Upgrading fast pyrolysis liquids:blends of biodiesel and pyrolysis oil

Fast pyrolysis liquid or bio-oil has been used in engines with limited success. It requires a pilot fuel and/or an additive for successful combustion and there are problems with materials and liquid properties. It is immiscible with all conventional hydrocarbon fuels. Biodiesel, a product of esterification of vegetable oil with an alcohol, is widely used as a renewable liquid fuel as an additive to diesel at up to 20%. There are however limits to its use in conventional engines due to poor low temperature performance and variability in quality from a variety of vegetable oil qualities and variety of esterification processes. Within the European Project Bioliquids-CHP - a joint project between the European Commission and Russia - a study was undertaken to develop small scale CHP units based on engines and microturbines fuelled with bioliquids from fast pyrolysis and methyl esters of vegetable oil. Blends of bio-oil and biodiesel were evaluated and tested to overcome some of the disadvantages of using either fuel by itself. An alcohol was used as the co-solvent in the form of ethanol, 1-butanol or 2-propanol. Visual inspection of the blend homogeneity after 48 h was used as an indicator of the product stability and the results were plotted in a three phase chart for each alcohol used. An accelerated stability test was performed on selected samples in order to predict its long term stability. We concluded that the type and quantity of alcohol is critical for the blend formation and stability. Using 1-butanol gave the widest selection of stable blends, followed by blends with 2-propanol and finally ethanol, thus 1-butanol blends accepted the largest proportion of bio-oil in the mixture. © 2013 Elsevier Ltd. All rights reserved.

Simultaneous clock recovery and data regeneration using a nonlinear optical loop mirror as an all-optical mixer

High-speed optical clock recovery, demultiplexing and data regeneration will be integral parts of any future photonic network based on high bit-rate OTDM. Much research has been conducted on devices that perform these functions, however to date each process has been demonstrated independently. A very promising method of all-optical switching is that of a semiconductor optical amplifier-based nonlinear optical loop mirror (SOA-NOLM). This has various advantages compared with the standard fiber NOLM, most notably low switching power, compact size and stability. We use the SOA-NOLM as an all-optical mixer in a classical phase-locked loop arrangement to achieve optical clock recovery, while at the same time achieving data regeneration in a single compact device

Environmental scanning electron microscopy offers real-time morphological analysis of liposomes and niosomes

Liposomes have been imaged using a plethora of techniques. However, few of these methods offer the ability to study these systems in their natural hydrated state without the requirement of drying, staining, and fixation of the vesicles. However, the ability to image a liposome in its hydrated state is the ideal scenario for visualization of these dynamic lipid structures and environmental scanning electron microscopy (ESEM), with its ability to image wet systems without prior sample preparation, offers potential advantages to the above methods. In our studies, we have used ESEM to not only investigate the morphology of liposomes and niosomes but also to dynamically follow the changes in structure of lipid films and liposome suspensions as water condenses on to or evaporates from the sample. In particular, changes in liposome morphology were studied using ESEM in real time to investigate the resistance of liposomes to coalescence during dehydration thereby providing an alternative assay of liposome formulation and stability. Based on this protocol, we have also studied niosome-based systems and cationic liposome/DNA complexes. Copyright © Informa Healthcare.

Biochemical markers and contact lens wear

The project objective was to develop a reliable selection procedure to match contact lens materials with individual wearers by the identification of a biochemical marker for assessment of in-eye performance of contact lenses. There is a need for such a procedure as one of the main reasons for contact lens wearers ceasing wearing contact lenses is poor end of day comfort i.e. the lenses become intolerable to the wearer as the day progresses. The selection of an optimal material for individual wearers has the potential benefit to reduce drop Qut, hence increasing the overall contact lens population, and to improve contact lens comfort for established wearers. Using novel analytical methods and statistical techniques, we were able to investigate the interactions between the composition of the tear film and of the biofilm deposited on the contact lenses and contact lens performance. The investigations were limited to studying the lipid components of the tear film; the lipid layer, which plays a key role in preventing evaporation and stabilising the tear film, has been reported to be significantly thinner and of different mixing characteristics during contact lens wear. Different lipid families were found to influence symptomatology, in vivo tear film structure and stability as well as ocular integrity. Whereas the symptomatology was affected by both the tear film lipid composition and the nature of the lipid deposition, the structure of the tear film and its stability were mainly influenced by the tear film lipid composition. The ocular integrity also appeared to be influenced by the nature of the lipid deposition. Potential markers within the lipid species have been identified and could be applied as follows: When required in order to identify a problematic wearer or to match the contact lens material to the contact lens wearer, tear samples collected by the clinician could be dispatched to an analytical laboratory where lipid analysis could be carried out by HPLC. A colorimetric kit based on the lipid markers could also be developed and used by clinician directly in the practice; such a kit would involve tear sampling and classification according to the colour into "Problem", "Border line" and "Good" contact lens wearers groups. A test kit would also have wider scope for marketing in other areas such as general dry-eye pathology.

The characterisation and optimisation of modified herbaceous grasses for identifying pyrolisis-oil quality traits

The primary objective of this work is to relate the biomass fuel quality to fast pyrolysis-oil quality in order to identify key biomass traits which affect pyrolysis-oil stability. During storage the pyrolysis-oil becomes more viscous due to chemical and physical changes, as reactions and volatile losses occur due to aging. The reason for oil instability begins within the pyrolysis reactor during pyrolysis in which the biomass is rapidly heated in the absence of oxygen, producing free radical volatiles which are then quickly condensed to form the oil. The products formed do not reach thermodynamic equilibrium and in tum the products react with each other to try to achieve product stability. The first aim of this research was to develop and validate a rapid screening method for determining biomass lignin content in comparison to traditional, time consuming and hence costly wet chemical methods such as Klason. Lolium and Festuca grasses were selected to validate the screening method, as these grass genotypes exhibit a low range of Klason /Acid Digestible Fibre lignin contents. The screening methodology was based on the relationship between the lignin derived products from pyrolysis and the lignin content as determined by wet chemistry. The second aim of the research was to determine whether metals have an affect on fast pyrolysis products, and if any clear relationships can be deduced to aid research in feedstock selection for fast pyrolysis processing. It was found that alkali metals, particularly Na and K influence the rate and yield of degradation as well the char content. Pre-washing biomass with water can remove 70% of the total metals, and improve the pyrolysis product characteristics by increasing the organic yield, the temperature in which maximum liquid yield occurs and the proportion of higher molecular weight compounds within the pyrolysis-oil. The third aim identified these feedstock traits and relates them to the pyrolysis-oil quality and stability. It was found that the mineral matter was a key determinant on pyrolysis-oil yield compared to the proportion of lignin. However the higher molecular weight compounds present in the pyrolysis-oil are due to the lignin, and can cause instability within the pyrolysis-oil. The final aim was to investigate if energy crops can be enhanced by agronomical practices to produce a biomass quality which is attractive to the biomass conversion community, as well as giving a good yield to the farmers. It was found that the nitrogen/potassium chloride fertiliser treatments enhances Miscanthus qualities, by producing low ash, high volatiles yields with acceptable yields for farmers. The progress of senescence was measured in terms of biomass characteristics and fast pyrolysis product characteristics. The results obtained from this research are in strong agreement with published literature, and provides new information on quality traits for biomass which affects pyrolysis and pyrolysis-oils.

Effect of extrusion and photo-oxidation on polyethylene/clay nanocomposites

Polyethylene (a 1:1 blend of m-LLDPE and z-LLDPE) double layer silicate clay nanocomposites were prepared by melt extrusion using a twin screw extruder. Maleic anhydride grafted polyethylene (PEgMA) was used as a compatibiliser to enhance the dispersion of two organically modified monmorilonite clays (OMMT): Closite 15A (CL15) and nanofill SE 3000 (NF), and natural montmorillonite (NaMMT). The clay dispersion and morphology obtained in the extruded nanocomposite samples were fully characterised both after processing and during photo-oxidation by a number of complementary analytical techniques. The effects of the compatibiliser, the organoclay modifier (quartenary alkyl ammonium surfactant) and the clays on the behaviour of the nanocomposites during processing and under accelerated weathering conditions were investigated. X-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy (SEM), rheometry and attenuated reflectance spectroscopy (ATR-FTIR) showed that the nanocomposite structure obtained is dependent on the type of clay used, the presence or absence of a compatibiliser and the environment the samples are exposed to. The results revealed that during processing PE/clay nanocomposites are formed in the presence of the compatibiliser PEgMA giving a hybrid exfoliated and intercalated structures, while microcomposites were obtained in the absence of PEgMA; the unmodified NaMMT-containing samples showed encapsulated clay structures with limited extent of dispersion in the polymer matrix. The effect of processing on the thermal stability of the OMMT-containing polymer samples was determined by measuring the additional amount of vinyl-type unsaturation formed due to a Hoffman elimination reaction that takes place in the alkyl ammonium surfactant of the modified clay at elevated temperatures. The results indicate that OMMT is responsible for the higher levels of unsaturation found in OMMT-PE samples when compared to both the polymer control and the NaMMT-PE samples and confirms the instability of the alkyl ammonium surfactant during melt processing and its deleterious effects on the durability aspects of nanocomposite products. The photostability of the PE/clay nanocomposites under accelerated weathering conditions was monitored by following changes in their infrared signatures and mechanical properties. The rate of photo-oxidation of the compatibilised PE/PEgMA/OMMT nanocomposites was much higher than that of the PE/OMMT (in absence of PEgMA) counterparts, the polymer controls and the PE–NaMMT sample. Several factors have been observed that can explain the difference in the photo-oxidative stability of the PE/clay nanocomposites including the adverse role played by the thermal decomposition products of the alkyl ammonium surfactant, the photo-instability of PEgMA, unfavourable interactions between PEgMA and products formed in the polymer as a consequence of the degradation of the surfactant on the clay, as well as a contribution from a much higher extent of exfoliated structures, determined by TEM, formed with increasing UV-exposure times.

Reactive processing of polymers: structural characterization of products by 1H and 13C NMR spectroscopy for glycidyl methacrylate grafting onto EPR in the absence and presence of a reactive comonomer

Grafted GMA on EPR samples were prepared in a Thermo-Haake internal mixer by free radical melt grafting reactions in the absence (conventional system; EPR-g-GMA(CONV)) and presence of the reactive comonomer divinyl benzene, DVB (EPR-g-GMA(DVB)). The GMA-homopolymer (poly-GMA), a major side reaction product in the conventional system, was almost completely absent in the DVB-containing system, the latter also resulted in a much higher level of GMA grafting. A comprehensive microstructure analysis of the formed poly-GMA was performed based on one-dimensional H-1 and C-13 NMR spectroscopy and the complete spectral assignments were supported by two-dimensional NMR techniques based on long range two and three bond order carbon-proton couplings from HMBC (Heteronuclear Multiple Bond Coherence) and that of one bond carbon-proton couplings from HSQC (Heteronuclear Single Quantum Coherence), as well as the use of Distortionless Enhancement by Polarization Transfer (DEPT) NMR spectroscopy. The unambiguous analysis of the stereochemical configuration of poly-GMA was further used to help understand the microstructures of the GMA-grafts obtained in the two different free radical melt grafting reactions, the conventional and comonomer-containing systems. In the grafted GMA, in the conventional system (EPR-g-GMA(CONV)), the methylene protons of the GMA were found to be sensitive to tetrad configurational sequences and the results showed that 56% of the GMA sequence in the graft is in atactic configuration and 42% is in syndiotactic configuration whereas the poly-GMA was predominantly syndiotactic. The differences in the microstructures of the graft in the conventional EPR-g-GMA(CONV) and the DVB-containing (EPR-g-GMA(DVB)) systems is also reported (C) 2009 Elsevier Ltd. All rights reserved.

Effect of contact surfaces on the thermal and photoxidation of dehydrated castor oil

The effect of stainless steel, glass, zirconium and titanium enamel surfaces on the thermal and photooxidative toughening mechanism of dehydrated castor oil films deposited on these surfaces was investigated using different analytical and spectroscopic methods. The conjugated and non-conjugated double bonds were identified and quantified using both Raman spectroscopy and 1D and 2D NMR spectroscopy. The disappearance of the double bonds in thermally oxidised oil-on-surface films was shown to be concomitant with the formation of hydroperoxides (determined by iodometric titration). The type of the surface had a major effect on the rate of thermal oxidation of the oil, but all of the surfaces examined had resulted in a significantly higher rate of oxidation compared to that of the neat oil. The highest effect was exhibited by the stainless steel surface followed by zirconium enamel, titanium enamel and glass. The rate of thermal oxidation of the oil-on-steel surface (at 100 °C, based on peroxide values) was more than five times faster than that of oil-on-glass and more than 21 times faster than the neat oil when compared under similar thermal oxidative conditions. The rate of photooxidation at 60 °C of oil-on-steel films was found to be about one and half times faster than their rate of thermal oxidation at the same temperature. Results from absorbance reflectance infrared microscopy with line scans taken across the depth of thermally oxidised oil-on-steel films suggest that the thermal oxidative toughening mechanism of the oil occurs by two different reaction pathways with the film outermost layers, i.e. furthest away from the steel surface, oxidising through a traditional free radical oxidation process involving the formation of various oxygenated products formed from the decomposition of allylic hydroperoxides, whereas, in the deeper layers closer to the steel surface, crosslinking reactions predominate.

Nonlinear spectral shaping and optical rogue events in fiber-based systems

We provide an overview of our recent work on the shaping and stability of optical continua in the long pulse regime. Fibers with normal group-velocity dispersion at all-wavelengths are shown to allow for highly coherent continua that can be nonlinearly shaped using appropriate initial conditions. In contrast, supercontinua generated in the anomalous dispersion regime are shown to exhibit large fluctuations in the temporal and spectral domains that can be controlled using a carefully chosen seed. A particular example of this is the first experimental observation of the Peregrine soliton which constitutes a prototype of optical rogue-waves.

Reactive processing of polymers:effect of bifunctional and tri-functional comonomers on melt grafting of glycidyl methacrylate onto polypropylene

Two reactive comonomers, divinyl benzene (DVB) and trimethylolpropane triacrylate (TRIS), were evaluated for their role in effecting the melt free radical grafting reaction of the monomer glycidyl methacrylate (GMA) onto polypropylene (PP). The characteristics of the GMA-grafting systems in the presence and absence of DVB or TRIS were examined and compared in terms of the yield of the grafting reaction and the extent of the main side reactions, namely homopolymerisation of GMA (poly-GMA) and polymer degradation, using different chemical compositions of the reactive systems and processing conditions. In the absence of the comonomers, i.e. in a conventional system, high initiator concentrations of peroxides were typically required to achieve the highest possible GMA grafting levels which were found to be generally low. Concomitantly, both poly-GMA and degradation of the polymer by chain scission takes place with increasing initiator amounts. On the other hand, the presence of a small amount of the comonomers, DVB or Tris, in the GMA-grafting system, was shown to bring about a significant increase in the grafting level paralleled by a large reduction in poly-GMA and PP degradation. In the presence of these highly reactive comonomers, the optimum grafting system requires a much lower concentration of the peroxide initiator and, consequently, would lead to the much lower degree of polymer degradation observed in these systems. The differences in the effects of the presence of DVB and that of TRIS in the grafting systems on the rate of the GMA-grafting and homopolymerisation reactions, and the extent of PP degradation (through melt flow changes), were compared and contrasted with a conventional GMA-grafting system.

Comparison of hydrophilic and hydrophobic active molecules release from polymer-phospholipid complexes

Hypercoiling polymers can be suited for application to living systems because they are similar in structure to the protein-based lipid assemblies found at fluid interfaces within the body. This leads to a range of exciting possibilities, not only in membrane transport applications but also in biosensors, drug delivery and mechanistic studies of biological membrane function. This study is focused in the study of the stability and suitability of nanostructures made of a hypercoiling polymer for drug delivery applications. The polymer poly (styrene-maleic acid) (PSMA) was combined with the phospholipid dimyristoylphosphatidylcholine (DMPC) to form amphiphilic nanostructures. The stability and suitability of these polymer-phospholipid nanocarriers for hydrophobic and hydrophilic molecules load and release was analyzed by several techniques. It was found that several of the studied molecules had a substantial effect on the surface charge and stability of the nanocarrier. It was also demonstrated that two types of nanocarriers, chemically modified and unmodified, were able to control the release of the molecules, especially in the case of hydrophobic compounds. In addition, as the hydrophobicity increased the release slowed down. These clear nanocarriers have the potential to behave very favorably at interfaces such as the tear lipid film were transparency is a requirement, giving a new way of controlled drug release in the eye.

Loan loss provisions, bank valuations and discretion : a comparative study between conventional and Islamic banks

This study investigates the use of reported loan loss provisions (LLP) by investors in their valuations of banks within the Middle East and North Africa region between the years 2006 and 2011. We decompose LLP into discretionary and non-discretionary components to test for differential valuations in the two banking sectors. We use alternative criteria to define the components of LLP in banks: loan quality/size and earnings management/ manipulation incentives. We employ a price-level valuation model estimated using two-stage analyses. We find that LLP has positive value relevance to investors in both banking sectors. Investors in Islamic banks price the discretionary component relatively lower than their conventional counterparts. We attribute this result to differences in product and governance structures as well as to the religious perception of Islamic banking. In both banking sectors, investors construe an increase in the non-discretionary component as irrelevant valuation information. Our results are relevant to bank regulators in showing the signalling effect of LLP to bank value and stability.

The study and measurements of the behaviour and characteristics of electromagnetic relays

The thesis presents a theoretical and practical study of the dynamic behaviour of electromagnetic relays. After discussing the problem of solving the dynamicc equations analytically and presenting a historical survey of the earlier works in the relay and its dynamics, the simulation of a relay on the analogue computer is discussed. It is shown that the simulation may be used to obtain specific solutions to the dynamic equations. The computer analysis provides the dynamic characteristics for design purposes and may be used in the study of bouncing, rebound oscillations and stability of the armature motion. An approximate analytical solution to the two dynamic equations is given based on the assumption that the dynamic variation of the pull with the position of the armature is linear. The assumption is supported by the Computer-aided analysis and experimental results. The solution is intended to provide a basis for a rational design. A rigorous method of analysing the dynamic performance by using Ahlberg's theory is also presented. This method may be justified to be the extension of Ahlberg's theory by taking the mass and frictional damping forces into account. While calculating the armature motion mathematically, Ahlberg considers the equilibrium of two kinds of forces, namely pull and load, and disregards the mass and friction forces, whereas the present method deals with the equilibrium of all four kinds of forces. It is shown how this can be utilised to calculate the dynamic characteristics for a specific design. The utility of this method also extends to the study of stability, contact bounce and armature rebound. The magnetic circuit and other related topics which are essential to the study of relay dynamics are discussed and some necessary experimental results are given.

Nonlinear spectral shaping and optical rogue events in fiber-based systems

We provide an overview of our recent work on the shaping and stability of optical continua in the long pulse regime. Fibers with normal group-velocity dispersion at all-wavelengths are shown to allow for highly coherent continua that can be nonlinearly shaped using appropriate initial conditions. In contrast, supercontinua generated in the anomalous dispersion regime are shown to exhibit large fluctuations in the temporal and spectral domains that can be controlled using a carefully chosen seed. A particular example of this is the first experimental observation of the Peregrine soliton which constitutes a prototype of optical rogue-waves. © 2012 Elsevier Inc. All rights reserved.

Simultaneous clock recovery and data regeneration using a nonlinear optical loop mirror as an all-optical mixer

High-speed optical clock recovery, demultiplexing and data regeneration will be integral parts of any future photonic network based on high bit-rate OTDM. Much research has been conducted on devices that perform these functions, however to date each process has been demonstrated independently. A very promising method of all-optical switching is that of a semiconductor optical amplifier-based nonlinear optical loop mirror (SOA-NOLM). This has various advantages compared with the standard fiber NOLM, most notably low switching power, compact size and stability. We use the SOA-NOLM as an all-optical mixer in a classical phase-locked loop arrangement to achieve optical clock recovery, while at the same time achieving data regeneration in a single compact device