Effects of the partial replacement of La by M (M=Ce, Ca and Sr) in La(2-x)M(x)CuO(4) perovskites on catalysis of the water-gas shift reaction

The performance of La(2-x)M(x)CuO(4) perovskites (where M = Ce, Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290 degrees C and 360 degrees C. The catalysts were characterized by EDS, XRD, N(2) adsorption-desorption, XPS and XANES. The XRD results showed that all the perovskites exhibited a single phase (the presence of perovskite structure), suggesting the incorporation of metals in the perovskite structure. The XPS and XANES results showed the presence of Cu(2+) on the surface. The perovskites that exhibited the best catalytic performance were La(2-x)Ce(x)CuO(4) perovslcites, with CO conversions of 85%-90%. Moreover, these perovskites have higher surface areas and larger amounts of Cu on the surface. And Ce has a higher filled energy level than the other metals, increasing the energy of the valence band of Ce and providing more electrons for the reaction. Besides, the La(1.80)Ca(0.20)CuO(4) perovskite showed a good catalytic performance.

An Experimental Study of Submerged Entry Nozzles (SEN) Focusing on Decarburization and Clogging

The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to the formation of a high-viscous alumina-rich glaze during the SEN preheating process. This, in turn, creates a very uneven surface at the SEN internal surface. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide a large REM-rich surface in contact with the primary inclusions in molten steel. This may facilitate the attraction and agglomeration of the primary REM oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. Trials were performed at non-isothermal heating conditions in a controlled atmosphere. Also, the applied temperature profile for the laboratory trials were defined based on the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as prevention of the decarburization even during heating in air. In addition, the interactions between the YSZ coated alumina-graphite refractory base materials in contact with a cerium alloyed molten stainless steel were surveyed. The YSZ coating provided a total prevention of the alumina reduction by cerium. Therefore, the prevention of the first clogging product formed on the surface of the SEN refractory base materials. Therefore, the YSZ plasma-PVD coating can be recommended for coating of the hot surface of the commercial SENs.

Mechanical and tribological properties of PVD-coated cemented carbide as evaluated by a new multi-pass scratch testing method

A new test method based on multipass scratch testing has been developed for evaluating the mechanical and tribological properties of thin, hard coatings. The proposed test method uses a pin-on-disc tribometer and during testing a Rockwell C diamond stylus is used as the “pin” and loaded against the rotating coated sample. The influence of normal load on the number of cycles to coating damage is investigated and the resulting coating damage mechanisms are evaluated by posttest scanning electron microscopy. The present study presents the test method by evaluating the performance of Ti0.86Si0.14N, Ti0.34Al0.66N, and (Al0.7Cr0.3)2O3 coatings deposited by cathodic arc evaporation on cemented carbide inserts. The results show that the test method is quick, simple, and reproducible and can preferably be used to obtain relevant data concerning the fatigue, wear, chipping, and spalling characteristics of different coating-substrate composites. The test method can be used as a virtually nondestructive test and, for example, be used to evaluate the fatigue and wear resistance as well as the cohesive and adhesive interfacial strength of coated cemented carbide inserts prior to cutting tests.

Wear of coated and uncoated PCBN cutting tool used in turning and milling

This licentiate thesis has the main focus on evaluation of the wear of coated and uncoated polycrystalline cubic boron nitride cutting tool used in cutting operations against hardened steel. And to exam the surface finish and integrity of the work material used. Harder work material, higher cutting speed and cost reductions result in the development of harder and more wear resistance cutting tools. Although PCBN cutting tools have been used in over 30 years, little work have been done on PVD coated PCBN cutting tools. Therefore hard turning and hard milling experiments with PVD coated and uncoated cutting tools have been performed and evaluated. The coatings used in the present study are TiSiN and TiAlN. The wear scar and surface integrity have been examined with help of several different characterization techniques, for example scanning electron microscopy and Auger electron spectroscopy.   The results showed that the PCBN cutting tools used displayed crater wear, flank wear and edge micro chipping. While the influence of the coating on the crater and flank wear was very small and the coating showed a high tendency to spalling. Scratch testing of coated PCBN showed that, the TiAlN coating resulted in major adhesive fractures. This displays the importance of understanding the effect of different types of lapping/grinding processes in the pre-treatment of hard and super hard substrate materials and the amount and type of damage that they can create. For the cutting tools used in turning, patches of a adhered layer, mainly consisting of FexOy were shown at both the crater and flank. And for the cutting tools used in milling a tribofilm consisting of SixOy covered the crater. A combination of tribochemical reactions, adhesive wear and mild abrasive wear is believed to control the flank and crater wear of the PCBN cutting tools. On a microscopic scale the difference phases of the PCBN cutting tool used in turning showed different wear characteristics. The machined surface of the work material showed a smooth surface with a Ra-value in the range of 100-200 nm for the turned surface and 100-150 nm for the milled surface. With increasing crater and flank wear in combination with edge chipping the machined surface becomes rougher and showed a higher Ra-value. For the cutting tools used in milling the tendency to micro edge chipping was significant higher when milling the tools steels showing a higher hard phase content and a lower heat conductivity resulting in higher mechanical and thermal stresses at the cutting edge.

Radiation properties of coil-coated steel in building envelope surfaces and the influence on building thermal performance

Recent studies have shown that the optical properties of building exterior surfaces are important in terms of energy use and thermal comfort. While the majority of the studies are related to exterior surfaces, the radiation properties of interior surfaces are less thoroughly investigated. Development in the coil-coating industries has now made it possible to allocate different optical properties for both exterior and interior surfaces of steel-clad buildings. The aim of this thesis is to investigate the influence of surface radiation properties with the focus on the thermal emittance of the interior surfaces, the modeling approaches and their consequences in the context of the building energy performance and indoor thermal environment. The study consists of both numerical and experimental investigations. The experimental investigations include parallel field measurements on three similar test cabins with different interior and exterior surface radiation properties in Borlänge, Sweden, and two ice rink arenas with normal and low emissive ceiling in Luleå, Sweden. The numerical methods include comparative simulations by the use of dynamic heat flux models, Building Energy Simulation (BES), Computational Fluid Dynamics (CFD) and a coupled model for BES and CFD. Several parametric studies and thermal performance analyses were carried out in combination with the different numerical methods. The parallel field measurements on the test cabins include the air, surface and radiation temperatures and energy use during passive and active (heating and cooling) measurements. Both measurement and comparative simulation results indicate an improvement in the indoor thermal environment when the interior surfaces have low emittance. In the ice rink arenas, surface and radiation temperature measurements indicate a considerable reduction in the ceiling-to-ice radiation by the use of low emittance surfaces, in agreement with a ceiling-toice radiation model using schematic dynamic heat flux calculations. The measurements in the test cabins indicate that the use of low emittance surfaces can increase the vertical indoor air temperature gradients depending on the time of day and outdoor conditions. This is in agreement with the transient CFD simulations having the boundary condition assigned on the exterior surfaces. The sensitivity analyses have been performed under different outdoor conditions and surface thermal radiation properties. The spatially resolved simulations indicate an increase in the air and surface temperature gradients by the use of low emittance coatings. This can allow for lower air temperature at the occupied zone during the summer. The combined effect of interior and exterior reflective coatings in terms of energy use has been investigated by the use of building energy simulation for different climates and internal heat loads. The results indicate possible energy savings by the smart choice of optical properties on interior and exterior surfaces of the building. Overall, it is concluded that the interior reflective coatings can contribute to building energy savings and improvement of the indoor thermal environment. This can be numerically investigated by the choice of appropriate models with respect to the level of detail and computational load. This thesis includes comparative simulations at different levels of detail.

Numerical simulation of heat and mass transfer in fluidised bed heat treatment furnaces

In this paper, a novel combined theoretical and computational model is developed to simulate the heat and mass transfer between a fluidised bed and a workpiece surface, and within the workpiece by considering the fluidised bed as a medium consisting of a double-particle layer and an even porous layer. The heat and mass-transfer flux from the fluidised bed to the workpiece surface is contributed by dense and bubble phases, respectively. The convective heat and mass transfer is simulated by analysing the gas dynamics in the fluidised bed, while radiative heat transfer is modelled by simulating photon emission in a three-dimensional particle array. The simulation shows that convection is approximately constant, while radiation contributes significantly to the heat transfer. The heat-transfer coefficient on an immersed surface near particles is about 6–10 times that on other areas. The transient heat and mass-transfer coefficient, heat and mass-transfer flux on any surface of the workpiece, transient temperature and carbon distributions at any position of the workpiece during the metal carburising process are studied with the simulation.

Effect of membrane stress on surface roughness changes in sheet forming

Friction plays an important role in sheet metal forming (SMF) and the roughness of the surface of the sheet is a major factor that influences friction. In finite element method (FEM) models of metal forming, the roughness has usually been assumed to be constant; even though it is commonly observed that sheet drawn under tension over a tool radius results in the surface becoming shiny, indicating a major change in surface morphology. An elastic–plastic FEM model for micro-contact between a flat surface and a single roughness peak has been developed. The model was used to investigate the effect of the membrane stress in the sheet on the deformation of an artificial roughness peak. From the simulation results, the change in asperity, or deformation of the local peak, for a given nominal tool contact stress is significantly influenced by the local substrate stress. The height of the asperity decreases with increasing substrate stress and the local pressure is much higher than the nominal pressure. In addition, the local contact stress decreases with an increase in the substrate stress levels.

Skin friction coefficient on a yarn package surface in ring spinning

The skin friction coefficient on the surface of a rotating yarn package affects the power required to drive the package. This paper examines the relationship between the skin friction coefficient on the package surface and its diameter and rotating speed, based on the fundamentals of aerodynamics and the experimental results of power consumption. Skin friction coefficients on the surfaces of an airplane, car top, and yarn package are discussed. The results indicate that the skin friction coefficient on the package surface without hairiness depends on the package diameter and spindle speed only. The skin friction coefficient on the yarn package surface is about three times that on the top surface of a car, and is about twenty times that on an airplane surface. The power consumed to overcome skin friction drag is more than that consumed to drive the spindle if the spindle speed is very slow. However, the situation reverses when the spindle speed is fast.

Surface spatial index structure of high-dimensional space

This paper proposes a spatial index structure based on a new space-partitioning method. Previous research proposed various high dimensional index structures. However, when dimensionality becomes high, the effectiveness of the spatial index structure disappears. This problem is called the “curse of dimensionality”. This paper focuses on the fact that the volume of high dimensional space is mostly occupied by its surface and then proposes a new surface index structure. The utility of this new surface spatial index structure is illustrated through a series of experiments.

Agents and the Grid: Service Discovery

The Grid is a large-scale computer system that is capable of coordinating resources that are not subject to centralised control, whilst using standard, open, general-purpose protocols and interfaces, and delivering non-trivial qualities of service. In this chapter, we argue that Grid applications very strongly suggest the use of agent-based computing, and we review key uses of agent technologies in Grids: user agents, able to customize and personalise data; agent communication languages offering a generic and portable communication medium; and negotiation allowing multiple distributed entities to reach service level agreements. In the second part of the chapter, we focus on Grid service discovery, which we have identified as a prime candidate for use of agent technologies: we show that Grid-services need to be located via personalised, semantic-rich discovery processes, which must rely on the storage of arbitrary metadata about services that originates from both service providers and service users. We present UDDI-MT, an extension to the standard UDDI service directory approach that supports the storage of such metadata via a tunnelling technique that ties the metadata store to the original UDDI directory. The outcome is a flexible service registry which is compatible with existing standards and also provides metadata-enhanced service discovery.

Local total and radiative heat-transfer coefficients during the heat treatment of a workpiece in a fluidised bed

The heat-transfer coefficients around a workpiece immersed in an electrically heated heat treatment fluidised bed were studied. A suspension probe designed to simulate a workpiece of complex geometry was developed to measure local total and radiative heat-transfer coefficients at a high bed temperature. The probe consisted of an energy-storage region separated by insulation from the fluidised bed, except for the measuring surface, and a multi-thermocouple measurement system. Experiments in the fluidised bed were performed for a fluidising medium of 120-mesh alumina, a wide temperature range of 110–1050 °C and a fluidising number range of 1.18–4.24. It was found that the workpiece surface temperature has a more significant effect on heat transfer than the bed temperature. The total heat-transfer coefficient at the upper surface of the workpiece sharply decreased at the start of heating, and then steadily increased as heating progressed, while a sharp decrease became a rapid increase and then a slow increase for the radiative heat-transfer coefficient. A great difference in the heat-transfer coefficients around the workpiece was observed.

Comparing external and internal dorsal-spine bands to interpret the age and growth of the giant lantern shark, Etmopterus baxteri (Squaliformes: Etmopteridae)

The giant lantern shark, Etmopterus baxteri, is taken as bycatch of commercial fisheries that operate in deepwater off southeastern Australia. Bands on the second dorsal spine were used to obtain age estimates. The number of bands on the external surface of the spine and within the inner dentine layer increased with animal length. Most spines had more bands on the external surface, and the rate of band formation was significantly different between the external surface and the inner dentine layer. Females had a maximum of 57 external bands and 26 internal bands, while males had up to 48 external bands and 22 internal bands. Age estimates from external bands suggest maturity (A ₅₀) at 20 years for males and 30 years for females. Internal band age estimates suggest maturity at 10.5 years for males and 11.5 years for females. Although there is a large discrepancy between these two preliminary (i.e., unvalidated) age estimates, they both suggest that E. baxteri is a long-lived and late maturing species that is likely to be susceptible to over fishing.

Microscopic nature and elemental composition of brown coal fly ash particles from a large coal fired power station

In this study, Australian brown coal fly ash particles have been collected from power station and analysed by scanning electron microscopy to obtain morphological information and elemental composition of individual particles. The most common particles found to be the irregular shape particle aggregates. Other shapes include ball shape with smooth surface and with some attachments; and crystal shape fine particles. The X-ray spectra of each fly ash particle revealed five groups of elemental composition, they are Si-rich particles; Ca-rich particles; Fe-rich particles; particles with Mg-Ca Matrix and particles with Si-Ca matrix. A particle sire distribution analysis has been conducted using particle size analyser and found to have a mean particle size of 21fim. The sample then was separated into fine and coarse fractions using aerodynamic classifier, and the elemental composition of both fractions were determined by ICP-AES. Borate fusion and acid dissolution method was used for sample preparation. It is found that some environmental sensitive elements such as Zn, Pb, Ni, K and Cu are enriched in fine fly ash particles. Ca has much higher contents in fine particles as well. Si and Mg have higher concentrations in coarse particles.

Carburising and carbon transfer coefficient in a fluidised bed furnance

The carburising of a steel workpiece with complex geometry in a fluidised bed hasbeen studied experimentally. This involved carburising experiment in an electrically heated fluidised bed at 900 - 970°C with natural gas and air as the atmosphere. The carbon transfer coefficient at the workpiece surface and diffusivity within the workpiece were determined from the carbon distribution within the diffusion layer of the sample. A reverse method and the Levenberg-Marquardt algorithm were used in the calculations. The methodology of the reverses method to extract the carbon transfer coefficient and diffusivity is also discussed in some detail.

Computational simulation of gas flow and heat transfer near an immersed object in fluidized beds

To improve the understanding of the heat transfer mechanism and to find a reliable and simple heat-transfer model, the gas flow and heat transfer between fluidized beds and the surfaces of an immersed object is numerically simulated based on a double particle-layer and porous medium model. The velocity field and temperature distribution of the gas and particles are analysed during the heat transfer process. The simulation shows that the change of gas velocity with the distance from immersed surface is consistent with the variation of bed voidage, and is used to validate approximately dimensional analysing result that the gas velocity between immersed surface and particles is 4.6Umf/εmf. The effects of particle size and particle residence time on the thermal penetration depth and the heat-transfer coefficients are also discussed.