Microchannelled chirped fibre Bragg grating based refractive index sensor formed by femto-second laser processing and HF-etching

The microchannelled chirped fibre Bragg grating (MCFBG) was fabricated using femtosecond laser processing and HF-etching. Intrinsical refractive-index sensitivity induced by the microchannel makes MCFBGs ideal for biochemical sensing.

Pyrolysis and gasification of biomass and acid hydrolysis residues

This research was carried for an EC supported project that aimed to produce ethyl levulinate as a diesel miscible biofuel from biomass by acid hydrolysis. The objective of this research was to explore thermal conversion technologies to recover further diesel miscible biofuels and/or other valuable products from the remaining solid acid hydrolysis residues (AHR). AHR consists of mainly lignin and humins and contains up to 80% of the original energy in the biomass. Fast pyrolysis and pyrolytic gasification of this low volatile content AHR was unsuccessful. However, successful air gasification of AHR gave a low heating value gas for use in engines for power or heat with the aim of producing all the utility requirements in any commercial implementation of the ethyl levulinate production process. In addition, successful fast pyrolysis of the original biomass gave organic liquid yields of up to 63.9 wt.% (dry feed basis) comparable to results achieved using a standard hardwood. The fast pyrolysis liquid can be used as a fuel or upgraded to biofuels. A novel molybdenum carbide catalyst was tested in fast pyrolysis to explore the potential for upgrading. Although there was no deoxygenation, some bio-oil properties were improved including viscosity, pH and homogeneity through decreasing sugars and increasing furanics and phenolics. AHR gasification was explored in a batch gasifier with a comparison with the original biomass. Refractory and low volatile content AHR gave relatively low gas yields (74.21 wt.%), low tar yields (5.27 wt.%) and high solid yields (20.52 wt.%). Air gasification gave gas heating values of around 5MJ/NM3, which is a typical value, but limitations of the equipment available restricted the extent of process and product analysis. In order to improve robustness of AHR powder for screw feeding into gasifiers, a new densification technique was developed based on mixing powder with bio-oil and curing the mixture at 150°C to polymerise the bio-oil.

Microchannelled chirped fibre Bragg grating based refractive index sensor formed by femto-second laser processing and HF-etching

The microchannelled chirped fibre Bragg grating (MCFBG) was fabricated using femtosecond laser processing and HF-etching. Intrinsical refractive-index sensitivity induced by the microchannel makes MCFBGs ideal for biochemical sensing.

Interdependent lateral interactions, hydrophobicity and acid strength and their influence on the catalytic activity of nanoporous sulfonic acid silicas

A series of propylsulfonic (MCM-SOH) and octyl co-functionalised propylsulfonic (MCM-Oc-SOH) catalysts have been prepared by post modification of MCM-41 with mercaptopropyltrimethoxysilane (MPTS) to achieve SOH surface coverages spanning the range 0.12-1 monolayer. Within the MCM-Oc-SOH series, samples with submonolayer MPTS coverages were further grafted with octyltrimethoxysilane to cap bare hydroxyl sites and tune the hydrophobicity of the support. For the MCM-SO H series NH calorimetry revealed acid strength increases as a function of sulfonic acid loading, with -ΔH(NH ) increasing from 87 to 118 kJ mol. In contrast, MCM-Oc-SOH exhibits a dramatic enhancement of acid strength for submonolayer SOH coverages, with -ΔH(NH ) found to increase to 103 kJ mol. In line with these acid strength measurements the per-site activity of the MCM-SOH series in the esterification of butanol with acetic acid was found to increase with SOH content. Incorporation of octyl groups further promotes esterification activity of all the samples within the MCM-Oc-SOH series, such that the turn over frequency of the sample with the lowest loading of SOH more than doubles. Molecular dynamic simulations indicate that the interaction of isolated sulfonic acid groups with the pore walls is the primary cause of the decrease in acid strength and activity of submonolayer samples within the MCM-SOH series. Incorporation of octyl groups results in a combination of increased hydrophobicity and lateral interactions between adjacent sulfonic acid head groups, resulting in a striking enhancement of acid strength and esterification activity. © 2010 The Royal Society of Chemistry.

Advanced optical fibre gratings and applications

DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY AND INFORMATION SERVICES WITH PRIOR ARRANGEMENT This thesis describes a detailed study of advanced optical fibre sensors based on fibre Bragg grating (FBG), tilted fibre Bragg grating (TFBG) and long-period grating (LPG) and their applications in optical communications and sensing. The major contributions presented in this thesis are summarised below.The most important contribution from the research work presented in this thesis is the implementation of in-fibre grating based refractive index (RI) sensors, which could be the good candidates for optical biochemical sensing. Several fibre grating based RI sensors have been proposed and demonstrated by exploring novel grating structures and different fibre types, and employing efficient hydrofluoric acid etching technique to enhance the RI sensitivity. All the RI devices discussed in this thesis have been used to measure the concentration of sugar solution to simulate the chemical sensing. Efforts have also been made to overcome the RI-temperature cross-sensitivity for practical application. The demonstrated in-fibre grating based RI sensors could be further implemented as potential optical biosensors by applying bioactive coatings to realise high bio-sensitivity and bio-selectivity.Another major contribution of this thesis is the application of TFBGs. A prototype interrogation system by the use of TFBG with CCD-array was implemented to perform wavelength division multiplexing (WDM) interrogation around 800nm wavelength region with the advantages of compact size, fast detection speed and low-cost. As a high light, a novel in-fibre twist sensors utilising strong polarisation dependant coupling behaviour of an 81°-TFBG was presented to demonstrate the high torsion sensitivity and capability of direction recognition.

Fabrication of micro-channels in optical fibers using femtosecond laser pulses and selective chemical etching

The fabrication of micro-channels in single-mode optical fibers is demonstrated using focused femtosecond laser processing and chemical etching. Straight line micro-channels are achieved based on a simple technique which overcomes limitations imposed by the fiber curved surface.

Fabrication of micro-channels in optical fibers using femtosecond laser pulses and selective chemical etching

The fabrication of micro-channels in single-mode optical fibers is demonstrated using focused femtosecond laser processing and chemical etching. Straight line micro-channels are achieved based on a simple technique which overcomes limitations imposed by the fiber curved surface. © 2005 Optical Society of America.

Optical biochemical sensors based on long-period fibre gratings UV-inscribed in D-fibre with enhanced sensitivity by HF etching process

We report a new concept of biochemical sensor device based on long-period grating structures UV-inscribed in D-fiber. The surrounding-medium refractive index sensitivity of the devices has been enhanced significantly by a hydrofluoric acid etching process. The devices have been used to measure the sugar concentrations showing clearly an encoding relation between the chemical concentration and the grating spectral response, demonstrating their capability for potential biochemical sensing applications.

Structure and reactivity of sol-gel sulphonic acid silicas

A range of mesoporous solid sulphonic acid catalysts have been prepared from a mercaptopropyl-trimethoxysilane (MPTS) precursor by sol-gel synthesis. The creation of surface sulphonic acid functionality via thiol oxidation has been followed by XPS and Raman spectroscopy. It is possible to continuously vary the sulphonic acid loading from 1 to 12wt.% while maintaining pore volume and mesostructure. The resulting materials exhibit high thermal stability and acid strength across the composition range and show good activity and selectivity in esterification and condensation reactions. © 2002 Elsevier Science B.V. All rights reserved.

Purification of phosphoric acid by solvent extraction

This work follows a feasibility study (187) which suggested that a process for purifying wet-process phosphoric acid by solvent extraction should be economically viable. The work was divided into two main areas, (i) chemical and physical measurements on the three-phase system, with or without impurities; (ii) process simulation and optimization. The object was to test the process technically and economically and to optimise the type of solvent. The chemical equilibria and distribution curves for the system water - phosphoric acid - solvent for the solvents n-amyl alcohol, tri-n-butyl phosphate, di-isopropyl ether and methyl isobutyl ketone have been determined. Both pure phosphoric acid and acid containing known amounts of naturally occurring impurities (Fe P0 4 , A1P0 4 , Ca3(P04)Z and Mg 3(P0 4 )Z) were examined. The hydrodynamic characteristics of the systems were also studied. The experimental results obtained for drop size distribution were compared with those obtainable from Hinze's equation (32) and it was found that they deviated by an amount related to the turbulence. A comprehensive literature survey on the purification of wet-process phosphoric acid by organic solvents has been made. The literature regarding solvent extraction fundamentals and equipment and optimization methods for the envisaged process was also reviewed. A modified form of the Kremser-Brown and Souders equation to calculate the number of contact stages was derived. The modification takes into account the special nature of phosphoric acid distribution curves in the studied systems. The process flow-sheet was developed and simulated. Powell's direct search optimization method was selected in conjunction with the linear search algorithm of Davies, Swann and Campey. The objective function was defined as the total annual manufacturing cost and the program was employed to find the optimum operating conditions for anyone of the chosen solvents. The final results demonstrated the following order of feasibility to purify wet-process acid: di-isopropyl ether, methylisobutyl ketone, n-amyl alcohol and tri-n-butyl phosphate.

Solvent extraction of phosphoric acid

This work investigated the purification of phosphoric acid using a suitable organic solvent, followed by re-extraction of the acid from the solvent using water. The work consisted of practical batch and continuous studies and the economics and design of a full scale plant, based on the experimental data. A comprehensive literature survey on the purification of wet process phosphoric acid by organic solvents is presented and the literature describing the design and operation of mixer-settlers has also been reviewed. In batch studies, the equilibrium and distribution curves for the systems water-phosphoric acid-solvent for Benzaldehyde, Cyclohexanol and Methylisobutylketone (MIBK) were determined together with hydrodynamic characteristics for both pure and impure systems. The settling time increased with acid concentration, but power input had no effect. Drop size was found to reduce with acid concentration and power input. For the continuous studies a novel horizontal mixer~settler cascade was designed, constructed and operated using pure and impure acid with MIBK as the solvent. The cascade incorporates three air turbine agitated, cylindrical 900 ml mixers, and three cylindrical 200 ml settlers with air-lift solvent interstage transfer. Mean drop size in the fully baffled mixer was correlated. Drop size distributions were log-normal and size decreased with acid concentration and power input and increased with dispersed phase hold-up. Phase inversion studies showed that the width of the ambivalent region depended upon rotor speed, hold-up and acid concentration. Settler characteristics were investigated by measuring wedge length. Distribution coefficients of impurities and acid were also investigated. The following optimum extraction conditions were found: initial acid concentration 63%, phase ratio of solvent to acid 1:1 (v/v), impeller speed recommended 900 r.p.m. In the washing step the maximum phase ratio of solvent to water was 8:1 (v/v). Work on phosphoric acid concentration involved constructing distillation equipment consisting of a 10& spherical still. A 100 T/d scale detailed process design including capital cost, operating cost and profitability was also completed. A profit model for phosphoric acid extraction was developed and maximised. Recommendations are made for both the application of the results to a practical design and for extensions of the study.

Optical chemsensors utilizing long-period fiber gratings UV-inscribed in D-fiber with enhanced sensitivity through cladding etching

A novel implementation of an optical chemsensor device is reported based on long-period fiber grating structures ultraviolet-inscribed in D-fiber, with sensitivity enhancement by cladding etching. The results of a comparative study using D-fiber devices and similar structures in standard optical fiber reveal that the D-fiber devices offer substantially greater sensitivity both with and without etching. Based on a calibrated response to changes in refractive index, the grating devices have been used to measure the concentrations of aqueous sugar solutions, demonstrating the potential capability to detect concentration changes as small as 0.2%.

Phosphorus bearing minerals in iron ores and their possible benefication

Modern electron optical techniques together with X-ray and mineralogical examination have been used to study the occurrence and form of phosphorus bearing minerals in iron ores. Three ores have been studied - Bahariya and Aswan from Egypt and Frodingham ironstone from U.K. The iron in the Bahariya iron ore is mainly as hematite and goethite. The gangue minerals are halite, gypsum, barytes, quartz and calcite. Iron content is between 49.8 to 63.2% and phosphorus 0.14 to 0.34%. The phosphorus occurs as very fine particles of apatite which are distributed throughout the ore. Removal of the phosphorus would require very fine grinding followed by acid leaching. Aswan iron ore is an oolitic iron ore; the iron content between 41-57% and phosphorus content 0.1 to 2.9%. It is mainly hematitic with variable quantities of quartz, apatite and small amount of clay minerals. In the oolitic iron ore beds, apatite occurs in the hematite matrix; filling in the pores of the oolithic surfaces, or as matrix cementing the ooliths with the hematite grains. In sandstone claybeds the distribution of the apatite is mainly in the matrix. It is suggested that the liberation size for the apatite would be -80 m and flotation concentration could be applied for the removal of apatite from Aswan ore. Frodingham ironstone occurs in the lower Jurassic bed of the South Humberside area. The average iron content is 25% and the phosphorus is 0.32%. Seven mineral phases were identified by X-ray; calcite, quartz, chamosite, hematite, siderite, apatite, and chlorite. Apatite occurs as very fine grains in the hematite and chamosite ooliths; as matrix of fine grains intergrown with chamosite and calcite grains; and as anhedral and sub rounded grains in the ooliths (8-28 m). It is suggested that two processes are possible for the dephosphorisation; the Flox process or a reduction roast followed by fine grinding, magnetic separation, and acid leaching.

Characteristics of the upper phase of bio-oil obtained from co-pyrolysis of sewage sludge with wood, rapeseed and straw

Sewage sludge was pyrolysed with 40% mixed wood, 40% rapeseed and 40% straw. The reason for the mixture of different biomass is to investigate the impact of co-pyrolysis on the upper phase of bio-oil in terms of changes to composition, elemental analysis, viscosity, water content, pH, higher heating value and acid number that could impact on their applications. The biomass was pyrolysed in a laboratory at 450 °C and bio-oil was collected from two cooling traps. The bio-oil obtained from co-pyrolysis of sewage sludge with wood, rapeseed and straw was analysed for composition using the gas chromatography mass spectrometry. The upper phase from the co-pyrolysis process was also characterised for ultimate analysis, higher heating values, water content, viscosity, pH and acid number. There was an increase in the amount of upper phase produced with co-pyrolysis of 40% rapeseed. It was also found that the upper phase from sewage sludge with mixed wood has the highest viscosity, acid number and lowest pH. The bio-oil containing 40% straw was found to have a pH of 6.5 with a very low acid number while the 40% rapeseed was found to have no acid number. Sewage sludge with 40% rapeseed was found to have the highest energy content of 34.8 MJ/kg, 40% straw has 32.5 MJ/kg while the 40% mixed wood pyrolysis oil has the lowest energy content of 31.3 MJ/kg. The 40% rapeseed fraction was found to have the highest water content of 8.2% compared to other fractions.