A fast XPS study of propene decomposition over clean and sulphated Pt{111}

The thermal decomposition of propene over clean and sulphate precovered Pt{111} has been followed by Fast XPS. The saturation propene coverage over the clean surface is 0.21 mL at 90 K. Propene is stable up to 200 K, above which molecular desorption and dehydrogenation result in the formation of a stable propylidyne intermediate adlayer at 300 K. Propylidyne decomposes above 400 K eventually forming graphitic carbon above 800 K. Preadsorbed surface sulphate promotes room temperature propene combustion associated with the decomposition of a thermally unstable alkyl--sulphate complex. Propylidyne also forms as on clean Pt{111}, but is less reactive, its decomposition above 450 K triggering partial oxidation with residual surface oxygen to liberate gas phase CO.

Effect of methane concentration in hydrogen plasma on hydrogen impurity incorporation in thick large-grained polycrystalline diamond films

We investigate the impact of methane concentration in hydrogen plasma on the growth of large-grained polycrystalline diamond (PCD) films and its hydrogen impurity incorporation. The diamond samples were produced using high CH4 concentration in H2 plasma and high power up to 4350 W and high pressure (either 105 or 110 Torr) in a microwave plasma chemical vapor deposition (MPCVD) system. The thickness of the free-standing diamond films varies from 165 µm to 430 µm. Scanning electron microscopy (SEM), micro-Raman spectroscopy and Fourier-transform infrared (FTIR) spectroscopy were used to characterize the morphology, crystalline and optical quality of the diamond samples, and bonded hydrogen impurity in the diamond films, respectively. Under the conditions employed here, when methane concentration in the gas phase increases from 3.75% to 7.5%, the growth rate of the PCD films rises from around 3.0 µm/h up to 8.5 µm/h, and the optical active bonded hydrogen impurity content also increases more than one times, especially the two CVD diamond specific H related infrared absorption peaks at 2818 and 2828 cm−1 rise strongly; while the crystalline and optical quality of the MCD films decreases significantly, namely structural defects and non-diamond carbon phase content also increases a lot with increasing of methane concentration. Based on the results, the relationship between methane concentration and diamond growth rate and hydrogen impurity incorporation including the form of bonded infrared active hydrogen impurity in CVD diamonds was analyzed and discussed. The effect of substrate temperature on diamond growth was also briefly discussed. The experimental findings indicate that bonded hydrogen impurity in CVD diamond films mainly comes from methane rather than hydrogen in the gas source, and thus can provide experimental evidence for the theoretical study of the standard methyl species dominated growth mechanism of CVD diamonds grown with methane/hydrogen mixtures.

A new regime for high rate growth of nanocrystalline diamond films using high power and CH4/H2/N2/O2 plasma

In this work, we report high growth rate of nanocrystalline diamond (NCD) films on silicon wafers of 2 inches in diameter using a new growth regime, which employs high power and CH4/H2/N2/O2 plasma using a 5 kW MPCVD system. This is distinct from the commonly used hydrogen-poor Ar/CH4 chemistries for NCD growth. Upon rising microwave power from 2000 W to 3200 W, the growth rate of the NCD films increases from 0.3 to 3.4 μm/h, namely one order of magnitude enhancement on the growth rate was achieved at high microwave power. The morphology, grain size, microstructure, orientation or texture, and crystalline quality of the NCD samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, and micro-Raman spectroscopy. The combined effect of nitrogen addition, microwave power, and temperature on NCD growth is discussed from the point view of gas phase chemistry and surface reactions. © 2011 Elsevier B.V. All rights reserved.

Catalyst studies on the ring opening of tetrahydrofuran-dimethanol to 1,2,6-hexanetriol

The metal catalyzed hydrogenolysis of the biomass-derived THF-dimethanol to 1,2,6-hexanetriol using heterogeneous catalysts was investigated. Bimetallic Rh-Re catalysts (4 wt% Rh and a Re/Rh (mol. ratio of 0.5) on a silica support gave the best performance and 1,2,6-hexanetriol was obtained in 84% selectivity at 31% conversion (120 C, 80 bar, 4 h); the selectivity reaches a maximum of 92% at 80 C. The product distribution at prolonged reaction times or higher temperatures or both shows the formation of diols and mono-alcohols, indicating that the 1,2,6-hexanetriol is prone to subsequent hydrodeoxygenation reactions. Different silica supports were investigated and optimal results were obtained with an amorphous silica featuring an intermediate surface area and an average mesopore size of about 6 nm. TPR and XPS surface analysis support the presence of mixed Rh and Re particles. The redox Reδ+/ReTotal surface ratio correlates with the conversion in a volcano type dependency. Both gas phase as well as Rh200Re1OH cluster DFT calculations support an acid-metal bifunctional mechanism and explain the products distribution. © 2013 Elsevier B.V. All rights reserved.

Gravimetric and density profiling using the combination of surface acoustic waves and neutron reflectivity

A new approach is described herein, where neutron reflectivity measurements that probe changes in the density profile of thin films as they absorb material from the gas phase have been combined with a Love wave based gravimetric assay that measures the mass of absorbed material. This combination of techniques not only determines the spatial distribution of absorbed molecules, but also reveals the amount of void space within the thin film (a quantity that can be difficult to assess using neutron reflectivity measurements alone). The uptake of organic solvent vapours into spun cast films of polystyrene has been used as a model system with a view to this method having the potential for extension to the study of other systems. These could include, for example, humidity sensors, hydrogel swelling, biomolecule adsorption or transformations of electroactive and chemically reactive thin films. This is the first ever demonstration of combined neutron reflectivity and Love wave-based gravimetry and the experimental caveats, limitations and scope of the method are explored and discussed in detail.

Studies in three phase gas-liquid-solid fluidised systems

The work is a logical continuation of research started at Aston some years ago when studies were conducted on fermentations in bubble columns. The present work highlights typical design and operating problems that could arise in such systems as waste water, chemical, biochemical and petroleum operations involving three-phase, gas-liquid-solid fluidisation; such systems are in increasing use. It is believed that this is one of few studies concerned with `true' three-phase, gas-liquid-solid fluidised systems, and that this work will contribute significantly to closing some of the gaps in knowledge in this area. The research work was mainly experimentally based and involved studies of the hydrodynamic parameters, phase holdups (gas and solid), particle mixing and segregation, and phase flow dynamics (flow regime and circulation patterns). The studies have focused particularly on the solid behaviour and the influence of properties of solids present on the above parameters in three-phase, gas-liquid-solid fluidised systems containing single particle components and those containing binary and ternary mixtures of particles. All particles were near spherical in shape and two particle sizes and total concentration levels were used. Experiments were carried out in two- and three-dimensional bubble columns. Quantitative results are presented in graphical form and are supported by qualitative results from visual studies which are also shown as schematic diagrams and in photographic form. Gas and solid holdup results are compared for air-water containing single, binary and ternary component particle mixtures. It should be noted that the criteria for selection of the materials used are very important if true three-phase fluidisation is to be achieved: this is very evident when comparing the results with those in the literature. The fluid flow and circulation patterns observed were assessed for validation of the generally accepted patterns, and the author believes that the present work provides more accurate insight into the modelling of liquid circulation in bubble columns. The characteristic bubbly flow at low gas velocity in a two-phase system is suppressed in the three-phase system. The degree of mixing within the system is found to be dependent on flow regime, liquid circulation and the ratio of solid phase physical properties. Evidence of strong `trade-off' of properties is shown; the overall solid holdup is believed to be a major parameter influencing the gas holdup structure.

Evaluation of new processes for the preparation of iron by gas/solid phase systems

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Optical fibre sensors with applications in gas and biological sensing

This thesis describes the study of various grating based optical fibre sensors for applications in refractive index sensing. The sensitivity of these sensors has been studied and in some cases enhanced using novel techniques. The major areas of development are as follows. The sensitivity of long period gratings (LPGs) to surrounding medium refractive index (SRI) for various periods was investigated. The most sensitive period of LPG was found to be around 160 µm and this was due to the core mode coupling to a single cladding mode but phase matching at two wavelength locations, creating two attenuation peaks, close to the waveguide dispersion turning point. Large angle tilted fibre gratings (TFGs) have similar behaviour to LPGs, in that they couple to the co-propagating cladding modes. The tilted structure of the index modulation within the core of the fibre gives rise to a polarisation dependency, differing the large angle TFG from a LPG. Since the large angle TFG couple to the cladding mode they are SRI sensitive, the sensitivity to SRI can be further increased through cladding etching using HF acid. The thinning of the cladding layer caused a reordering of the cladding modes and shifted to more SRI sensitive cladding modes as the investigation discovered. In a SRI range of 1.36 to 1.40 a sensitivity of 506.9 nm/URI was achieved for the etched large angle TFG, which is greater than the dual resonance LPG. UV inscribed LPGs were coated with sol-gel materials with high RIs. The high RI of the coating caused an increase in cladding mode effective index which in turn caused an increase in the LPG sensitivity to SRI. LPGs of various periods of LPG were coated with sol-gel TiO2 and the optimal thickness was found to vary for each period. By coating of the already highly SRI sensitive 160µm period LPG (which is a dual resonance) with a sol-gel TiO2, the SRI sensitivity was further increased with a peak value of 1458 nm/URI, which was an almost 3 fold increase compared to the uncoated LPG. LPGs were also inscribed using a femtosecond laser which produced a highly focused index change which was no uniform throughout the core of the optical fibre. The inscription technique gave rise to a large polarisation sensitivity and the ability to couple to multiple azimuthal cladding mode sets, not seen with uniform UV inscribed gratings. Through coupling of the core mode to multiple sets of cladding modes, attenuation peaks with opposite wavelength shifts for increasing SRI was observed. Through combining this opposite wavelength shifts, a SRI sensitivity was achieved greater than any single observed attenuations peak. The maximum SRI achieved was 1680 nm/URI for a femtosecond inscribed LPG of period 400 µm. Three different types of surface plasmon resonance (SPR) sensors with a multilayer metal top coating were investigated in D shape optical fibre. The sensors could be separated into two types, utilized a pre UV inscribed tilted Bragg grating and the other employed a post UV exposure to generate surface relief grating structure. This surface perturbation aided the out coupling of light from the core but also changed the sensing mechanism from SPR to localised surface plasmon resonance (LSPR). This greatly increased the SRI sensitivity, compared to the SPR sensors; with the gold coated top layer surface relief sensor producing the largest SRI sensitivity of 2111.5nm/URI was achieved. While, the platinum and silver coated top layer surface relief sensors also gave high SRI sensitivities but also the ability to produce resonances in air (not previously seen with the SPR sensors). These properties were employed in two applications. The silver and platinum surface relief devices were used as gas sensors and were shown to be capable of detecting the minute RI change of different gases. The calculated maximum sensitivities produced were 1882.1dB/URI and 1493.5nm/URI for silver and platinum, respectively. Using a DFB laser and power meter a cheap alternative approach was investigated which showed the ability of the sensors to distinguish between different gases and flow rates of those gases. The gold surface relief sensor was coated in a with a bio compound called an aptamer and it was able to detect various concentrations of a biological compound called Thrombin, ranging from 1mM to as low as 10fM. A solution of 2M NaCl was found to give the best stripping results for Thrombin from the aptamer and showed the reusability of the sensor. The association and disassociation constants were calculated to be 1.0638×106Ms-1 and 0.2482s-1, respectively, showing the high affinity of the Aptamer to thrombin. This supports existing working stating that aptamers could be alternative to enzymes for chemical detection and also helps to explain the low detection limit of the gold surface relief sensor.

Low refractive index gas sensing using a Surface Plasmon Resonance fibre device

A series of surface plasmonic fibre devices were fabricated using multiple coatings deposited on a lapped section of a single mode fibre. Coupling from the guided mode to surface plasmons was promoted following UV laser irradiation of the coated region through a phase mask, which generated a surface relief grating structure. The devices showed high spectral sensitivities and strong coupling for low refractive indices as compared to other grating-type fibre devices. The plasmonic devices were used to detect the variation in the refractive indices of alkane gases with measured wavelength and coupling sensitivity to index of 3400 nm RIU-1 and 8300 dB RIU-1, respectively. As a demonstration of the performance of these gas sensors, a minimum concentration of 2% by volume of butane in ethane was achieved.

A methodology for evaluating and selecting processes for natural gas conditioning

The aim of this work was to develop a generic methodology for evaluating and selecting, at the conceptual design phase of a project, the best process technology for Natural Gas conditioning. A generic approach would be simple and require less time and would give a better understanding of why one process is to be preferred over another. This will lead to a better understanding of the problem. Such a methodology would be useful in evaluating existing, novel and hybrid technologies. However, to date no information is available in the published literature on such a generic approach to gas processing. It is believed that the generic methodology presented here is the first available for choosing the best or cheapest method of separation for natural gas dew-point control. Process cost data are derived from evaluations carried out by the vendors. These evaluations are then modelled using a steady-state simulation package. From the results of the modelling the cost data received are correlated and defined with respect to the design or sizing parameters. This allows comparisons between different process systems to be made in terms of the overall process. The generic methodology is based on the concept of a Comparative Separation Cost. This takes into account the efficiency of each process, the value of its products, and the associated costs. To illustrate the general applicability of the methodology, three different cases suggested by BP Exploration are evaluated. This work has shown that it is possible to identify the most competitive process operations at the conceptual design phase and illustrate why one process has an advantage over another. Furthermore, the same methodology has been used to identify and evaluate hybrid processes. It has been determined here that in some cases they offer substantial advantages over the separate process techniques.

Models of gas-liquid solubilities

A recent method for phase equilibria, the AGAPE method, has been used to predict activity coefficients and excess Gibbs energy for binary mixtures with good accuracy. The theory, based on a generalised London potential (GLP), accounts for intermolecular attractive forces. Unlike existing prediction methods, for example UNIFAC, the AGAPE method uses only information derived from accessible experimental data and molecular information for pure components. Presently, the AGAPE method has some limitations, namely that the mixtures must consist of small, non-polar compounds with no hydrogen bonding, at low moderate pressures and at conditions below the critical conditions of the components. Distinction between vapour-liquid equilibria and gas-liquid solubility is rather arbitrary and it seems reasonable to extend these ideas to solubility. The AGAPE model uses a molecular lattice-based mixing rule. By judicious use of computer programs a methodology was created to examine a body of experimental gas-liquid solubility data for gases such as carbon dioxide, propane, n-butane or sulphur hexafluoride which all have critical temperatures a little above 298 K dissolved in benzene, cyclo-hexane and methanol. Within this methodology the value of the GLP as an ab initio combining rule for such solutes in very dilute solutions in a variety of liquids has been tested. Using the GLP as a mixing rule involves the computation of rotationally averaged interactions between the constituent atoms, and new calculations have had to be made to discover the magnitude of the unlike pair interactions. These numbers have been seen as significant in their own right in the context of the behaviour of infinitely-dilute solutions. A method for extending this treatment to "permanent" gases has also been developed. The findings from the GLP method and from the more general AGAPE approach have been examined in the context of other models for gas-liquid solubility, both "classical" and contemporary, in particular those derived from equations-of-state methods and from reference solvent methods.

The chemistry of British bituminous coals : an assessment of phase transfer catalysed reactions in the determination of coal structure

Three British bituminous coals, (Gedling, Cresswell, and Cortonwood Silkstone) were selected for study. Procedures were developed, using phase transfer catalysts (PTC's), to degrade the solvent insoluble fractions of the coals. PTC's are of interest because they have the potential to bring about selective high conversion reactions, under mild conditions, (often in the past, severe reaction conditions have had to be used to degrade the coals, this in turn resulted in the loss of much of the structural information). We have applied a variety of physical and chemical techniques to maximise the amount of structural information, these include, elemental analysis, 1H-NMR, 13C-CPMAS-NMR, GPC, GC-MS, FTIR spectroscopy, DRIFT spectroscopy, and gas adsorption measurements. The main conclusions from the work are listed below:- ( 1 ) PTC O-methylation; This reaction removes hydrogen bonds within the coal matrix by 'capping' the phenolic groups. It was found that the polymer-like matrix could be made more flexible, but not significantly more soluble, by O-methylation. I.E. the trapped or 'mobile' phase of the coals could be removed at a faster rate after this reaction had been carried out. ( 2 ) PTC Reductive and Acidic Ether Cleavage; The three coals were found to contain insignificant amounts of dialkyl and alkyl aryl ethers. The number of diaryl ethers could not be estimated, by reductive ether cleavage, (even though a high proportion of all three coals was solublised). The majority of the ethers present in the coals were inert to both cleavage methods, and are therefore assumed to be heterocyclic ethers. ( 3 ) Trif!uoroperacetic Acid Oxidation; This oxidant was used to study the aliphatic portions of the polymer-like macromolecular matrix of the coals. Normally this reagent will only solublise low rank coals, we however have developed a method whereby trifluoroperacetic acid can be used to degrade high rank bituminous coals. ( 4 ) PTC/Permanganate Oxidation; This reagent has been found to be much more selective than the traditional alkaline permanganate oxidation, with a lot more structural information being retained within the various fractions. This degradative method therefore has the potential of yielding new information about the molecular structure of coals.

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.

Preparation and characterization of gas-filled liposomes:Can they improve oil recovery?

Although well known for delivering various pharmaceutical agents, liposomes can be prepared to entrap gas rather than aqueous media and have the potential to be used as pressure probes in magnetic resonance imaging (MRI). Using these gas-filled liposomes (GFL) as tracers, MRI imaging of pressure regions of a fluid flowing through a porous medium could be established. This knowledge can be exploited to enhance recovery of oil from the porous rock regions within oil fields. In the preliminary studies, we have optimized the lipid composition of GFL prepared using a simple homogenization technique and investigated key physico-chemical characteristics (size and the physical stability) and their efficacy as pressure probes. In contrast to the liposomes possessing an aqueous core which are prepared at temperatures above their phase transition temperature (Tc), homogenization of the phospholipids such as 1,2-dipalmitoyl-sn-glycero-3- phosphocholine (DPPC) or 1,2-distearoyl-sn-glycero-3-phosphocoline (DSPC) in aqueous medium below their Tc was found to be crucial in formation of stable GFL. DSPC based preparations yielded a GFL volume of more than five times compared to their DPPC counter part. Although the initial vesicle sizes of both DSPC and DPPC based GFL were about 10 μm, after 7 days storage at 25°C, the vesicle sizes of both formulations significantly (p < 0.05) increased to 28.3 ± 0.3 μm and 12.3 ± 1.0 μm, respectively. When the DPPC preparation was supplemented with cholesterol at a 1:0.5 or 1:1 molar ratio, significantly (p < 0.05) larger vesicles were formed (12-13 μm), however, compared to DPPC only vesicles, both cholesterol supplemented formulations displayed enhanced stability on storage indicating a stabilizing effect of cholesterol on these gas-filled vesicles. In order to induce surface charge on the GFL, DPPC and cholesterol (1: 0.5 molar ratio) liposomes were supplemented with a cationic surfactant, stearylamine, at a molar ratio of 0.25 or 0.125. Interestingly, the ζ potential values remained around neutrality at both stearylamine ratios suggesting the cationic surfactant was not incorporated within the bilayers of the GFL. Microscopic analysis of GFL confirmed the presence of spherical structures with a size distribution between 1-8 μm. This study has identified that DSPC based GFL in aqueous medium dispersed in 2% w/v methyl cellulose although yielded higher vesicle sizes over time were most stable under high pressures exerted in MRI. Copyright © Informa Healthcare USA, Inc.