Experimental investigation of the fuel properties of glidfuel, palm oil mill effluent biodiesel and blends

Biofuels derived from industry waste have potential to substitute fossil fuels (Diesel and Gasoline) in internal combustion (IC) engines. Use of waste streams as fuels would help to reduce considerably life-cycle greenhouse gas emissions and minimise waste processing costs. In this study an investigation into the fuel properties of two waste derived biofuels were carried out, they are: (i) Glidfuel (GF) biofuel - a waste stream from paper industry, and (ii) Palm Oil Mill Effluent (POME) biodiesel - biodiesel produced from palm oil industry effluent through various treatment and transesterification process. GF and POME was mixed together at various proportions and separately with fossil diesel (FD) to assess the miscibility and various physical and chemical properties of the blends. Fuel properties such as kinematic viscosity, higher heating value, water content, acid number, density, flash point temperature, CHNO content, sulphur content, ash content, oxidation stability, cetane number and copper corrosion ratings of all the fuels were measured. The properties of GF, POME and various blends were compared with the corresponding properties of the standard FD. Significance of the fuel properties and their expected effects on combustion and exhaust emission characteristics of the IC engine were discussed. Results showed that most properties of both GF and POME biodiesel were comparable to FD. Both GF and POME were miscible with each other, and also separately with the FD. Flash point temperatures of GF and POME biodiesel were 40.7°C and 158.7°C respectively. The flash point temperature of GF was about 36% lower than corresponding FD. The water content in GF and FD were 0.74 (% wt) and 0.01 (% wt) respectively. Acidity values and corrosion ratings of both GF and POME biodiesel were low compared to corresponding value for FD. The study concluded that optimum GF-POME biofuel blends can substitute fossil diesel use in IC engines.

On thermodynamics in the primary power conversion of oscillating water column wave energy converters

The paper presents an investigation to the thermodynamics of the air flow in the air chamber for the oscillating water column wave energy converters, in which the oscillating water surface in the water column pressurizes or de-pressurises the air in the chamber. To study the thermodynamics and the compressibility of the air in the chamber, a method is developed in this research: the power take-off is replaced with an accepted semi-empirical relationship between the air flow rate and the oscillating water column chamber pressure, and the thermodynamic process is simplified as an isentropic process. This facilitates the use of a direct expression for the work done on the power take-off by the flowing air and the generation of a single differential equation that defines the thermodynamic process occurring inside the air chamber. Solving the differential equation, the chamber pressure can be obtained if the interior water surface motion is known or the chamber volume (thus the interior water surface motion) if the chamber pressure is known. As a result, the effects of the air compressibility can be studied. Examples given in the paper have shown the compressibility, and its effects on the power losses for large oscillating water column devices.

The use of binary polymeric networks in stabilising polyethylene oxide solid dispersions

The objective of this study was to determine if a high Tg polymer (Eudragit® S100) could be used to stabilize amorphous domains of polyethylene oxide (PEO) and hence improve the stability of binary polymer systems containing celecoxib (CX). We propose a novel method of stabilizing the amorphous PEO solid dispersion through inclusion of a miscible, high Tg polymer, namely, that can form strong inter-polymer interactions. The effects of inter-polymer interactions and miscibility between PEO and Eudragit S100 are considered. Polymer blends were first manufactured via hot-melt extrusion at different PEO/S100 ratios (70/30, 50/50, and 30/70 wt/wt). Differential scanning calorimetry and dynamic mechanical thermal analysis data suggested a good miscibility between PEO and S100 polymer blends, particularly at the 50/50 ratio. To further evaluate the system, CX/PEO/S100 ternary mixtures were extruded. Immediately after hot-melt extrusion, a single Tg that increased with increasing S100 content (anti-plasticization) was observed in all ternary systems. The absence of powder X-ray diffractometry crystalline Bragg’s peaks also suggested amorphization of CX. Upon storage (40°C/75% relative humidity), the formulation containing PEO/S100 at a ratio of 50:50 was shown to be most stable. Fourier transform infrared studies confirmed the presence of hydrogen bonding between Eudragit S100 and PEO suggesting this was the principle reason for stabilization of the amorphous CX/PEO solid dispersion system.

Fabrication, Optical Analysis and Photonic Applications of Certain Metallic Nanostructure-Integrated Dye Doped Polymer Optical Fibers” submitted by Ms. Suneetha Sebastian

Polymer Optical Fibers have occupied historically a place for large core flexible fibers operating in short distances. In addition to their practical passive application in short-haul communication they constitute a potential research field as active devices with organic dopants. Organic dyes are preferred as dopants over organic semiconductors due to their higher optical cross section. Thus organic dyes as gain media in a polymer fiber is used to develop efficient and narrow laser sources with a tunability throughout the visible region or optical amplifier with high gain. Dyes incorporated in fiber form has added advantage over other solid state forms such as films since the pump power required to excite the molecules in the core of the fiber is less thereby utilising the pump power effectively. In 1987, Muto et.al investigated a dye doped step index polymer fiber laser. Afterwards, numerous researches have been carried out in this area demonstrating laser emission from step index, graded index and hollow optical fibers incorporating various dyes. Among various dyes, Rhodamine6G is the most widely and commonly used laser dye for the last four decades. Rhodamine6G has many desirable optical properties which make it preferable over other organic dyes such as Coumarin, Nile Blue, Curcumin etc. The research focus on the implementation of efficient fiber lasers and amplifiers for short fiber distances. Developing efficient plastic lasers with electrical pumping can be a new proposal in this field which demands lowest possible threshold pump energy of the gain medium in the cavity as an important parameter. One way of improving the efficiency of the lasers, through low threshold pump energy, is by modifying the gain of the amplifiers in the resonator/cavity. Success in the field of Radiative Decay Engineering can pave way to this problem. Laser gain media consisting of dye-nanoparticle composites can improve the efficiency by lowering the lasing threshold and enhancing the photostability. The electric field confined near the surface of metal nanoparticles due to Localized Surface Plasmon Resonance can be very effective for the excitation of active centers to impart high optical gain for lasing. Since the Surface Plasmon Resonance of nanoparticles of gold and silver lies in the visible range, it can affect the spectral emission characteristics of organic dyes such as Rhodamine6G through plasmon field generated by the particles. The change in emission of the dye placed near metal nanoparticles depend on plasmon field strength which in turn depends on the type of metal, size of nanoparticle, surface modification of the particle and the wavelength of incident light. Progress in fabrication of different types of nanostructures lead to the advent of nanospheres, nanoalloys, core-shell and nanowires to name a few. The thesis deals with the fabrication and characterisation of polymer optical fibers with various metallic and bimetallic nanostructures incorporated in the gain media for efficient fiber lasers with low threshold and improved photostability.

Investigations on the structural, optical and magnetic properties of nanostructured cerium oxide in pure and doped forms and its polymer nanocomposites

In recent years, nanoscience and nanotechnology has emerged as one of the most important and exciting frontier areas of research interest in almost all fields of science and technology. This technology provides the path of many breakthrough changes in the near future in many areas of advanced technological applications. Nanotechnology is an interdisciplinary area of research and development. The advent of nanotechnology in the modern times and the beginning of its systematic study can be thought of to have begun with a lecture by the famous physicist Richard Feynman. In 1960 he presented a visionary and prophetic lecture at the meeting of the American Physical Society entitled “there is plenty of room at the bottom” where he speculated on the possibility and potential of nanosized materials. Synthesis of nanomaterials and nanostructures are the essential aspects of nanotechnology. Studies on new physical properties and applications of nanomaterials are possible only when materials are made available with desired size, morphology, crystal structure and chemical composition. Cerium oxide (ceria) is one of the important functional materials with high mechanical strength, thermal stability, excellent optical properties, appreciable oxygen ion conductivity and oxygen storage capacity. Ceria finds a variety of applications in mechanical polishing of microelectronic devices, as catalysts for three-way automatic exhaust systems and as additives in ceramics and phosphors. The doped ceria usually has enhanced catalytic and electrical properties, which depend on a series of factors such as the particle size, the structural characteristics, morphology etc. Ceria based solid solutions have been widely identified as promising electrolytes for intermediate temperature solid oxide fuel cells (SOFC). The success of many promising device technologies depends on the suitable powder synthesis techniques. The challenge for introducing new nanopowder synthesis techniques is to preserve high material quality while attaining the desired composition. The method adopted should give reproducible powder properties, high yield and must be time and energy effective. The use of a variety of new materials in many technological applications has been realized through the use of thin films of these materials. Thus the development of any new material will have good application potential if it can be deposited in thin film form with the same properties. The advantageous properties of thin films include the possibility of tailoring the properties according to film thickness, small mass of the materials involved and high surface to volume ratio. The synthesis of polymer nanocomposites is an integral aspect of polymer nanotechnology. By inserting the nanometric inorganic compounds, the properties of polymers can be improved and this has a lot of applications depending upon the inorganic filler material present in the polymer.

The effect of poly(lactide)-poly(carbonate) based block copolymers on the morphology and crystallization of double crystalline poly(lactide)/poly(ε-caprolactone) blends

Block copolymers of poly(lactide) and poly(carbonate) were synthetized in three different compositions and characterized by 1H-NMR and ATR analyses. The compatibilization effect of this copolymers on 80/20 (w/w%) PLA/PCL blend was evaluated. SEM micrographs show that all the blends exhibit the typical sea-island morphology characteristic of immiscible blends with PCL finely dispersed in droplets on a PLA matrix. Upon the addiction of the copolymers a reduction on PCL droplets size is observable. At the same time, a Tg depression of the PLA phase is detected when the copolymers are added in the blend. These results indicate that these copolymers are effective as compatibilizers. The copolymer that acts as the best compatibilizer is the one characterized by the same amount of PLA and PC as repeating units. As result, in the blend containing this copolymer PLA phase exhibits the highest spherulitic growth rate. An analyses on PLA phase crystallization behaviour from the glassy state within the blends was evaluated by DSC experiments. Isothermal cold crystallization of the PLA phase is enhanced up an order of magnitude upon the blending with PCL. Annealing experiments demonstrated that the crystallization of the PCL phase induces the formation of active nuclei in PLA when cooled above cooled below Tg. When the crystallization rate of PCL is retarded, a reduction on PLA nucleation is observed.

Design of luminescent metal complexes for polymer science

The program of my PhD studies has been dealing with the investigation of the research outcomes that may result from the use of luminescent Iridium(III) cyclometalated complexes in the field of polymer science. In particular, my activity has been focused on exploring two main applicative contexts, i.e. Ir(III) complexes for preparing polymers and in combination with polymers. In the first part, a new set of luminescent Ir(III) complexes was exploited as photocatalysts for light-assisted atom transfer radical polymerization of methyl methacrylate. The decoration of both cyclometalated and ancillary ligands with sp3 hybridized nitrogen substituents together with the use of specific counterions, imparted suitable photophysical and redox properties for an efficient photocatalyzed process. The second part has been focused on the employment of Ir(III) tetrazole complexes as phosphorescent dyes in polymeric materials. Colourless luminescent solar concentrators were prepared blending two Ir(III) cyclometalates with acrylate polymers. Their performances were investigated, leading to promising outcomes comparable, or superior, to those obtained from colourless LSCs based on organic fluorophores. As a complementary approach, Ir(III) complexes were covalently linked to polymers in the side chain, to obtain a new class of metallopolymers. To this extent, a bifunctional tetrazolate molecule, equipped with a coordination site and a polymerizable unit, was designed. The photophysical properties of the resultant luminescent polymeric films were discussed. In the end, an additional project involving both polymers and metal compounds was carried out during my experience as a visiting PhD student at Humboldt – University of Berlin. Polystyrene and polyethylene glycol -based ion-exchange resins were functionalized with peptides through a ligation pathway, for the selective chelation of Copper(II) in aqueous solutions. The coordinating capability of the materials towards Cu2+ ions was tested by ICP-MS analysis. The resins strategically modified with ion-selective peptides, may be exploited in the preparation of water-processing devices.

Compositional and textural properties of milkfat-soybean oil enzymatic interesterification

Milkfat-soybean oil blends were enzymatically interesterified (EIE) by Aspergillus niger lipase immobilized on SiO(2)-PVA hybrid composite in a solvent free system. An experimental mixture design was used to study the effects of binary blends of milkfat-soybean oil (MF:SBO) at different proportions (0:100; 25:75; 33:67; 50:50; 67:33; 75:25; 100:0) on the compositional and textural properties of the EIE products, considering, as response variables, the interesterification yield (IY), consistency and hardness. Lipase-catalysed interesterification reactions increased the relative proportion of TAGs` C(46)-C(52) and decreased the TAGs` C(40)-C(42) and C(54) concentrations. The highest IY was attained (10.8%) for EIE blend of MF:SBO 67:33 resulting in a more spreadable material at refrigerator temperature in comparison with butter, milkfat or non-interesterified (NIE) blend. In this case, consistency and hardness values were at least 32% lower than values measured for butter. Thus, using A. niger lipase immobilized on SiO(2)-PVA improves the textural properties of milkfat and has potential for development of a product incorporating unsaturated and essential fatty acids from soybean oil. (C) 2010 Elsevier Ltd. All rights reserved.

Electronic scraps - Recovering of valuable materials from parallel wire cables

Every year, the number of discarded electro-electronic products is increasing. For this reason recycling is needed, to avoid wasting non-renewable natural resources. The objective of this work is to study the recycling of materials from parallel wire cable through Unit operations of mineral processing. Parallel wire cables are basically composed of polymer and copper. The following unit operations were tested: grinding, size classification, dense medium separation, electrostatic separation, scrubbing, panning, and elutriation. It was observed that the operations used obtained copper and PVC concentrates with a low degree of cross contamination. It was Concluded that total liberation of the materials was accomplished after grinding to less than 3 mm, using a cage mill. Separation using panning and elutriation presented the best results in terms of recovery and cross contamination. (C) 2007 Elsevier Ltd. All rights reserved.

Synthesis and characterization of semiconductor polymers having different phenylene-vinylene conjugation lengths

We have synthesized phenylene-vinylene (PV) polymers containing segments with different conjugation lengths interspaced by random distributed aliphatic segments. Infrared (IR) and ultraviolet-visible (UV-vis) spectroscopies, hydrogen nuclear magnetic resonance ((1)H NMR) spectrometry and differential scanning calorimetry (DSC) were used to characterize the prepared copolymers` structures. Polymers molecular weights were determined by gel permeation chromatography (GPC). The effect of polymer structure and composition on emission properties was studied by fluorescence (PL) spectroscopy under different irradiation wavelength. The emission energy shift due to segments with longer conjugation lengths was minor owed to the low polymerization degree achieved.

Structured lipids obtained by chemical interesterification of olive oil and palm stearin

Interesterification of palm stearin (PS) with liquid vegetable oils could yield a good solid fat stock that may impart desirable physical properties, because PS is a useful source of vegetable hard fat, providing beta` stable solid fats Dietary ingestion of olive oil (OO) has been reported to have physiological benefits such as lowering serum cholesterol levels Fat blends, formulated by binary blends of palm stearin and olive oil in different ratios, were subjected to chemical interesterification with sodium methoxide The original and interesterified blends were examined for fatty acid and triacylglycerol composition, melting point, solid fat content (SFC) and consistency. Interestenfication caused rearrangement of triacylglycerol species, reduction of trisaturated and triunsaturated triacylglycerols content and increase in diunsaturated-monosaturated triacylglycerols of all blends, resulting in lowering of melting point and solid fat content The incorporation of OO to PS reduced consistency, producing more plastic blends The mixture and chemical interesterification allowed obtaining fats with various degrees of plasticity, increasing the possibilities for the commercial use of palm stearin and olive oil (C) 2009 Elsevier Ltd All rights reserved

Free volume and water uptake in a copolymer hydrogel series

A copolymer of X-hydroxyethyl methacrylate (HEMA) with 2-ethoxy ethyl methacrylate (EEMA) was synthesized and the molecular mobility, free volume, and density properties examined as a function of composition. These properties were correlated with the equilibrium water uptake in order to determine which of the properties were most influential in causing high water sorption, as these materials are suitable candidates for hydrogel systems. It was found that the polar HEMA repeat unit results in a rigid, glassy sample at room temperature due to the high degree of hydrogen bonding between chains whereas high EEMA content leads to rubbery samples with subambient glass transition temperatures. The free volume properties on the molecular scale measured by positron annihilation Lifetime spectroscopy (PALS) showed that higher HEMA content led to smaller, fewer holes and a lower free volume fraction than EEMA. Therefore the high water uptake of HEEMA-containing copolymers is largely related to the high polarity of the HEMA unit compared to EEMA, despite the low content of free volume into which the water can initially diffuse. Trends in density with copolymer composition, as measured on a macroscopic level, differs to that seen by PALS and indicates that the two techniques are measuring different scales of packing. (C) 1998 John Wiley & Sons, Inc.

Oxidation mechanism of Si3N4-bonded SiC ceramics by CO, CO2 and steam

This paper presents a theoretical and experimental investigation into the oxidation reactions of Si3N4-bonded SiC ceramics. Such ceramics which contain a small amount of silicon offer increased oxidation and wear resistance and are widely used as lining refractories in blast furnaces. The thermodynamics of oxidation reactions were studied using the JANAF tables. The weight gain was measured using a thermogravimetric analysis technique to study the kinetics. The temperature range of oxidation measurements is from 1073 to 1573 K and the oxidation atmosphere is water vapour, pure CO and CO-CO2 gas mixtures with various CO-to-CO2 ratios. Thermodynamic simulations showed that the oxidation mechanism of Si3N4-bonded SiC ceramics is passive oxidation and all components contribute to the formation of a silica film. The activated energies of the reactions follow the sequence Si3N4>SiC>Si. The kinetic study revealed that the oxidation of Si3N4-bonded SiC ceramics occurred in a mixed regime controlled by both interface reaction and diffusion through the silica film. Under the atmosphere conditions prevailing in the blast furnace, this ceramic is predicted to be passively oxidized with the chemical reaction rate becoming more dominant as the CO concentration increases. (C) 1998 Chapman & Hall.

Encoding combinatorial libraries: A novel application of fluorescent silica colloids

A major challenge associated with using large chemical libraries synthesized on microscopic solid support beads is the rapid discrimination of individual compounds in these libraries. This challenge can be overcome by encoding the beads with 1 mum silica colloidal particles (reporters) that contain specific and identifiable combinations of fluorescent byes. The colored bar code generated on support beads during combinatorial library synthesis can be easily, rapidly, and inexpensively decoded through the use of fluorescence microscopy. All reporters are precoated with polyelectrolytes [poly(acrylic acid), PAA, poly(sodium 4-styrenesulfonate PSSS, polyethylenimine, PEI, and/or poly(diallyldimethylammonium chloride), PDADMAC] with the aim of enhancing surface charge, promoting electrostatic attraction to the bead, and facilitating polymer bridging between the bead and reporter for permanent adhesion. As shown in this article, reporters coated with polyelectrolytes clearly outperform uncoated reporters with regard to quantity of attached reporters per bead (54 +/- 23 in 2500 mum(2) area for PEI/PAA coated and 11 +/- 6 for uncoated reporters) and minimization of cross-contamination (1 red reporter in 2500 mum(2) area of green-labeled bead for PEI/PAA coated and 26 +/- 15 red reporters on green-labeled beads for uncoated reporters after 10 days). Examination of various polyelectrolyte systems shows that the magnitude of the xi -potential of polyelectrolyte-coated reporters (-64 mV for PDADMAC/PSSS and -42 mV for PEI/PAA-coated reporters) has no correlation with the number of reporters that adhere to the solid support beads (21 +/- 16 in 2500 mum(2) area for PDADMAC/PSSS and 54 +/- 23 for PEI/PAA-coated reporters). The contribution of polymer bridging to the adhesion has a far greater influence than electrostatic attraction and is demonstrated by modification of the polyelectrolyte multilayers using gamma irradiation of precoated reporters either in aqueous solution or in polyelectrolyte solution.

The relationship between radiation-induced chemical processes and transverse relaxation times in polymer gel dosimeters

The effects of ionizing radiation in different compositions of polymer gel dosimeters are investigated using FT-Raman spectroscopy and NMR T-2 relaxation times. The dosimeters are manufactured from different concentrations of comonomers (acrylamide and N,N'-methylene-bis-acrylamide) dispersed in different concentrations of an aqueous gelatin matrix. Results are analysed using a model of fast exchange of magnetization between three proton pools. The fraction of protons in each pool is determined using the known chemical composition of the dosimeter and FT-Raman spectroscopy. Based on these results, the physical and chemical processes in interplay in the dosimeters are examined in view of their effect on the changes in T-2 The precipitation of growing macroradicals and the scavenging of free radicals by gelatin are used to explain the rate of polymerization. The model describes the changes in T-2 as a function of the absorbed dose up to 50 Gy for the different compositions. This is expected to aid the theoretical design of new, more efficient dosimeters, since it was demonstrated that the optimum dosimeter (i.e, with the lowest dose resolution) must have a range of relaxation times which match the range of T-2 values which can be determined with the lowest uncertainty using an MRI scanner.