The effects of additives and chemical modification on the solution properties of thermo-sensitive polymers

Cette thèse concerne l’étude de phase de séparation de deux polymères thermosensibles connus-poly(N-isopropylacylamide) (PNIPAM) et poly(2-isopropyl-2-oxazoline) (PIPOZ). Parmi des études variées sur ces deux polymères, il y a encore deux parties de leurs propriétés thermiques inexplicites à être étudiées. Une partie concerne l’effet de consolvant de PNIPAM dans l’eau et un autre solvant hydromiscible. L’autre est l’effet de propriétés de groupes terminaux de chaînes sur la séparation de phase de PIPOZ. Pour ce faire, nous avons d’abord étudié l’effet de l’architecture de chaînes sur l’effet de cosolvant de PNIPAMs dans le mélange de méthanol/eau en utilisant un PNIPAM en étoile avec 4 branches et un PNIPAM cyclique comme modèles. Avec PNIPAM en étoile, l’adhérence de branches PNIPAM de à un cœur hydrophobique provoque une réduction de Tc (la température du point de turbidité) et une enthalpie plus faible de la transition de phase. En revanche, la Tc de PNIPAM en étoile dépend de la masse molaire de polymère. La coopérativité de déhydratation diminue pour PNIPAM en étoile et PNIPAM cyclique à cause de la limite topologique. Une étude sur l’influence de concentration en polymère sur l’effet de cosolvant de PNIPAM dans le mélange méthanol/eau a montré qu’une séparation de phase liquide-liquide macroscopique (MLLPS) a lieu pour une solution de PNIPAM dans le mélange méthanol/eau avec la fraction molaire de méthanol entre 0.127 et 0.421 et la concentration en PNIPAM est constante à 10 g.L-1. Après deux jours d’équilibration à température ambiante, la suspension turbide de PNIPAM dans le mélange méthanol/eau se sépare en deux phases dont une phase possède beaucoup plus de PNIPAM que l’autre. Un diagramme de phase qui montre la MLLPS pour le mélange PNIPAM/eau/méthanol a été établi à base de données expérimentales. La taille et la morphologie de gouttelettes dans la phase riche en polymère condensée dépendent de la fraction molaire de méthanol. Parce que la présence de méthanol influence la tension de surface des gouttelettes liquides, un équilibre lent de la séparation de phase pour PNIPAM/eau/méthanol système a été accéléré et une séparation de phase liquide-liquide macroscopique apparait. Afin d’étudier l’effet de groupes terminaux sur les propriétés de solution de PIPOZ, deux PIPOZs téléchéliques avec groupe perfluorodécanyle (FPIPOZ) ou groupe octadécyle (C18PIPOZ) comme extrémités de chaîne ont été synthétisés. Les valeurs de Tc des polymères téléchéliques ont beaucoup diminué par rapport à celle de PIPOZ. Des micelles stables se forment dans des solutions aqueuses de polymères téléchéliques. La micellization et la séparation de phase de ces polymères dans l’eau ont été étudiées. La séparation de phase de PIPOZs téléchéliques suit le mécanisme de MLLPS. Des différences en tailles de gouttelettes formées à l’intérieur de solutions de deux polymères ont été observées. Pour étudier profondément les différences dans le comportement d’association entre deux polymères téléchéliques, les intensités des signaux de polymères correspondants et les temps de relaxation T1, T2 ont été mesurés. Des valeurs de T2 de protons correspondants aux IPOZs sont plus hautes.

Investigations on the cation induced liquid crystalline phases of high molecular weight DNA

Liquid Crystalline DNA is emerging as an active area of research, due to its potential applications in diverse fields, ranging from nanoelectronics to therapeutics. Since, counter ion neutralization is an essential requirement for the expression of LC DNA, and the present level of understanding on the LC phase behavior of high molecular weight DNA is inadequate, a thorough investigation is required to understand the nature and stability of these phases under the influence of various cationic species. The present study is, therefore mainly focused on a comparative investigation of the effect of metal ions of varying charge, size, hydration and binding modes on the LC phase behavior of high molecular weight DNA. The main objectives of the works are investigations on the induction and stabilization of LC phases of high molecular weight DNA by alkali metal ions, investigations on the induction and stabilization of LC phases of high molecular weight DNA by alkaline earth metal ions, effects of multivalent, transition and heavy metal ions on the LC phase behavior of high molecular weight DNA and investigations on spermine induced LC behavior of high molecular weight DNA in the presence of alkali and alkaline earth metal ions. The critical DNA concentration (CD) required for the expression of LC phases, phase transitions and their stability varied considerably when the binding site of the metal ions changed from phosphate groups to the nitrogenous bases of DNA, with Li+ giving the highest stability. Multiple LC phases with different textures, sometimes diffused and unstable or otherwise mainly distinct and clear, were observed on mixing metal ions with DNA solutions, which in turn depended on the charge, size, hydration factor, binding modes, concentration of the metal ions and time. Molecular modeling studies on binding of selected metal ions to DNA supported the experimental findings

Dynamic characteristics of Atmospheric boundary Layer during different phases of Monsoon

Atmospheric Boundary layer (ABL) is the layer just above the earth surface and is influenced by the surface forcing within a short period of an hour or less. In this thesis, characteristics of the boundary layer over ocean, coastal and inland areas of the atmosphere, especially over the monsoon regime are thoroughly studied. The study of the coastal zone is important due to its high vulnerability mainly due to sea breeze circulation and associated changes in the atmospheric boundary layer. The major scientific problems addressed in this thesis are diurnal and seasonal variation of coastal meteorological properties, the characteristic difference in the ABL during active and weak monsoons, features of ABL over marine environment and the variation of the boundary layer structure over an inland station. The thesis describes the various features in the ABL associated with the active and weak monsoons and, the surface boundary layer properties associated with the active and weak epochs. The study provides knowledge on MABL and can be used as the estimated values of boundary layer parameters over the marine atmosphere and to know the values and variabilities of the ABL parameters such as surface wind, surface friction, drag coefficient, wind stress and wind stress curl.

Thermal transport across incommensurate phases in potassium selenate: photo-pyroelectric and calorimetric measurements

The thermal transport properties—thermal diffusivity, thermal conductivity and specific heat capacity—of potassium selenate crystal have been measured through the successive phase transitions, following the photo-pyroelectric thermal wave technique. The variation of thermal conductivity with temperature through the incommensurate (IC) phase of this crystal is measured. The enhancement in thermal conductivity in the IC phase is explained in terms of heat conduction by phase modes, and the maxima in thermal conductivity during transitions is due to enhancement in the phonon mean free path and the corresponding reduction in phonon scattering. The anisotropy in thermal conductivity and its variation with temperature are reported. The variation of the specific heat with temperature through the high temperature structural transition at 745 K is measured, following the differential scanning calorimetric method. By combining the results of photo-pyroelectric thermal wave methods and differential scanning calorimetry, the variation of the specific heat capacity with temperature through all the four phases of K2SeO4 is reported. The results are discussed in terms of phonon mode softening during transitions and phonon scattering by phase modes in the IC phase.

HRTEM assessment of Wurtzite and Zinc-Blende phases in GaAs nanowires for optoelectronic devices

Màster en Nanociència i Nanotecnologia. Curs 2007-2008. Directors: Francesca Peiró i Martínez and Jordi Arbiol i Cobos

Integer filling facfor phases and isospin in vertical diatomic artificial molecules

Integer filling factor phases of many-electron vertically coupled diatomic artificial quantum dot molecules are investigated for different values of the interdot coupling. The experimental results are analyzed within local-spin density functional theory for which we have determined a simple lateral confining potential law that can be scaled for the different coupling regimes, and Hartree-Fock theory. Maximum density droplets composed of electrons in both bonding and antibonding or just bonding states are revealed, and interesting isospin-flip physics appears for weak interdot coupling when the systematic depopulation of antibonding states leads to changes in isospin.

Characteristics of ABL during active and weak phases of monsoon

Understanding of the Atmospheric Boundary Layer (ABL) is imperative in the arena of the monsoon field. Here, the features of the ABL are studied employing Conserved Variable Analysis (CVA) using equivalent potential temperature and humidity. In addition, virtual potential temperature and wind are used during active and weak phases of monsoon. The analysis is carried out utilising the radiosonde observations during the monsoon months for two stations situated in the west coast of India. All these parameters show considerable variations during active and weak monsoon phases in both the stations. The core speed and core height vary with these epochs. The core speed is found to be more than 38 knots in the active monsoon phase around 1.2 km over Trivandrum and around 2 km over Mangalore. But during weak monsoon phase the core wind speed is decreased and core height is elevated over both stations. The wind direction shows an additional along shore component during weak monsoon period. The Convective Boundary Layer (CBL) height shows increase during weak monsoon phase over both stations due to less cloudiness and subsequent insolation. The CBL height during the southwest monsoon is more over Mangalore and is attributed by the orographic lifting in the windward side of the Western Ghats while the influence of the Ghats is less over Trivandrum.

Computer-mediated communication and time pressure induce higher cardiovascular responses in the preparatory and execution phases of cooperative tasks

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Multiple phases of North African humidity recorded in lacustrine sediments from the Fazzan Basin, Libyan Sahara

The Fazzan Basin of south-west Libya is at present arid with less than 20 mm of rainfall per annum. However, regionally extensive limestones, lacustrine sands and coquina (fossiliferous carbonate rock) deposits show that the Fazzan Basin previously contained a large palaeolake, indicating that the climate in the past was more humid. Optically stimulated luminescence (OSL) dating techniques have been applied to key lacustrine deposits within the basin in an attempt to provide an internally consistent chronology for this humidity record. Results indicate that palaeolake sediments within the Fazzan Basin record a very long history of palacohydrological change, ranging from present day and conditions to humidity capable of sustaining a lake with an approximate area of 76,250 km(2). The existence of humid periods in mid oxygen isotope stage 5 and the early Holocene is confirmed. An older lacustrine event, tentatively correlated to oxygen isotope stage 11, is also recognized. In addition, evidence is presented for at least two humid phases beyond the age range over which the conventional OSL dating technique is applicable. This study demonstrates that OSL dating of palaeolake sediments within the Fazzan Basin offers the potential to provide a detailed record of North African humidity spanning several glacial-interglacial cycles. (c) 2006 Elsevier Ltd. All rights reserved.

Subglacial bedform evidence for a major palaeo-ice stream and its retreat phases in Amundsen Gulf, Canadian Arctic Archipelago

Ascertaining the location of palaeo-ice streams is crucial in order to produce accurate reconstructions of palaeo-ice sheets and examine interactions with the ocean-climate system. This paper reports evidence for a major ice stream in Amundsen Gulf, Canadian Arctic Archipelago. Mapping from satellite imagery (Landsat ETM+) and digital elevation models, including bathymetric data, is used to reconstruct flow-patterns on southwestern Victoria Island and the adjacent mainland (Nunavut and Northwest Territories). Several flow-sets indicative of ice streaming are found feeding into the marine trough and cross-cutting relationships between these flow-sets (and utilising previously published radiocarbon dates) reveal several phases of ice stream activity centred in Amundsen Gulf and Dolphin and Union Strait. A large erosional footprint on the continental shelf indicates that the ice stream (ca. 1000 km long and ca. 150 km wide) filled Amundsen Gulf, probably at the Last Glacial Maximum. Subsequent to this, the ice stream reorganised as the margin retreated back along the marine trough, eventually splitting into two separate low-gradient lobes in Prince Albert Sound and Dolphin and Union Strait. The location of this major ice stream holds important implications for ice sheet-ocean interactions and specifically, the development of Arctic Ocean ice shelves and the delivery of icebergs into the western Arctic Ocean during the late Pleistocene. Copyright (C) 2006 John Wiley & Sons, Ltd.