Development of alpha-SiAlON-SiC ceramic composites by liquid phase sintering

In this work, in situ alpha-SiAlON-SiC ceramic composites were obtained,by, liquid phase sintering, using SiC as reinforcement. Different beta-SiC powder contents (0-20 wt.%), were added to Si3N4-AlN-RE2O3. powder mixtures, and compacted by cold isostatic pressing. The samples were sintered at 1950 degrees C for 1 h, in N-2 atmosphere. Sintered: samples were characterized by relative density, weight loss, X-ray diffraction and scanning electron microscopy. Furthermore, mechanical properties such as hardness and fracture toughness were determined by Vickers indentation method. Lattice parameters of the alpha' phase did not considerably change with increase of SiC content. However, morphology, average grain size and aspect ratio of the alpha' phase were considerably changed with increase of the SiC content. These behavior influences significantly the mechanical properties of this hard ceramic composite. (C) 2006 Elsevier Ltd. All rights reserved.

Pore size evolution during sintering of ceramic oxides

This paper reviews the influence of particle size distribution, agglomerates, rearrangement, sintering atmospheres and impurities on the pore evolution of some commonly studied oxides. These factors largely affect sintering mechanisms due to modifications of diffusion coefficients or evaporation-condensation. Very broad particle size distribution leads to grain growth and agglomerates densify first. Rearrangement of particles due to neck asymmetry mainly in the early stage of sintering is responsible for a high rate of densification in the first minutes of sintering by collapse of large pores. Sintering atmospheres play an important role in both densification and pore evolution. The chemical interaction of water molecules with several oxides like MgO, ZnO and SnO2 largely affects surface diffusion. As a consequence, there is an increase in the rates of pore growth and densification for MgO and ZnO and in the rate of pore growth for SnO2. Carbon dioxide does not affect the rate of sintering of MgO but greatly affects both rates of pore growth and densification of ZnO. Oxygen concentration in the atmosphere can especially affect semiconductor oxides but significantly affects the rate of pore growth of SnO2. Impurities like chlorine ions increase the rate of pore growth in MgO due to evaporation of HCl and Mg(OH)Cl, increasing the rate of densification and particle cuboidization. CuO promotes densification in SnO2, and is more effective in dry air. The rate of densification decrease and pore widening are promoted in argon. An inert atmosphere favors SnO2 evaporation due to reduction of CuO. © 1990.

High-pressure assisted sintering of Ti-20Si-10B and Ti-10Si-5B powders

This work presents the structural characterization of Ti-10Si-5B and Ti-20Si-10B (at-%) alloys produced by high-pressure assisted sintering. Sintering was performed in air at 1100 and 1200°C for 60 s using pressure levels of 5 GPa. Structural evaluation of sintered samples was conducted by means of scanning electron microscopy and energy dispersive spectrometry. Samples were successfully consolidated after sintering, which presented theoretical density values higher than 99%. The microstructures of the sintered Ti-10Si-5B and Ti-20Si-10B alloys revealed the presence of the TiSS, TiB, TiB2, Ti5Si3, Ti5Si4, TiSi, and TiSi2.phases. A small amount of Ti6Si2B was formed after high-pressure assisted sintering of the Ti-20Si-10B alloy (5GPa, 1100°C for 60 s) indicating that equilibrium structures were not achieved during short sintering times. No oxygen and carbon contamination was detected in structures of Ti-Si-B alloys after high-pressure sintering at 1100 and 1200°C without controlled atmosphere. © (2012) Trans Tech Publications, Switzerland.

alpha-SiAlON-SiC composites obtained by gas-pressure sintering and hot-pressing

The objective of this work was the obtaining in situ of alpha-SiAlON-SiC composite, using an alternative rare-earth oxide mixture, RE2O3, as sintering additive, by two different sintering processes. As sintering additive, 20 vol.% of AlN-RE2O3 in a molar ratio of 90: 10 was mixed to the alpha-Si3N4 powder. In the Si3N4-AlN-RE2O3 powder mixture, 0, 10, 15 and 20wt.% of SiC were added. The powder batches were milled, dried and compacted by cold isostatic pressing. Two different sintering processes were used: gas-pressure sintering at 1950 degrees C for 1 h under 1.5 MPa of N-2 atmosphere, or uniaxial hot-pressing at 1750 degrees C, for 30 min under pressure of 20 MPa. The sintered samples were characterized by X-ray diffraction, scanning electron microscopy and mechanical properties. XRD patterns indicate only alpha-SiAlON (alpha') and beta-SiC as crystalline phases. It was observed that the SiC addition did not influence the alpha-SiAlON formation, although the growth of elongated alpha'-grains is substantially decreased. The hot-pressed composites presented better mechanical properties, exhibiting fracture toughness of 5 MPa m(1/2) and hardness around 21.5 GPa. (c) 2007 Elsevier B.V. All rights reserved.

On Ti-18Si-6B and Ti-7.5Si-22.5B powder alloys prepared by high-energy ball milling and sintering

Recently, a new ternary phase was discovered in the Ti-Si-B system, located near the Ti6Si2B composition. The present study concerns the preparation of titanium alloys that contain such phase mixed with α-titanium and other intermetallic phases. High-purity powders were initially processed in a planetary ball-mill under argon atmosphere with Ti-18Si-6B and Ti-7.5Si-22.5B at. (%) initial compositions. Variation of parameters such as rotary speed, time, and ball diameters were adopted. The as-milled powders were pressureless sintered and hot pressed. Both the as-milled and sintered materials were characterized by X-ray diffraction, scanning electron microscopy and energy-dispersive spectrometry. Sintered samples have presented equilibrium structures formed mainly by the α-Ti+Ti6Si2B+Ti5Si3+TiB phases. Silicon and boron peaks disappear throughout the milling processes, as observed in the powder diffraction data. Furthermore, an iron contamination of up to 10 at. (%) is measured by X-ray spectroscopy analysis on some regions of the sintered samples. Density, hardness and tribological results for these two compositions are also presented here.

Synthesis and characterization of nano-hetero-structured dy doped CeO2 solid electrolytes using a combination of spark plasma sintering and conventional sintering

Doped ceria (CeO2) compounds are fluorite-type oxides that show oxide ionic conductivity higher than yttria-stabilized zirconia in oxidizing atmosphere. As a consequence of this, considerable interest has been shown in application of these materials for low (500 degrees-650 degrees C) temperature operation of solid oxide fuel cells (SOFCs). To improve the conductivity in dysprosium (Dy) doped CeO2, nano-size round shape particles were prepared using a coprecipitation method. The dense sintered bodies with small grain sizes (< 300 nm) were fabricated using a combined process of spark plasma sintering (SPS) and conventional sintering (CS). Dy-doped CeO2 sintered body with large grains (1.1 mu m) had large micro-domains. The conductivity in the sintered body was low (-3.2 S/cm at 500 degrees C). On the other hand, the conductivity in the specimens obtained by the combined process was considerably improved. The micro-domain size in the grain was minimized using the present process. It is concluded that the enhancement of conductivity in dense specimens produced by the combined process (SPS+CS) is attributable to the microstructural changes within the grains.

Long-term trends in fine particle number concentrations in the urban atmosphere of Brisbane : the relevance of traffic emissions and new particle formation

The measurement of submicrometre (< 1.0 m) and ultrafine particles (diameter < 0.1 m) number concentration have attracted attention since the last decade because the potential health impacts associated with exposure to these particles can be more significant than those due to exposure to larger particles. At present, ultrafine particles are not regularly monitored and they are yet to be incorporated into air quality monitoring programs. As a result, very few studies have analysed their long-term and spatial variations in ultrafine particle concentration, and none have been in Australia. To address this gap in scientific knowledge, the aim of this research was to investigate the long-term trends and seasonal variations in particle number concentrations in Brisbane, Australia. Data collected over a five-year period were analysed using weighted regression models. Monthly mean concentrations in the morning (6:00-10:00) and the afternoon (16:00-19:00) were plotted against time in months, using the monthly variance as the weights. During the five-year period, submicrometre and ultrafine particle concentrations increased in the morning by 105.7% and 81.5% respectively whereas in the afternoon there was no significant trend. The morning concentrations were associated with fresh traffic emissions and the afternoon concentrations with the background. The statistical tests applied to the seasonal models, on the other hand, indicated that there was no seasonal component. The spatial variation in size distribution in a large urban area was investigated using particle number size distribution data collected at nine different locations during different campaigns. The size distributions were represented by the modal structures and cumulative size distributions. Particle number peaked at around 30 nm, except at an isolated site dominated by diesel trucks, where the particle number peaked at around 60 nm. It was found that ultrafine particles contributed to 82%-90% of the total particle number. At the sites dominated by petrol vehicles, nanoparticles (< 50 nm) contributed 60%-70% of the total particle number, and at the site dominated by diesel trucks they contributed 50%. Although the sampling campaigns took place during different seasons and were of varying duration these variations did not have an effect on the particle size distributions. The results suggested that the distributions were rather affected by differences in traffic composition and distance to the road. To investigate the occurrence of nucleation events, that is, secondary particle formation from gaseous precursors, particle size distribution data collected over a 13 month period during 5 different campaigns were analysed. The study area was a complex urban environment influenced by anthropogenic and natural sources. The study introduced a new application of time series differencing for the identification of nucleation events. To evaluate the conditions favourable to nucleation, the meteorological conditions and gaseous concentrations prior to and during nucleation events were recorded. Gaseous concentrations did not exhibit a clear pattern of change in concentration. It was also found that nucleation was associated with sea breeze and long-range transport. The implications of this finding are that whilst vehicles are the most important source of ultrafine particles, sea breeze and aged gaseous emissions play a more important role in secondary particle formation in the study area.

The effects of sintering profiles on the resistance and flatness of transparent conducting oxide substrates for DSC

The effects of sintering on several properties of FTO and ITO substates used in DSC have been investigated. FTO & ITO substrates were prepared with a range of sizes and aspect ratios - emulated laboratory style test cells through to prototype modules. Time and temperature of the sintering profiles were varied and sheet resistance and flatness measured. Electrical properties of the substrates were then further characterized by electrochemical impedance spectroscopy, and module sized devices were assembled and thickness variations over the device area were determined and related to performance.

Influence of historic land use change on the biosphere-atmosphere-exchange of C and N trace gases in the humid, subtropical region of Queensland

Increases in atmospheric concentrations of the greenhouse gases (GHGs) carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) due to human activities have been linked to climate change. GHG emissions from land use change and agriculture have been identified as significant contributors to both Australia’s and the global GHG budget. This is expected to increase over the coming decades as rates of agriculture intensification and land use change accelerate to support population growth and food production. Limited data exists on CO2, CH4 and N2O trace gas fluxes from subtropical or tropical soils and land uses. To develop effective mitigation strategies a full global warming potential (GWP) accounting methodology is required that includes emissions of the three primary greenhouse gases. Mitigation strategies that focus on one gas only can inadvertently increase emissions of another. For this reason, detailed inventories of GHGs from soils and vegetation under individual land uses are urgently required for subtropical Australia. This study aimed to quantify GHG emissions over two consecutive years from three major land uses; a well-established, unfertilized subtropical grass-legume pasture, a 30 year (lychee) orchard and a remnant subtropical Gallery rainforest, all located near Mooloolah, Queensland. GHG fluxes were measured using a combination of high resolution automated sampling, coarser spatial manual sampling and laboratory incubations. Comparison between the land uses revealed that land use change can have a substantial impact on the GWP on a landscape long after the deforestation event. The conversion of rainforest to agricultural land resulted in as much as a 17 fold increase in GWP, from 251 kg CO2 eq. ha-1 yr-1 in the rainforest to 889 kg CO2 eq. ha-1 yr-1 in the pasture to 2538 kg CO2 eq. ha-1 yr-1 in the lychee plantation. This increase resulted from altered N cycling and a reduction in the aerobic capacity of the soil in the pasture and lychee systems, enhancing denitrification and nitrification events, and reducing atmospheric CH4 uptake in the soil. High infiltration, drainage and subsequent soil aeration under the rainforest limited N2O loss, as well as promoting CH4 uptake of 11.2 g CH4-C ha-1 day-1. This was among the highest reported for rainforest systems, indicating that aerated subtropical rainforests can act as substantial sink of CH4. Interannual climatic variation resulted in significantly higher N2O emission from the pasture during 2008 (5.7 g N2O-N ha day) compared to 2007 (3.9 g N2O-N ha day), despite receiving nearly 500 mm less rainfall. Nitrous oxide emissions from the pasture were highest during the summer months and were highly episodic, related more to the magnitude and distribution of rain events rather than soil moisture alone. Mean N2O emissions from the lychee plantation increased from an average of 4.0 g N2O-N ha-1 day-1, to 19.8 g N2O-N ha-1 day-1 following a split application of N fertilizer (560 kg N ha-1, equivalent to 1 kg N tree-1). The timing of the split application was found to be critical to N2O emissions, with over twice as much lost following an application in spring (emission factor (EF): 1.79%) compared to autumn (EF: 0.91%). This was attributed to the hot and moist climatic conditions and a reduction in plant N uptake during the spring creating conditions conducive to N2O loss. These findings demonstrate that land use change in subtropical Australia can be a significant source of GHGs. Moreover, the study shows that modifying the timing of fertilizer application can be an efficient way of reducing GHG emissions from subtropical horticulture.

Ultrafast near infrared sintering of TiO2 layers on metal substrates for dye-sensitized solar cells

A limiting step to roll-to-roll production of dye-sensitized solar cells on metals is TiO2 sintering (10-30 min). Near infrared (NIR) heating is a novel process innovation which directly heats titanium substrates giving rapid binder removal and sintering. NIR heating (for 12.5 s) at varying power gave titanium temperatures of 545, 685 and 817 degrees Celsius yielding cells with efficiencies of 2.9, 2.8 and 2.5%. Identical cells prepared in a conventional oven (1800 s) at 500, 600 and 800 degrees Celsius gave 2.9, 2.6 and 0.2% efficiency. NIR sintering is ultrafast and has a wide process window making it ideal for rapid manufacturing on metals.

Effect of biochar amendment on the soil-atmosphere exchange of greenhouse gases from an intensive subtropical pasture in northern New South Wales, Australia

We assessed the effect of biochar incorporation into the soil on the soil-atmosphere exchange of the greenhouse gases (GHG) from an intensive subtropical pasture. For this, we measured N2O, CH4 and CO2 emissions with high temporal resolution from April to June 2009 in an existing factorial experiment where cattle feedlot biochar had been applied at 10 t ha-1 in November 2006. Over the whole measurement period, significant emissions of N2O and CO2 were observed, whereas a net uptake of CH4 was measured. N2O emissions were found to be highly episodic with one major emission pulse (up to 502 µg N2O-N m-2 h 1) following heavy rainfall. There was no significant difference in the net flux of GHGs from the biochar amended vs. the control plots. Our results demonstrate that intensively managed subtropical pastures on ferrosols in northern New South Wales of Australia can be a significant source of GHG. Our hypothesis that the application of biochar would lead to a reduction in emissions of GHG from soils was not supported in this field assessment. Additional studies with longer observation periods are needed to clarify the long term effect of biochar amendment on soil microbial processes and the emission of GHGs under field conditions.

The role of vegetation in enhancing radon concentration and ion production in the atmosphere

The role of ions in the production of atmospheric particles has gained wide interest due to their profound impact on climate. Away from anthropogenic sources, molecules are ionized by alpha radiation from radon exhaled from the ground and cosmic gamma radiation from space. These molecular ions quickly form into ‘cluster ions’, typically smaller than about 1.5 nm. Using our measurements and the published literature, we present evidence to show that cluster ion concentrations in forest areas are consistently higher than outside. Since alpha radiation cannot penetrate more than a few centimetres of soil, radon present deep in the ground cannot directly contribute to the measured cluster ion concentrations. We propose an additional mechanism whereby radon, which is water soluble, is brought up by trees and plants through the uptake of groundwater and released into the atmosphere by transpiration. We estimate that, in a forest comprising eucalyptus trees spaced 4m apart, approximately 28% of the radon in the air may be released by transpiration. Considering that 24% of the earth’s land area is still covered in forests; these findings have potentially important implications for atmospheric aerosol formation and climate.

Development of an autonomous unmanned aerial system to collect time-stamped samples from the atmosphere and localize potential pathogen sources

This paper presents the hardware development and testing of a new concept for air sampling via the integration of a prototype spore trap onboard an unmanned aerial system (UAS).We propose the integration of a prototype spore trap onboard a UAS to allow multiple capture of spores of pathogens in single remote locations at high or low altitude, otherwise not possible with stationary sampling devices.We also demonstrate the capability of this system for the capture of multiple time-stamped samples during a single mission.Wind tunnel testing was followed by simulation, and flight testing was conducted to measure and quantify the spread during simulated airborne air sampling operations. During autonomous operations, the onboard autopilot commands the servo to rotate the sampling device to a new indexed location once the UAS vehicle reaches the predefined waypoint or set of waypoints (which represents the region of interest). Time-stamped UAS data are continuously logged during the flight to assist with analysis of the particles collected. Testing and validation of the autopilot and spore trap integration, functionality, and performance is described. These tools may enhance the ability to detect new incursions of spores

Deformation behaviours of coarse-grained and nanocrystalline Mg-5wt% Al alloys

Magnesium alloys have been of growing interest to various engineering applications, such as the automobile, aerospace, communication and computer industries due to their low density, high specific strength, good machineability and availability as compared with other structural materials. However, most Mg alloys suffer from poor plasticity due to their Hexagonal Close Packed structure. Grain refinement has been proved to be an effective method to enhance the strength and alter the ductility of the materials. Several methods have been proposed to produce materials with nanocrystalline grain structures. So far, most of the research work on nanocrystalline materials has been carried out on Face-Centered Cubic and Body-Centered Cubic metals. However, there has been little investigation of nanocrystalline Mg alloys. In this study, bulk coarse-grained and nanocrystalline Mg alloys were fabricated by a mechanical alloying method. The mixed powder of Mg chips and Al powder was mechanically milled under argon atmosphere for different durations of 0 hours (MA0), 10 hours (MA10), 20 hours (MA20), 30 hours (MA30) and 40 hours (MA40), followed by compaction and sintering. Then the sintered billets were hot-extruded into metallic rods with a 7 mm diameter. The obtained Mg alloys have a nominal composition of Mg–5wt% Al, with grain sizes ranging from 13 μm down to 50 nm, depending on the milling durations. The microstructure characterization and evolution after deformation were carried out by means of Optical microscopy, X-Ray Diffraction, Scanning Electron Microscopy, Transmission Electron Microscopy, Scanning Probe Microscopy and Neutron Diffraction techniques. Nanoindentaion, compression and micro-compression tests on micro-pillars were used to study the size effects on the mechanical behaviour of the Mg alloys. Two kinds of size effects on the mechanical behaviours and deformation mechanisms were investigated: grain size effect and sample size effect. The nanoindentation tests were composed of constant strain rate, constant loading rate and indentation creep tests. The normally reported indentation size effect in single crystal and coarse-grained crystals was observed in both the coarse-grained and nanocrystalline Mg alloys. Since the indentation size effect is correlated to the Geometrically Necessary Dislocations under the indenter to accommodate the plastic deformation, the good agreement between the experimental results and the Indentation Size Effect model indicated that, in the current nanocrystalline MA20 and MA30, the dislocation plasticity was still the dominant deformation mechanism. Significant hardness enhancement with decreasing grain size, down to 58 nm, was found in the nanocrystalline Mg alloys. Further reduction of grain size would lead to a drop in the hardness values. The failure of grain refinement strengthening with the relatively high strain rate sensitivity of nanocrystalline Mg alloys suggested a change in the deformation mechanism. Indentation creep tests showed that the stress exponent was dependent on the loading rate during the loading section of the indentation, which was related to the dislocation structures before the creep starts. The influence of grain size on the mechanical behaviour and strength of extruded coarse-grained and nanocrystalline Mg alloys were investigated using uniaxial compression tests. The macroscopic response of the Mg alloys transited from strain hardening to strain softening behaviour, with grain size reduced from 13 ìm to 50 nm. The strain hardening was related to the twinning induced hardening and dislocation hardening effect, while the strain softening was attributed to the localized deformation in the nanocrystalline grains. The tension–compression yield asymmetry was noticed in the nanocrystalline region, demonstrating the twinning effect in the ultra-fine-grained and nanocrystalline region. The relationship k tensions < k compression failed in the nanocrystalline Mg alloys; this was attributed to the twofold effect of grain size on twinning. The nanocrystalline Mg alloys were found to exhibit increased strain rate sensitivity with decreasing grain size, with strain rate ranging from 0.0001/s to 0.01/s. Strain rate sensitivity of coarse-grained MA0 was increased by more than 10 times in MA40. The Hall-Petch relationship broke down at a critical grain size in the nanocrystalline region. The breakdown of the Hall-Petch relationship and the increased strain rate sensitivity were due to the localized dislocation activities (generalization and annihilation at grain boundaries) and the more significant contribution from grain boundary mediated mechanisms. In the micro-compression tests, the sample size effects on the mechanical behaviours were studied on MA0, MA20 and MA40 micro-pillars. In contrast to the bulk samples under compression, the stress-strain curves of MA0 and MA20 micro-pillars were characterized with a number of discrete strain burst events separated by nearly elastic strain segments. Unlike MA0 and MA20, the stress-strain curves of MA40 micro-pillars were smooth, without obvious strain bursts. The deformation mechanisms of the MA0 and MA20 micro-pillars under micro-compression tests were considered to be initially dominated by deformation twinning, followed by dislocation mechanisms. For MA40 pillars, the deformation mechanisms were believed to be localized dislocation activities and grain boundary related mechanisms. The strain hardening behaviours of the micro-pillars suggested that the grain boundaries in the nanocrystalline micro-pillars would reduce the source (nucleation sources for twins/dislocations) starvation hardening effect. The power law relationship of the yield strength on pillar dimensions in MA0, MA20 supported the fact that the twinning mechanism was correlated to the pre-existing defects, which can promote the nucleation of the twins. Then, we provided a latitudinal comparison of the results and conclusions derived from the different techniques used for testing the coarse-grained and nanocrystalline Mg alloy; this helps to better understand the deformation mechanisms of the Mg alloys as a whole. At the end, we summarized the thesis and highlighted the conclusions, contributions, innovations and outcomes of the research. Finally, it outlined recommendations for future work.

Environmental factors controlling temporal and spatial variability in the soil-atmosphere exchange of CO2, CH4 and N2O from an Australian subtropical rainforest

The temporal variations in CO2, CH4 and N2O fluxes were measured over two consecutive years from February 2007 to March 2009 from a subtropical rainforest in south-eastern Queensland, Australia, using an automated sampling system. A concurrent study using an additional 30 manual chambers examined the spatial variability of emissions distributed across three nearby remnant rainforest sites with similar vegetation and climatic conditions. Interannual variation in fluxes of all gases over the 2 years was minimal, despite large discrepancies in rainfall, whereas a pronounced seasonal variation could only be observed for CO2 fluxes. High infiltration, drainage and subsequent high soil aeration under the rainforest limited N2O loss while promoting substantial CH4 uptake. The average annual N2O loss of 0.5 ± 0.1 kg N2O-N ha−1 over the 2-year measurement period was at the lower end of reported fluxes from rainforest soils. The rainforest soil functioned as a sink for atmospheric CH4 throughout the entire 2-year period, despite periods of substantial rainfall. A clear linear correlation between soil moisture and CH4 uptake was found. Rates of uptake ranged from greater than 15 g CH4-C ha−1 day−1 during extended dry periods to less than 2–5 g CH4-C ha−1 day−1 when soil water content was high. The calculated annual CH4 uptake at the site was 3.65 kg CH4-C ha−1 yr−1. This is amongst the highest reported for rainforest systems, reiterating the ability of aerated subtropical rainforests to act as substantial sinks of CH4. The spatial study showed N2O fluxes almost eight times higher, and CH4 uptake reduced by over one-third, as clay content of the rainforest soil increased from 12% to more than 23%. This demonstrates that for some rainforest ecosystems, soil texture and related water infiltration and drainage capacity constraints may play a more important role in controlling fluxes than either vegetation or seasonal variability