seraient pas dynamiquement libres, mais élastiquement corrélées.En utilisant les propriétés biréfringentes des fluctuations prétransitionnelles qui coexistent dans la phase isotrope des cristaux liquides, nous montrons qu'il est possible de visualiser ces corrélations « cachées ». Dans des conditionssimilaires aux mesures VE, une biréfringence optique synchrone à la déformation est observée dans la phase isotrope à des fréquences aussi basses que 0.01 Hz et des températures éloignées de toute transition. Le comportement dela biréfringence basses-fréquences a des similitudes avec l'élasticité; elle est en phase avec la déformation à faibles amplitudes de déformation, puis en phase avec le taux de déformation à plus grandes amplitudes. La biréfringence basses- fréquences est forte, sans défaut et réversible. Elle indique un ordre à longue portée. La synchronisation de la réponse à la sollicitation en fréquence et l’état ordonné qu’elle produit ne sont pas compatibles avec un état liquide isotrope mais montrent qu’il s’agit d’un état élastique soumis à déformation (entropie élastique). / Liquids differ from solids by a delayed response to a shear mechanical solicitation; i.e. they have no shearelasticity and exhibit a flow behaviour at low frequency (<1 Hz). This postulate might be not verified at thesub-millimeter scale. By optimizing the measurement in particular by improving the liquid/substrate interactions (wetting), a low frequency shear elasticity has been found in liquids including molten polymers, glass-formers, H-bond polar, ionic or van der Waals liquids. This result implies that molecules in the liquid state may not be dynamically free but weaklyelastically correlated. Using the birefringent properties of the pretransitional fluctuations coexisting in the isotropic phase of liquid crystals, we show that it is possible to visualize these “hidden” shear-elastic correlations. We detect a synchronized birefringent optical response in the isotropic phase that is observable at frequencies as low as 0.01 Hz and at temperatures far away from anyphase transition. The low-frequency birefringence exhibits a strain dependence similar to the low frequency elasticity: An optical signal that is in-phase with the strain at low strain amplitudes and in-phase with the strain-rate at larger strain amplitudes. The birefringent response is strong, defect-free, reversible and points out a collective response. This long-range ordering rules out the condition of an isotropic liquid and its synchronized response supports the existenceof long-range elastic (solid-like) correlations. In the light of this, the strain dependence of the harmonic birefringent signal and the shear elasticity may correspond to an entropy-driven transition.

Yes / A recent development of the Molecular Stress Function constitutive model, the Hierarchical Multi-Mode Molecular Stress Function (HMMSF) model has been shown to fit a large range of rheometrical data with accuracy, for a large range of polymer melts. We develop a 3D simulation of the HMMSF model and compare it to experimental data for the flow of Lupolen 1840H LDPE through an abrupt 3D contraction flow. We believe this to be the first finite element implementation of the HMMSF model. It is shown that the model gives a striking agreement with experimental vortex opening angles, with very good agreement to full-field birefringence measurements, over a wide range of flow rates. A method to give fully-developed inlet boundary conditions is implemented (in place of using parabolic inlet boundary conditions), which gives a significantly improved match to birefringence measurements in the inlet area, and in low stress areas downstream from the inlet. Alternative constitutive model parameters are assessed following the principle that extensional rheometer data actually provides a ‘lower bound’ for peak extensional viscosity. It is shown that the model robustly maintains an accurate fit to vortex opening angle and full-field birefringence data, provided that both adjustable parameters are kept such that both shear and extensional data are well fitted.

Glaucoma is the second leading cause of blindness in the world. The disease is characterized by irreversible damage to retinal ganglion cells. Once glaucoma is detected, further vision loss can be prevented by pharmacological or surgical treatment. However, current diagnostic methods lack the necessary sensitivity and up to 40% of vision maybe irreversibly lost before detection occurs. A Swept Source Polarization-Sensitive Optical Coherence Tomography (SS-PSOCT) instrument for high sensitivity cross-sectional imaging of optical anisotropy in turbid media has been designed, constructed, and verified. A multiple-state nonlinear fitting algorithm was used to measure birefringence of the retinal nerve fiber layer with less than 1%± average uncertainty. To perform eye imaging efficiently a slit-lamp based interface for the SS-PSOCT instrument with a Line Scanning Laser Ophthalmoscope (LSLO) was used. This interface allowed for repeatable, stable, and registered measurements of the retina. A fixation target was used to stabilize the volunteer’s eye and image desired areas of the retina. The LSLO allowed for an optimization of the location of OCT scans on the retina and provided a fundus blood vessel signature for registration between different imaging sessions. The SS-PSOCT system was used to measure depth-resolved thickness, birefringence, phase retardation and optic axis orientation of the retinal nerve fiber layer in normal volunteers. The peripapillary area around the optic nerve head (ONH) is most sensitive to glaucoma changes and hence data was acquired as concentric ring scans about the ONH with increasing diameters from 2mm to 5mm. Imaging of normal patients showed that higher values of phase retardation occurred superior and inferior to the optic nerve head especially next to blood vessels and thicker parts of the retinal nerve fiber layer. / text