Low liquid-solid ratio (LSR) hot water pretreatment of sugarcane bagasse

Low liquid-solid ratio (LSR) can be used to obtain high-content xylo-oligosaccharide (XOS) spend liquor by hot water pretreatment. Developing a technology based on low LSR results in more efficient water usage in the system and thus in lower capital and operating costs. Xylans from xylan rich agro-industrial waste are abundant hemicellulosic polymers with enormous potential for industrial applications. Currently, freeze-dried xylo-oligosaccharides are used as bio-based polymers and hydrolysates containing high xylose contents are converted to several chemical products. In this study, sugarcane bagasse was treated with water at low LSRs and mild temperatures in order to assess the effects of varying the pretreatment conditions on the xylo-oligosaccharide and xylose concentrations, and use a central composite experimental design to optimize the process parameters. The pretreatments were performed in the ranges temperature: 143.3-176.7 degrees C, time: 20-70 min and LSR: 1 : 1 to 11 : 1 (g g(-1)). The maximum concentrations of xylose and xylan were 13.76 and 36.18 g L-1 (equivalent to 48.29 g L-1 of xylan), respectively, which were achieved by treating bagasse at 170 degrees C for 60 min, with LSR of 3 g g(-1). The amount of xylan removed under these conditions was almost 57%. The soluble xylan consisted mainly of xylo-oligosaccharides (74 wt% of the identified compound in the spent liquor).

Multilayer thin films by layer-by-layer (LBL) assembly of functional polyelectrolytes

Nanoscience aims at manipulating atoms, molecules and nano-size particles in a precise and controlled manner. Nano-scale control of the thin film structures of organic/polymeric materials is a prerequisite to the fabrication of sophisticated functional devices. The work presented in this thesis is a compilation of various polymer thin films with newly synthesized functional polymers. Cationic and anionic LC amphotropic polymers, p-type and n-type semiconducting polymers with triarylamine, oxadiazole, thiadiazole and triazine moieties are suitable materials to fabricate multilayers by layer-by-layer (LBL) self-assembly with a well defined internal structure. The LBL assembly is the ideal processing technique to prepare thin polymer film composites with fine control over morphology and composition at nano-scale thickness, which may have applications in photo-detectors, light-emitting diodes (LEDs), displays and sensors, as well as in solar cells. The multilayer build-up was investigated with amphotropic LC polymers individually by solution-dipping and spin-coating methods; they showed different internal orders with respect to layering and orientation of the mesogens, as a result of the liquid crystalline phase. The synthesized p-type and n-type semiconducting polymers were examined optically and electrochemically, suggesting that they are favorably promising as hole-(p-type) or electron-(n-type) transport materials in electronic and optoelectronic devices. In addition, we report a successful film deposition of polymers by the vacuum deposition method. The vapor deposition method provides a clean environment; it is solvent free and well suited to sequential depositions in hetero-structured multilayer system. As the potential applications, the fabricated polymer thin films were used as simple electrochromic films and also used as hole transporting layers in LEDs. Electrochemical and electrochromic characterizations of assembled films reveal that the newly synthesized polymers give rise to high contrast ratio and fast switching electrochromic films. The LEDs with vacuum deposited films show dramatic improvements in device characteristics, indicating that the films are promising as hole transporting layers. These are the result of not only the thin nano-scale film structures but also the combination with the high charge carrier mobility of synthesized semiconducting polymers.

Manufacturing of self-passivating tungsten based alloys by different powder metallurgical routes

Self-passivating tungsten based alloys will provide a major safety advantage compared to pure tungsten when used as first wall armor of future fusion reactors, due to the formation of a protective oxide layer which prevents the formation of volatile and radioactive WO3 in case of a loss of coolant accident with simultaneous air ingress. Bulk WCr10Ti2 alloys were manufactured by two different powder metallurgical routes: (1) mechanical alloying (MA) followed by hot isostatic pressing (HIP) of metallic capsules, and (2) MA, compaction, pressureless sintering in H2 and subsequent HIPing without encapsulation. Both routes resulted in fully dense materials with homogeneous microstructure and grain sizes of 300 nm and 1 μm, respectively. The content of impurities remained unchanged after HIP, but it increased after sintering due to binder residue. It was not possible to produce large samples by route (2) due to difficulties in the uniaxial compaction stage. Flexural strength and fracture toughness measured on samples produced by route (1) revealed a ductile-to-brittle-transition temperature (DBTT) of about 950 °C. The strength increased from room temperature to 800 °C, decreasing significantly in the plastic region. An increase of fracture toughness is observed around the DBTT.

Evaluation of thermo-physical properties and drying kinetics of carrots in a convective hot air drying system

This paper presents an experimental study on the evolution of carrot properties along convective drying by hot air at different temperatures (50ºC, 60ºC and 70ºC). The thermo-physical properties calculated were: specific heat, thermal conductivity, diffusivity, enthalpy, heat and mass transfer coefficients. Furthermore, the data of drying kinetics were treated and adjusted according to the three empirical models: Page, Henderson & Pabis and Logarithmic. The sorption isotherms were also determined and fitted using the GAB model. The results showed that, generally, the thermo-physical properties presented a decline during the drying process, and the decrease was faster for the temperature of 70ºC. It was possible to verify that the Page model presented the best prediction ability for the representation of kinetics of the drying process. The GAB model used to fit the sorption isotherms showed a good prediction capacity and, at a given water activity, despite some variations, the amount of water sorbed increased with the decrease of drying temperature.

Preparation of manganese oxide - graphite electrodes by electrophoretic deposition

Manganese oxide is a promising active material for supercapacitors (SCs) with pseudocapacitance due to its high capacitance and its environmentally friendly character. This paper deals with the preparation of electrodes for supercapacitors consisting of manganese oxide supported onto graphite by electrophoretic deposition. Manganese oxide powders were characterized and dispersed in water by controlling the colloidal and rheological behavior in order to obtain stable suspensions. Optimized manganese oxide suspensions were deposited onto graphite electrodes by electrophoretic deposition. The deposited mass per unit area in the electrodes was optimized by controlling the applied current density and the deposition time. It has been demonstrated that the introduction of a binder helped to improve the adherence to graphite; otherwise the deposit thickness obtained by EPD is limited and no films can be obtained by simply dipping. These conditions allowed us to obtain more homogeneous deposits with higher specific energy than without binder.

Basin analysis and economic geology of the Northern Mount Isa Basin

The Mount Isa Basin is a new concept used to describe the area of Palaeo- to Mesoproterozoic rocks south of the Murphy Inlier and inappropriately described presently as the Mount Isa Inlier. The new basin concept presented in this thesis allows for the characterisation of basin-wide structural deformation, correlation of mineralisation with particular lithostratigraphic and seismic stratigraphic packages, and the recognition of areas with petroleum exploration potential. The northern depositional margin of the Mount Isa Basin is the metamorphic, intrusive and volcanic complex here referred to as the Murphy Inlier (not the "Murphy Tectonic Ridge"). The eastern, southern and western boundaries of the basin are obscured by younger basins (Carpentaria, Eromanga and Georgina Basins). The Murphy Inlier rocks comprise the seismic basement to the Mount Isa Basin sequence. Evidence for the continuity of the Mount Isa Basin with the McArthur Basin to the northwest and the Willyama Block (Basin) at Broken Hill to the south is presented. These areas combined with several other areas of similar age are believed to have comprised the Carpentarian Superbasin (new term). The application of seismic exploration within Authority to Prospect (ATP) 423P at the northern margin of the basin was critical to the recognition and definition of the Mount Isa Basin. The Mount Isa Basin is structurally analogous to the Palaeozoic Arkoma Basin of Illinois and Arkansas in southern USA but, as with all basins it contains unique characteristics, a function of its individual development history. The Mount Isa Basin evolved in a manner similar to many well described, Phanerozoic plate tectonic driven basins. A full Wilson Cycle is recognised and a plate tectonic model proposed. The northern Mount Isa Basin is defined as the Proterozoic basin area northwest of the Mount Gordon Fault. Deposition in the northern Mount Isa Basin began with a rift sequence of volcaniclastic sediments followed by a passive margin drift phase comprising mostly carbonate rocks. Following the rift and drift phases, major north-south compression produced east-west thrusting in the south of the basin inverting the older sequences. This compression produced an asymmetric epi- or intra-cratonic clastic dominated peripheral foreland basin provenanced in the south and thinning markedly to a stable platform area (the Murphy Inlier) in the north. The fmal major deformation comprised east-west compression producing north-south aligned faults that are particularly prominent at Mount Isa. Potential field studies of the northern Mount Isa Basin, principally using magnetic data (and to a lesser extent gravity data, satellite images and aerial photographs) exhibit remarkable correlation with the reflection seismic data. The potential field data contributed significantly to the unravelling of the northern Mount Isa Basin architecture and deformation. Structurally, the Mount Isa Basin consists of three distinct regions. From the north to the south they are the Bowthorn Block, the Riversleigh Fold Zone and the Cloncurry Orogen (new names). The Bowthom Block, which is located between the Elizabeth Creek Thrust Zone and the Murphy Inlier, consists of an asymmetric wedge of volcanic, carbonate and clastic rocks. It ranges from over 10 000 m stratigraphic thickness in the south to less than 2000 min the north. The Bowthorn Block is relatively undeformed: however, it contains a series of reverse faults trending east-west that are interpreted from seismic data to be down-to-the-north normal faults that have been reactivated as thrusts. The Riversleigh Fold Zone is a folded and faulted region south of the Bowthorn Block, comprising much of the area formerly referred to as the Lawn Hill Platform. The Cloncurry Orogen consists of the area and sequences equivalent to the former Mount Isa Orogen. The name Cloncurry Orogen clearly distinguishes this area from the wider concept of the Mount Isa Basin. The South Nicholson Group and its probable correlatives, the Pilpah Sandstone and Quamby Conglomerate, comprise a later phase of now largely eroded deposits within the Mount Isa Basin. The name South Nicholson Basin is now outmoded as this terminology only applied to the South Nicholson Group unlike the original broader definition in Brown et al. (1968). Cored slimhole stratigraphic and mineral wells drilled by Amoco, Esso, Elf Aquitaine and Carpentaria Exploration prior to 1986, penetrated much of the stratigraphy and intersected both minor oil and gas shows plus excellent potential source rocks. The raw data were reinterpreted and augmented with seismic stratigraphy and source rock data from resampled mineral and petroleum stratigraphic exploration wells for this study. Since 1986, Comalco Aluminium Limited, as operator of a joint venture with Monument Resources Australia Limited and Bridge Oil Limited, recorded approximately 1000 km of reflection seismic data within the basin and drilled one conventional stratigraphic petroleum well, Beamesbrook-1. This work was the first reflection seismic and first conventional petroleum test of the northern Mount Isa Basin. When incorporated into the newly developed foreland basin and maturity models, a grass roots petroleum exploration play was recognised and this led to the present thesis. The Mount Isa Basin was seen to contain excellent source rocks coupled with potential reservoirs and all of the other essential aspects of a conventional petroleum exploration play. This play, although high risk, was commensurate with the enormous and totally untested petroleum potential of the basin. The basin was assessed for hydrocarbons in 1992 with three conventional exploration wells, Desert Creek-1, Argyle Creek-1 and Egilabria-1. These wells also tested and confrrmed the proposed basin model. No commercially viable oil or gas was encountered although evidence of its former existence was found. In addition to the petroleum exploration, indeed as a consequence of it, the association of the extensive base metal and other mineralisation in the Mount Isa Basin with hydrocarbons could not be overlooked. A comprehensive analysis of the available data suggests a link between the migration and possible generation or destruction of hydrocarbons and metal bearing fluids. Consequently, base metal exploration based on hydrocarbon exploration concepts is probably. the most effective technique in such basins. The metal-hydrocarbon-sedimentary basin-plate tectonic association (analogous to Phanerozoic models) is a compelling outcome of this work on the Palaeo- to Mesoproterozoic Mount lsa Basin. Petroleum within the Bowthom Block was apparently destroyed by hot brines that produced many ore deposits elsewhere in the basin.

Indentation size effect and strain rate sensitivity of nanocrystalline Mg-Al alloys

Deformation Behaviour of microcrystalline (mc) and nanocrystalline (nc) Mg-5%Al alloys produced by hot extrusion of ball-milled powders were investigated using instrumented indentation tests. The hardness values of the mc and nc metals exhibited indentation size effect (ISE), with nc alloys showing weaker ISE. The highly localized dislocation activities resulted in a small activation volume, hence enhanced strain rate sensitivity. Relative higher strain rate sensitivity and the negative Hall-Petch Relationship suggested the increasingly important role of grain boundary mediated mechanisms when the grain size decreased to nanometer region.

Preparation and characterisation of composites from starch and sugar cane fibre

The aim of this study was to prepare and characterise composites of Soluble potato starch or hydroxypropylated maize starch with milled sugar cane fibre (i.e., bagasse). Prior to the preparation of the starch-fibre composites, the ‘cast’ and the ‘hot-pressed’ methods were investigated for the preparation of starch films in order to select the preferred preparation method. The physicochemical and mechanical properties of films conditioned at different relative humidities (RHs) were determined through moisture uptake, crystallinity, glass transition temperature (Tg), thermal properties, molecular structure and tensile tests. Hot-pressed starch films have ~5.5% less moisture, twice the crystallinity (~59%), higher Tg and Young’s modulus than cast starch films. The VH-type starch polymorph was observed to be present in the hot-pressed films. The addition of bagasse fibre to both starch types, prepared by hot-pressing, reduced the moisture uptake by up to 30% (cf., cast film) at 58% RH. The addition of 5 wt% fibre increased the tensile strength and Young’s modulus by 16% and 24% respectively. It significantly decreased the tensile strain by ~53%. Fourier Transform infrared (FT-IR) spectroscopy revealed differences in hydrogen bonding capacity between the films with fibre and those without fibre. The results have been explained on the basis of the intrinsic properties of starch and bagasse fibres.

Simulating a latent susceptible pool to examine the impact on cardiovascular mortality

The health effects of cold and hot temperatures are strongest in the frail and elderly. A large number of deaths in this "susceptible pool" after heat waves and cold snaps can cause mortality displacement, where an immediate increase in mortality is somewhat offset by a subsequent decrease in the following weeks. There may also be longer-term implications, as reductions in the pool caused by hot summers can reduce cold-related mortality in the following winter. A state-space model was used to simulate the numbers in the susceptible pool over time. We simulated the effects of harsh winters and heat waves, and varied the size of the susceptible pool. The larger the susceptible pool the smaller the mortality displacement. When 1% of the population were susceptible a harsh winter lead to an average of just 3 months of life lost per cold-related death, whereas a pool size of 10% meant that 24 months of life were lost per death. The impact of a cold spell on months of life lost was greater when the increased risk of death also applied to healthy people. The number of deaths caused by an August heat wave were reduced when there was a prior heat wave in June which reduced the susceptible pool. We were able to mimic some observed seasonal patterns in mortality using a simple state-space model. A better understanding of the size and dynamics of the susceptible pool will improve our understanding of the health effects of temperature.

Bacillus cereus spores and cereulide in food-borne illness

B. cereus is a gram-positive bacterium that possesses two different forms of life:the large, rod-shaped cells (ca. 0.002 mm by 0.004 mm) that are able to propagate and the small (0.001 mm), oval shaped spores. The spores can survive in almost any environment for up to centuries without nourishment or water. They are insensitive towards most agents that normally kill bacteria: heating up to several hours at 90 ºC, radiation, disinfectants and extreme alkaline (≥ pH 13) and acid (≤ pH 1) environment. The spores are highly hydrophobic and therefore make them tend to stick to all kinds of surfaces, steel, plastics and live cells. In favorable conditions the spores of B. cereus may germinate into vegetative cells capable of producing food poisoning toxins. The toxins can be heat-labile protein formed after ingestion of the contaminated food, inside the gastrointestinal tract (diarrhoeal toxins), or heat stable peptides formed in the food (emesis causing toxin, cereulide). Cereulide cannot be inactivated in foods by cooking or any other procedure applicable on food. Cereulide in consumed food causes serious illness in human, even fatalities. In this thesis, B. cereus strains originating from different kinds of foods and environments and 8 different countries were inspected for their capability of forming cereulide. Of the 1041 isolates from soil, animal feed, water, air, used bedding, grass, dung and equipment only 1.2 % were capable of producing cereulide, whereas of the 144 isolates originating from foods 24 % were cereulide producers. Cereulide was detected by two methods: by its toxicity towards mammalian cells (sperm assay) and by its peculiar chemical structure using liquid-chromatograph-mass spectrometry equipment. B. cereus is known as one of the most frequent bacteria occurring in food. Most foods contain more than one kind of B. cereus. When randomly selected 100 isolates of B. cereus from commercial infant foods (dry formulas) were tested, 11% of these produced cereulide. Considering a frequent content of 103 to 104 cfu (colony forming units) of B. cereus per gram of infant food formula (dry), it appears likely that most servings (200 ml, 30 g of the powder reconstituted with water) may contain cereulide producers. When a reconstituted infant formula was inoculated with >105 cfu of cereulide producing B. cereus per ml and left at room temperature, cereulide accumulated to food poisoning levels (> 0.1 mg of cereulide per serving) within 24 hours. Paradoxically, the amount of cereulide (per g of food) increased 10 to 50 fold when the food was diluted 4 - 15 fold with water. The amount of the produced cereulide strongly depended on the composition of the formula: most toxin was formed in formulas with cereals mixed with milk, and least toxin in formulas based on milk only. In spite of the aggressive cleaning practices executed by the modern dairy industry, certain genotypes of B. cereus appear to colonise the silos tanks. In this thesis four strategies to explain their survival of their spores in dairy silos were identified. First, high survival (log 15 min kill ≤ 1.5) in the hot alkaline (pH >13) wash liquid, used at the dairies for cleaning-in-place. Second, efficient adherence of the spores to stainless steel from cold water. Third, a cereulide producing group with spores characterized by slow germination in rich medium and well preserved viability when exposed to heating at 90 ºC. Fourth, spores capable of germinating at 8 ºC and possessing the psychrotolerance gene, cspA. There were indications that spores highly resistant to hot 1% sodium hydroxide may be effectively inactivated by hot 0.9% nitric acid. Eight out of the 14 dairy silo tank isolates possessing hot alkali resistant spores were capable of germinating and forming biofilm in whole milk, not previously reported for B. cereus. In this thesis it was shown that cereulide producing B. cereus was capable of inhibiting the growth of cereulide non-producing B. cereus occurring in the same food. This phenomenon, called antagonism, has long been known to exist between B. cereus and other microbial species, e.g. various species of Bacillus, gram-negative bacteria and plant pathogenic fungi. In this thesis intra-species antagonism of B. cereus was shown for the first time. This brother-killing did not depend on the cereulide molecule, also some of the cereulide non-producers were potent antagonists. Interestingly, the antagonistic clades were most frequently found in isolates from food implicated with human illness. The antagonistic property was therefore proposed in this thesis as a novel virulence factor that increases the human morbidity of the species B. cereus, in particular of the cereulide producers.

High vacuum tribology of polycrystalline diamond coatings

Polycrystalline diamond coatings have been grown on unpolished side of Si(100) wafers by hot filament chemical vapour deposition process. The morphology of the grown coatings has been varied from cauliflower morphology to faceted morphology by manipulation of the growth temperature from 700 degrees C to 900 degrees C and methane gas concentration from 3% to 1.5%. It is found that the coefficient of friction of the coatings under high vacuum of 133.32 x 10(-7) Pa (10(-7) torr) with nanocrystalline grains can be manipulated to 0.35 to enhance tribological behaviour of bare Si substrates.

Influence of tool rake angle on the quality of pure magnesium chip-consolidated product

Chips were produced by orthogonal Cutting of cast pure magnesium billet with three different tool rake angles viz., -15 degrees, -5 degrees and +15 degrees on a lathe. Chip consolidation by solid state recycling technique involved cold compaction followed by hot extrusion. The extruded products were characterized for microstructure and mechanical properties. Chip-consolidated products from -15 degrees rake angle tools showed 19% increase in tensile strength, 60% reduction ingrain size and 12% increase in hardness compared to +15 degrees rake chip-consolidated product indicating better chip bonding and grain refinement. Microstructure of the fracture specimen Supports the abovefinding. On the overall, the present work high lights the importance of tool take angle in determining the quality of the chip-consolidated products. (C) 2009 Elsevier B.V. All rights reserved.

Influence of temperature and strain rate on the flow stress of an FeAl alloy

The deformation behavior of an FeAl alloy processed by hot extrusion of water atomized powder has been investigated. Compression tests are performed in the temperature range 1073–1423 K and in the strain rate range 0.001–100 s−1 up to a true plastic strain of 0.5. The flow stress has been found to be strongly dependent on temperature as well as strain rate. The stress exponent in the power law rate equation is estimated to be in the range 7.0–4.0, decreasing with temperature. The activation energy for plastic flow in the range 1073–1373 K varies from 430 kJ mol−1 at low stresses to 340 kJ mol−1 at high stresses. However, it is fairly independent of strain rate and strain. The activation area has similarly shown a stress dependence and lies in the range 160–45b2. At 1423 K and at strain rates lower than 0.1 s−1 a strain rate sensitivity of 0.3 is observed with an associated activation energy of 375 kJ mol−1. The plastic flow in the entire range of temperature and strain rate investigated appears to be controlled by a diffusion mechanism. The results have revealed that it is possible to process the alloy by superplastic forming in the range 1373–1423 K at strain rates lower than 0.1 s−1.

Microstructure and damping behaviour of consolidated magnesium chips

Chips produced by turning a commercial grade pure magnesium billet were consolidated by solid state recycling technique of cold compaction followed by hot extrusion. The cold compacted billets were extruded at four different temperatures: 250 degrees C, 300 degrees C, 350 degrees C and 400 degrees C. For the purpose of comparison, cast magnesium (pure) billets were extruded under similar conditions. Extruded products were characterized for damping properties. Damping capacity and dynamic modulus was measured as a function of time and temperature at a fixed frequency of 5 Hz 10 to 14% increase in damping capacity was observed in chip consolidated products compared to reference material. Microstructural changes after the temperature sweep tests were examined. Chip boundaries present in consolidated products were observed to suppress grain coarsening which otherwise was significant in reference material. The present work is significant from the viewpoint of recycling of machined chips and development of sustainable manufacturing processes. (C) 2012 Elsevier B.V. All rights reserved.

Microstructure and tensile properties of consolidated magnesium chips

In this study tensile properties of consolidated magnesium chips obtained from solid state re-cycling (SSR) has been examined and correlated with the microstructure. Chips machined from as-cast billet of pure magnesium were consolidated through SSR technique, comprising of compaction at ambient conditions followed by hot extrusion at four different temperatures viz., 250, 300, 350 and 400 degrees C. The extruded rods were characterized for microstructure and their room temperature tensile properties. Both ultimate tensile strength and 0.2% proof stress of these consolidated materials are higher by 15-35% compared to reference material (as cast and extruded). Further these materials obey Hall-Petch relation with respect to strength dependence of grain size. Strain hardening behavior, measured in terms of hardening exponent, hardening capacity and hardening rate was found to be distinctly different in chip consolidated material compared to reference material. Strength asymmetry, measured as a ratio of compressive proof stress to tensile proof stress was higher in chip consolidated material. (C) 2012 Elsevier B.V. All rights reserved.