Power tapping function in near infra-red region based on 45° tilted fiber gratings

We report an efficient power tapping device working in near infra-red (800 nm) wavelength region based on UV-in- scribed 45° tilted fiber grating (45°-TFG) structure. Five 45°-TFGs were UV-inscribed in hydrogenated PS750 fiber using a custom-designed phase mask with different grating lengths of 3 mm, 5 mm, 9 mm, 12 mm and 15 mm, showing polarization dependent losses (PDLs) of 1 dB, 3 dB, 7 dB, 10 dB and 13 dB, respectively. The power side-tapping efficiency is clearly depending on the grating strength. It has been identified that the power tapping efficiency increases with the grating strength and deceases along the grating length. The side-tapped power profile has also been examined in azimuthal direction, showing a near-Gaussian distribution. These experimental results clearly demonstrated that 45°- TFGs may be used as in-fiber power tapping devices for applications requiring in-line signal monitoring.

Multilayered coated infra-red surface plasmon resonance fibre sensors for aqueous chemical sensing

A series of surface plasmonic fibre devices were fabricated by depositing multiple thin coatings on a lapped section of a standard single mode telecoms fibre forming a D-shaped section and then inscribing a grating-type structure using UV light. The coatings consisted of base coatings of semi-conductor (germanium) and dielectric (silicon dioxide) materials, followed by different metals. These fibre devices showed high spectral refractive index sensitivity with high coupling efficiency in excess of 40 dB for indices in the aqueous regime and below, with estimated index sensitivities of Lambda lambda/Lambda n = 90-800 nm from 1 to 1.15 index range and Lambda lambda/Lambda n = 1200-4000 nm for refractive indices from 1.33 to 1.39. (C) 2009 Elsevier Inc. All rights reserved.

A survey of urban open space using colour infra-red aerial photographs

There has been a dramatic change in the U.K. government policy regarding the establishment of new towns. The emphasis is now on the redevelopment of existing cities rather than on building new ones. This has created an urgent need to carry out detailed surveys and inventories of many aspects of urban land use in metropolitan areas: this study concentrates on just one aspect - urban open space. In the first stage a comparison was made between 1:10,000 scale black and white and 1:10,000 scale colour infra-red aerial photographs, to compare the type and amount of open space information which could be obtained from these two sources. The advantages of using colour infra-red photography were clearly demonstrated in this comparison. The second stage was the use of colour infra-red photography as the sole source of data to survey and map the urban open space of a sample area in Merseyside Metropolitan County. This sample area comprised eleven 1/4km2 squares, on each of which a 20m x 20m grid cell was placed to record, directly from the photography, 625 sets of data. Each set of data recorded the type and amount of open space, its surface cover, maintenance status and management. The data recorded were fed into a computer and a suite of programs was developed to provide output in both computer map and statistical form, for each of the eleven -1/4km2 -sample areas. The third stage involved a comparison of open space data with socio-economic status. Merseyside County Planning Authority had previously conducted a socio-economic survey of the county, and this information was used to identify ' the socio-economic status of the population in the eleven ilkm2 areas of this project. This comparison revealed many interesting and useful relationships between the provision of urban open space and socio-economic status.

Using an Infra-red sensor to measure the dynamic behaviour of N2O gas escaping through different sized holes

An anastomosis is a surgical procedure that consists of the connection of two parts of an organ and is commonly required in cases of colorectal cancer. About 80% of the patients diagnosed with this problem require surgery. The malignant tissue located on the gastrointestinal track must be resected and the most common procedure adopted is the anastomosis. Therefore, an anastomotic leak represents a significant problem and increases the duration of hospital stay, which is associated with remedial treatment and recovery, causing, as a result, a negative financial impact. A number of techniques to treat, prevent and even detect an anastomotic leakage are under investigation. However, studies show that these techniques are not always able to prevent an anastomotic leak from occurring. This paper discusses the monitoring of leakage through differently sized and differently positioned leak holes in phantom colons, using physical experiments and a Computational Fluid Dynamics package called FloWorks. © 2011 Taylor & Francis Group.

Using an infra-red sensor to measure the dynamic behaviour of N2O gas escaping through different sized holes

An anastomosis is a surgical procedure that consists of the re-connection of two parts of an organ and is commonly required in cases of colorectal cancer. Approximately 80% of the patients diagnosed with this problem require surgery. The malignant tissue located on the gastrointestinal track must be resected and the most common procedure adopted is the anastomosis. Studies made with 2,980 patients that had this procedure, show that the leakage through the anastomosis was 5.1%. This paper discusses the dynamic behavior of N2O gas through different sized leakages as detected by an Infra-Red gas sensor and how the sensors response time changes depending on the leakage size. Different sized holes were made in the rigid tube to simulate an anastomostic leakage. N2O gas was injected into the tube through a pipe and the leakage rate measured by the infra-red gas sensor. Tests were also made experimentally also using a CFD (Computational Fluid Dynamics) package called FloWorks. The results will be compared and discussed in this paper.

Discrimination between strain and temperature effects using first and second-order diffraction from a long period grating

We study the effects of temperature and strain on the spectra of the first and second-order diffraction attenuation bands of a single long-period grating (LPG) in step-index fibre. The primary and second-order attenuation bands had comparable strength with the second-order bands appearing in the visible and near-infra red parts of the spectrum. Using first and second-order diffraction to the eighth cladding mode a sensitivity matrix was obtained with limiting accuracy given by cross-sensitivity of ~1.19% of the measurement. The sensing scheme presented as a limiting temperature and strain resolution of ±0.7 °C and ~±25 µ.

Functional polymers for biomedical application : synthesis and applications

Aromatic and aliphatic diacid chlorides were used to condense naturally occurring diamino acids and their esterified derivatives. It was anticipated the resulting functional polyamides would biodegrade to physiologically acceptable compounds and show pH dependant solubility could be used for biomedical applications ranging from enteric coatings to hydrosoluble drug delivery vehicles capable of targeting areas of low physiological pH. With these applications in mind the polymers were characterised by infra red spectroscopy, gel permeation chromatography and in the case of aqueous soluble polymers by potentiometric titration. Thin films of poly (lysine ethyl ester isophthalamide) plasticised with poly (caprolactone) were cast from DMSO/chloroform solutions and their mechanical properties measured on a Hounsfield Hti tensiometer. Interfacial synthesis was investigated as a synthetic route for the production of linear functional polyamides. High molecular weight polymer was obtained only when esterified diamino acids were condensed with aromatic diacid chlorides. The method was unsuitable for the production of copolymers of free and esterified amino acids with a diacid chloride. A novel miscible mixed solvent single phase reaction was investigated for production of copolymers of esterified and non-esterified amino acids with diacid chlorides. Aliphatic diacid chlorides were unsuitable for condensing diamino acids using this technique because of high rates of hydrolysis. The technique gave high molecular weight homopolymers from esterified diamino acids and aromatic diacid chlorides.

The synthesis, characterisation and electrical conductivity of poly(styrene-co-acetylene)

A novel metathesis catalyst for the polymerisation of acetylene has been developed. The polyacetylene produced by this new catalyst has been characterised by infra-red and NMR spectroscopy. The conductivity of the pristine material has been studied as a function of temperature, pressure and frequency. The effect on the conductivity of doping the material has also been investigated. The new metathesis catalyst has been incorporated into an anionic-to-metathesis transformation reaction. This novel reaction has been used to prepare samples of poly(styrene-co-acetylene). The copolymer has been characterised using U.V./Visible, NMR, infra-red spectroscopy and the surface morphology looked at using scanning electron microscopy. GPC was also used to give some idea of the molecular weights of the materials prepared. The conductivity of the copolymer has been studied as a function of temperature, pressure and frequency. The effect of doping on the conductivity the material has also been investigated. The conductivity results obtained from both materials have been used to try and gain an insight into the mechanism of the conduction processes occurring within the materials. An attempt has also been made to synthesise polyacetylene oligomers (polyenes) by modifying the Ziegler/Natta type catalysts commonly used to synthesise polyacetylene. The polyenes were characterised using U.V./Visible and infra-red spectroscopy together with GPC and GCMS.

The analysis of organic matter in oil-shales

The organic matter in five oil shales (three from the Kimmeridge Clay sequence, one from the Oxford Clay sequence and one from the Julia Creek deposits in Australia) has been isolated by acid demineralisation, separated into kerogens and bitumens by solvent extraction and then characterised in some detail by chromatographic, spectroscopic and degradative techniques. Kerogens cannot be characterised as easily as bitumens because of their insolubility, and hence before any detailed molecular information can be obtained from them they must be degraded into lower molecular weight, more soluble components. Unfortunately, the determination of kerogen structures has all too often involved degradations that were far too harsh and which lead to destruction of much of the structural information. For this reason a number of milder more selective degradative procedures have been tested and used to probe the structure of kerogens. These are: 1. Lithium aluminium hydride reduction. - This procedure is commonly used to remove pyrite from kerogens and it may also increase their solubility by reduction of labile functional groups. Although reduction of the kerogens was confirmed, increases in solubility were correlated with pyrite content and not kerogen reduction. 2. O-methylation in the presence of a phase transfer catalyst. - By the removal of hydrogen bond interactions via O-methylation, it was possible to determine the contribution of such secondary interactions to the insolubility of the kerogens. Problems were encountered with the use of the phase transfer catalyst. 3. Stepwise alkaline potassium permanganate oxidation. - Significant kerogen dissolution was achieved using this procedure but uncontrolled oxidation of initial oxidation products proved to be a problem. A comparison with the peroxytrifluoroaceticacid oxidation of these kerogens was made. 4. Peroxytrifluoroacetic acid oxidation. - This was used because it preferentially degrades aromatic rings whilst leaving any benzylic positions intact. Considerable conversion of the kerogens into soluble products was achieved with this procedure. At all stages of degradation the products were fully characterised where possible using a variety of techniques including elemental analysis, solution state 1H and 13C nuclear magnetic resonance, solid state 13C nuclear magnetic resonance, gel-permeationchromatography, gas chromatography-mass spectroscopy, fourier transform infra-red spectroscopy and some ultra violet-visible spectroscopy.

Organotellurium compounds for metal organic vapour phase epitaxy

The infra-red detector material cadmium mercury telluride can be grown by the technique of Metal Organic Vapour Phase Epitaxy using simple alkyl telluride compounds as the source of tellurium. New tellurium precursors are required in order to overcome handling and toxicity problems and to reduce the growth temperature in preparing the material. A range of diaryltellurium(IV) dicarboxylates and some 2-(2'-pyridyl)phenyl-tellurium(II) and tellurium(IV) monocarboxylates have been synthesised and characterised by infra-red, 13C N.M.R. and mass spectroscopy. Infra-red spectroscopy has been used to determine the mode of bonding of the carboxylate ligand to tellurium. Synthetic methods have been devised for the preparation of diorganotritellurides (R2Te3) and mixed diorganotetrachalcogenides (RTeSeSeTeR). A mechanism for the formation of the tritellurides based on aerobic conditions is proposed. The reaction of ArTe- with (ClCH2CH2)3N leads to tripod-like multidentate ligands (ArTeCH2CH2)3N which form complexes with the ions Hg(II), Cd(II), Cu(I), Pt(II) and Pd(II). Synthetic routes to aryltelluroalkylamines and arylselenoalkylamines are also reported. The crystal structure of 2-(2'-pyridyl)phenyltellurium(II) bromide has been solved in which there are six molecules present within the unit cell. There are no close intermolecular Te---Te interactions and the molecules are stabilised by short Te---N intramolecular contacts. The crystal structure of 2-(2'-pyridyl)phenylselenium(II)-tribromomercurate(II) is also presented. A study of the Raman vibrational spectra of some tellurated azobenzenes and 2-phenylpyridines shows spectra of remarkably far superior quality to those obtained using infra-red spectroscopy.

Surface coating deterioration studies

This project is concerned with the deterioration of surface coatings as a result of weathering and exposure to a pollutant gas (in this case nitric oxide). Poly(vinyl chloride) (PVC) plastisol surface coatings have been exposed to natural and artificial weathering and a comparison of the effects of these two types of weathering has been made by use of various analytical techniques. These techniques have each been assessed as to their value in providing information regarding changes taking place in the coatings during ageing, and include, goniophotometry, micro-penetrometry, surface energy measurements, weight loss measurements, thermal analysis and scanning electron microscopy. The results of each of these studies have then been combined to show the changes undergone by PVC plastisol surface coatings during ageing and to show the effects which additives to the coatings have on their behaviour and in particular the effects of plasticiser, pigment and uv and thermal stabilisers. Finally a preliminary study of the interaction between five commercial polymers and nitric oxide has been carried out, the polymers being polypropylene, cellulose acetate butyrate, polystyrene, polyethylene terephthalate and polycarbonate. Each of the samples was examined using infra-red spectroscopy in the transmission mode.

Mechanism of the hydropyrolysis of Manvers coal

Manvers coal has been pyrolysed to 500ºC in a stirred autoclave under various pressures of nitrogen (pyrolysis) and hydrogen (hydropyrolysis). All products were investigated. Pyrolysis of coals involves the transfer of hydrogen atoms from one part of their structure to another. In the above experiments there was no way of labelling the hydrogen or of distinguishing between hydrogen which was initially part of the coal and hydrogen originating in the external atmosphere. Consequently, Manvers coal has been pyrolysed in an atmosphere of deuterium in order to obtain greater insight into the mechanism of hydropyrolysis. In particular it was hoped to distinguish between direct hydrogenation (deuteration!) of the coal and the products of pyrolysis and the 'shuttling' of hydrogen atoms between different parts of the pyrolysing coal. The addition to the coal of 5% (wt.% of coal) of either tetralin or pyrite was also studied. A variety of techniques were used to analyse the products of pyrolysis: gas chromatography - mass spectrometry and high performance liquid chromatography for tars; thermal conductivity gas chromatography and high resolution mass spectrometry for gases; methanol densities, microporosities and diffuse reflectance infra red spectroscopy for the cokes (chars); refractive index to determine deuterium in the liquor. An attempt has been made to apply basic thermodynamics to reactions which are likely to occur in the hydropyrolysis of coals. Diffusion and effusion rates for hydrogen and tar molecules have also been estimated.

Photochemical degradation of polystyrene

In this work the oxidative degradation of pure polystyrene, polybutadiene and butadiene-modified polystyrene (normally called high impact polystyrene or HIPS) have been studied using a variety of physical and chemical techniques. The changes in dynamic-mechanical properties occurring during the ultra-violet light accelerated weathering of these polymers were followed by a visco-elastometric technique (Rheovibron) in the solid phase over a wide temperature range. Selective cross-linking of the polybutadiene in high-impact polystyrene caused the depression of the low temperature damping peak (tan d) with a corresponding sharp peak in tan d at ambient temperature accompanied by an integral rise in complex modulus. During the same period of photoxidation, the hydroperoxide concentration and gel content increased rapidly, reaching a maximum before decomposing photolytically with the destruction of unsaturation and with the formation of stable oxidation products. Infra-red spectroscopy showed the formation of carbonyl and hydroxyl groups. a,ß-unsaturated carbonyl was also identified and was formed by decomposition of both allylic hydroperoxide and initial peroxidic gel by ß-scission of the graft between polybutadiene and polystyrene. With further photoxidation a more stable ether gel was formed involving the destruction of the conjugating double bond of a,ß-unsaturated carbonyl. Addition of saturated and unsaturated ketones which are potential sensitisers of photoxidation to high-impact polystyrene and polybutadiene failed to photo-initiate the oxygen absorption of the polymers. A prior thermal oxidative treatment on the other hand eliminated the auto- accelerating stage leading to linear kinetics as the concentration of thermally-produced hydroperoxide approached a maximum. Antioxidants which act by destroying hydroperoxide lengthened the induction period to rapid oxygen absorption, whilst a phenolic antioxidant behaved as a weak photo-activator initially and a retarder later. Prior photolysis of high-impact polystyrene photo-activated the unsaturated component and caused similar changes in dynamic-mechanical properties to those found during photoxidation although at a much lower rate. Polybutadiene behaves as a photo-pro-oxidant for the destruction of polystyrene in high-impact polystyrene.

Characterisation and modification of hydrogel polymers

The work described in this thesis can be broadly divided into two sections. The first being the characterisation of hydrogel polymers in both their hydrated and dehydrated states and the second some aspects of the structural modification of polymers. The characterisation of hydrogel polymers in their dehydrated state (xerogels) involves such techniques as elemental analysis, pyrolysis gas liquid chromatography, infra-red spectroscopy, density determination and surface characterisation by contact angle measurements. The characterisation of some commercially available hydrogel materials was undertaken using such techniques and the results obtained were compared to laboratory synthesised systems in an attempt to assess the value of the combination of techniques employed. In the characterisation of hydrated polymers the amoumt and nature of water present is the single most important factor. The most convenient method of characterising this water involves the use of differential scanning calorimetry (DSC), coupled with total equilibrium water content measurements. DSC distinguishes between non-freezing and freezing water but in addition provides some information on the continuum of states in the freezing water fraction. Two aspects of the structural modification of hydrogel polymers were studied. The first involved the incorporation of acrylamide and substituted acryamide monomers into a copolymer system and an examination of the effect of this on the amino acid interaction of the polymers. The second was the attempted synthesis of cell surface analogues by the attachment of sugar type molecules to the polymer using a variety of reaction methods.

Surfactant coated aerosol powders and their properties

The hygroscopic growth of aerosols is an important factor effecting particle size. The consequence of the hygroscopic growth of pharrnaceutical aerosols is a change in their deposition characteristics, such that there is an increase in the total amount deposited in the lung. In this study the hygroscopic growth of disodium fluorescein (DF) aerosol powders was investigated by coating the powders with lauric and capric acids. The coating procedure was carried out in dichloromethane and chloroform, which acted as cosolvents for the fatty acids. An assessment of the extent and the nature of the coating was carried out. The qualitative assessment of the coating was achieved by infra-red spectroscopy, electronscanning chemical analysis and scanning electron microscopy. The quantitative analysis was carried out by differential refractometry, ultra-violet spectroscopy and gas liquid chromatography. These powders were generated under conditions approaching those in the lung, of 97 % relative humidity and 37"C. Coated and uncoated DF aerosol powders were introduced into a controlled temperature and relative humidity apparatus, designed and constructed for the investigation of hygroscopic growth in these studies. A vertical spinning disc device was used to generate the powders. Under conditions of controlled temperature and relative humidity mentioned, the growth ratio of disodium fluorescein alone was 1.45 compared with 1.68, for a nominal coating of DF with lauric acid of 0.12 gg-1, 1.0 for a nominal lauric acid coating of 0.2 gg-1, and 1.02 for a nominal capric acid coating of 0.18 gg-1. The range of control of hygroscopic growth of these aerosols has implications for the deposition of these preparations in the respiratory tract. These implications are discussed in the light of the current knowledge of the effects of hygroscopic growth on the deposition of pharmaceutical and environmental aerosols. A series of experiments in which pulmonary ventilation using a simple radioaerosol generator and delivery system are reported showing that particle size determination may be used to aid the design of diagnostic aerosol generators.