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.

Dynamic and Thermodynamic Structure of the Monsoon Boundary Layer over India

The objective of the study is to examine the dynamic and thermodynamic structure and the variations that occur in the surface layer during the pre-monsoon, onset and post-monsoon periods over the Indian region. The variations caused during the occurrence of micro and mesoscale systems, structure and variation in the marine boundary layer over the Indian region is also investigated. The drag coefficient computed indirectly also shows variation during various seasons. The thermodynamic structure of the atmosphere shows variation during the various seasons. The onset monsoon causes lowering of the Lifting Condensation Levels. The outcome of the study is expected to provide a better understanding of the structure and variations in the boundary layer over India, which is useful for many applications especially for numerical modeling studies.

Evanescent Wave Fibre Optic Sensors for Trace Analysis of Fe3+ in Water

In this communication, we discuss the details of fabricating an off-line fibre optic sensor (FOS) based on evanescent wave absorption for detecting trace amounts of Fe3+ in water. Two types of FOS are developed; one type uses the unclad portion of a multimode silica fibre as the sensing region whereas the other employs the microbent portion of a multimode plastic fibre as the sensing region. Sensing is performed by measuring the absorption of the evanescent wave in a reagent medium surrounding the sensing region. To evaluate the relative merits of the two types of FOS in Fe3+ sensing, a comparative study of the sensors is made, which reveals the superiority of the latter in many respects, such as smaller sensing length, use of a double detection scheme (for detecting both core and cladding modes) and higher sensitivity of cladding mode detection at an intermediate range of concentration along with the added advantage that plastic fibres are inexpensive. A detection limit of 1 ppb is observed in both types of fibre and the range of detection can be as large as 1 ppb–50 ppm. All the measurements are carried out using a LabVIEW set-up.

Evanescent wave fibre optic sensors for trace analysis of Fe3+ in water

In this communication, we discuss the details of fabricating an off-line fibre optic sensor (FOS) based on evanescent wave absorption for detecting trace amounts of Fe3+ in water. Two types of FOS are developed; one type uses the unclad portion of a multimode silica fibre as the sensing region whereas the other employs the microbent portion of a multimode plastic fibre as the sensing region. Sensing is performed by measuring the absorption of the evanescent wave in a reagent medium surrounding the sensing region. To evaluate the relative merits of the two types of FOS in Fe3+ sensing, a comparative study of the sensors is made, which reveals the superiority of the latter in many respects, such as smaller sensing length, use of a double detection scheme (for detecting both core and cladding modes) and higher sensitivity of cladding mode detection at an intermediate range of concentration along with the added advantage that plastic fibres are inexpensive. A detection limit of 1 ppb is observed in both types of fibre and the range of detection can be as large as 1 ppb–50 ppm. All the measurements are carried out using a LabVIEW set-up.

Evanescent wave fibre optic sensors for trace analysis of Fe3+ in water

In this communication, we discuss the details of fabricating an off-line fibre optic sensor (FOS) based on evanescent wave absorption for detecting trace amounts of Fe3+ in water. Two types of FOS are developed; one type uses the unclad portion of a multimode silica fibre as the sensing region whereas the other employs the microbent portion of a multimode plastic fibre as the sensing region. Sensing is performed by measuring the absorption of the evanescent wave in a reagent medium surrounding the sensing region. To evaluate the relative merits of the two types of FOS in Fe3+ sensing, a comparative study of the sensors is made, which reveals the superiority of the latter in many respects, such as smaller sensing length, use of a double detection scheme (for detecting both core and cladding modes) and higher sensitivity of cladding mode detection at an intermediate range of concentration along with the added advantage that plastic fibres are inexpensive. A detection limit of 1 ppb is observed in both types of fibre and the range of detection can be as large as 1 ppb–50 ppm. All the measurements are carried out using a LabVIEW set-up.

Evanescent wave fibre optic sensors for trace analysis of Fe3+ in water

In this communication, we discuss the details of fabricating an off-line fibre optic sensor (FOS) based on evanescent wave absorption for detecting trace amounts of Fe3+ in water. Two types of FOS are developed; one type uses the unclad portion of a multimode silica fibre as the sensing region whereas the other employs the microbent portion of a multimode plastic fibre as the sensing region. Sensing is performed by measuring the absorption of the evanescent wave in a reagent medium surrounding the sensing region. To evaluate the relative merits of the two types of FOS in Fe3+ sensing, a comparative study of the sensors is made, which reveals the superiority of the latter in many respects, such as smaller sensing length, use of a double detection scheme (for detecting both core and cladding modes) and higher sensitivity of cladding mode detection at an intermediate range of concentration along with the added advantage that plastic fibres are inexpensive. A detection limit of 1 ppb is observed in both types of fibre and the range of detection can be as large as 1 ppb–50 ppm. All the measurements are carried out using a LabVIEW set-up.

A fibre optic evanescent wave sensor for monitoring the rate of pulsed laser deposition of metal thin films

A novel sensing technique for the in situ monitoring of the rate of pulsed laser deposition (PLD) of metal thin films has been developed. This optical fibre based sensor works on the principle of the evanescent wave penetration of waveguide modes into the uncladded portion of a multimode fibre. The utility of this optical fibre sensor is demonstrated in the case of PLD of silver thin films obtained by a Q-switched Nd:YAG laser which is used to irradiate a silver target at the required conditions for the preparation of thin films. This paper describes the performance and characteristics of the sensor and shows how the device can be used as an effective tool for the monitoring of the deposition rate of silver thin films. The fibre optic sensor is very simple, inexpensive and highly sensitive compared with existing techniques for thin film deposition rate measurements

A fibre optic evanescent wave sensor for monitoring the rate of pulsed laser deposition of metal thin films

A novel sensing technique for the in situ monitoring of the rate of pulsed laser deposition (PLD) of metal thin films has been developed. This optical fibre based sensor works on the principle of the evanescent wave penetration of waveguide modes into the uncladded portion of a multimode fibre. The utility of this optical fibre sensor is demonstrated in the case of PLD of silver thin films obtained by a Q-switched Nd:YAG laser which is used to irradiate a silver target at the required conditions for the preparation of thin films. This paper describes the performance and characteristics of the sensor and shows how the device can be used as an effective tool for the monitoring of the deposition rate of silver thin films. The fibre optic sensor is very simple, inexpensive and highly sensitive compared with existing techniques for thin film deposition rate measurements.

A fibre optic evanescent wave sensor used for the detection of trace nitrites in water

A fibre optic technique for detecting trace amounts of nitrite compounds in water is described. The off-line fibre optic sensor outlined here is based on evanescent field absorption in a test solution formed by the reaction of nitrite compounds in water with suitable chemical reagents. A short unclad portion of a plastic clad silica fibre acts as the sensing region. The experimental results clearly establish the usefulness of the present technique for detecting very low concentrations of the order of 1 ppb (parts per billion) of nitrite compounds with a large dynamic range of 1–1000 ppb. Such a high sensitivity enables the present device to be used for measuring the nitrite content in drinking water.

A sensitive fibre optic pH sensor using multiple sol–gel coatings

The fabrication and characterization of a fibre optic pH sensor based on evanescent wave absorption is presented. The unclad portion of a multi-mode optical fibre is coated with a pH sensitive dye, which is immobilized by the sol–gel route. The sensitivity of the device has been found to increase when multiple sol–gel coatings are used as the sensing region. The dynamic range and the temporal response of the sensor are investigated for two different dyes, namely bromocresol purple and bromocresol green. The performance of the device is evaluated in terms of the results obtained during actual measurements.

A sensitive fibre optic pH sensor using multiple sol–gel coatings

The fabrication and characterization of a fibre optic pH sensor based on evanescent wave absorption is presented. The unclad portion of a multi-mode optical fibre is coated with a pH sensitive dye, which is immobilized by the sol–gel route. The sensitivity of the device has been found to increase when multiple sol–gel coatings are used as the sensing region. The dynamic range and the temporal response of the sensor are investigated for two different dyes, namely bromocresol purple and bromocresol green. The performance of the device is evaluated in terms of the results obtained during actual measurements

A sensitive fibre optic pH sensor using multiple sol–gel coatings

The fabrication and characterization of a fibre optic pH sensor based on evanescent wave absorption is presented. The unclad portion of a multi-mode optical fibre is coated with a pH sensitive dye, which is immobilized by the sol–gel route. The sensitivity of the device has been found to increase when multiple sol–gel coatings are used as the sensing region. The dynamic range and the temporal response of the sensor are investigated for two different dyes, namely bromocresol purple and bromocresol green. The performance of the device is evaluated in terms of the results obtained during actual measurements

Fibre optic sensor for the detection of adulterant traces in coconut oil

The design and development of a fibre optic evanescent wave refractometer for the detection of trace amounts of paraffin oil and palm oil in coconut oil is presented. This sensor is based on a side-polished plastic optical fibre. At the sensing region, the cladding and a small portion of the core are removed and the fibre nicely polished. The sensing region is fabricated in such a manner that it sits perfectly within a bent mould. This bending of the sensing region enhances its sensitivity. The oil mixture of different mix ratios is introduced into the sensing region and we observed a sharp decrease in the output intensity. The observed variation in the intensity is found to be linear and the detection limit is 2% (by volume) paraffin oil/palm oil in coconut oil. The resolution of this refractometric sensor is of the order of 10−3. Since coconut oil is consumed in large volumes as edible oil in south India, this fibre optic sensor finds great relevance for the detection of adulterants such as paraffin oil or palm oil which are readily miscible in coconut oil. The advantage of this type of sensor is that it is inexpensive and easy to set up. Another attraction of the side-polished fibre is that only a very small amount of analyte is needed and its response time is only 7 s.

Development of Photorefractive Polymers: Evaluation of Photoconducting and Electro-optic Properties

This Thesis discussed molecules suitable for photorefractive effect. Out of the molecules studied, only one system was used to make photorefractive polymers system. Other molecules, especially, the electro-optic polymer, Poly(3-methacrloyl-1-(4'-nitro-4-azo-1'-phenyl)phenylalanine-co- methyl methacrylate) can be subjected to more detailed studies to explore the possibilities of using them for electro-optic applications. Though not included in the thesis, the efficient photoconductor, Poly(6-tert-butyl-3- phenyl-3,4-dihydro-2H-1,3-benzoxazine) sensitized with C60, which was described in Chapter 3 showed a low magnitude photovoltaic effect. This hints at the possibility of using this system for organic solar cells also. The thesis presented the initial observation of photorefractive effect in a polybenzoxazine based polymer system. A detailed analysis of the effect of C60, ECZ and DR1 can be carried out to check for the possibility of a high efficiency photorefractive system.