The correlation of indentation size effect experiments with pyramidal and spherical indenters

Experiments were conducted in annealed iridium using pyramidal and spherical indenters over a wide range of load. For a Berkovich pyramidal indenter, the hardness increased with decreasing depth of penetration. However, for spherical indenters, hardness increased with decreasing sphere radius. Based on the number of geometrically necessary dislocations generated during indentation, a theory that takes into account the work hardening differences between pyramidal and spherical indenters is developed to correlate the indentation size effects measured with the two indenters. The experimental results verify the theoretical correlation.

Size anomalies in EU bank stock returns

Mestrado em Finanças

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.

Setting water quality objectives for the health of freshwater fish

An important responsibility of the Environment Protection Authority, Victoria, is to set objectives for levels of environmental contaminants. To support the development of environmental objectives for water quality, a need has been identified to understand the dual impacts of concentration and duration of a contaminant on biota in freshwater streams. For suspended solids contamination, information reported by Newcombe and Jensen [ North American Journal of Fisheries Management , 16(4):693--727, 1996] study of freshwater fish and the daily suspended solids data from the United States Geological Survey stream monitoring network is utilised. The study group was requested to examine both the utility of the Newcombe and Jensen and the USA data, as well as the formulation of a procedure for use by the Environment Protection Authority Victoria that takes concentration and duration of harmful episodes into account when assessing water quality. The extent to which the impact of a toxic event on fish health could be modelled deterministically was also considered. It was found that concentration and exposure duration were the main compounding factors on the severity of effects of suspended solids on freshwater fish. A protocol for assessing the cumulative effect on fish health and a simple deterministic model, based on the biology of gill harm and recovery, was proposed. References D. W. T. Au, C. A. Pollino, R. S. S Wu, P. K. S. Shin, S. T. F. Lau, and J. Y. M. Tang. Chronic effects of suspended solids on gill structure, osmoregulation, growth, and triiodothyronine in juvenile green grouper epinephelus coioides . Marine Ecology Press Series , 266:255--264, 2004. J.C. Bezdek, S.K. Chuah, and D. Leep. Generalized k-nearest neighbor rules. Fuzzy Sets and Systems , 18:237--26, 1986. E. T. Champagne, K. L. Bett-Garber, A. M. McClung, and C. Bergman. {Sensory characteristics of diverse rice cultivars as influenced by genetic and environmental factors}. Cereal Chem. , {81}:{237--243}, {2004}. S. G. Cheung and P. K. S. Shin. Size effects of suspended particles on gill damage in green-lipped mussel perna viridis. Marine Pollution Bulletin , 51(8--12):801--810, 2005. D. H. Evans. The fish gill: site of action and model for toxic effects of environmental pollutants. Environmental Health Perspectives , 71:44--58, 1987. G. C. Grigg. The failure of oxygen transport in a fish at low levels of ambient oxygen. Comp. Biochem. Physiol. , 29:1253--1257, 1969. G. Holmes, A. Donkin, and I.H. Witten. {Weka: A machine learning workbench}. In Proceedings of the Second Australia and New Zealand Conference on Intelligent Information Systems , volume {24}, pages {357--361}, {Brisbane, Australia}, {1994}. {IEEE Computer Society}. D. D. Macdonald and C. P. Newcombe. Utility of the stress index for predicting suspended sediment effects: response to comments. North American Journal of Fisheries Management , 13:873--876, 1993. C. P. Newcombe. Suspended sediment in aquatic ecosystems: ill effects as a function of concentration and duration of exposure. Technical report, British Columbia Ministry of Environment, Lands and Parks, Habitat Protection branch, Victoria, 1994. C. P. Newcombe and J. O. T. Jensen. Channel suspended sediment and fisheries: A synthesis for quantitative assessment of risk and impact. North American Journal of Fisheries Management , 16(4):693--727, 1996. C. P. Newcombe and D. D. Macdonald. Effects of suspended sediments on aquatic ecosystems. North American Journal of Fisheries Management , 11(1):72--82, 1991. K. Schmidt-Nielsen. Scaling. Why is animal size so important? Cambridge University Press, NY, 1984. J. S. Schwartz, A. Simon, and L. Klimetz. Use of fish functional traits to associate in-stream suspended sediment transport metrics with biological impairment. Environmental Monitoring and Assessment , 179(1--4):347--369, 2011. E. Al Shaw and J. S. Richardson. Direct and indirect effects of sediment pulse duration on stream invertebrate assemb ages and rainbow trout ( Oncorhynchus mykiss ) growth and survival. Canadian Journal of Fish and Aquatic Science , 58:2213--2221, 2001. P. Tiwari and H. Hasegawa. {Demand for housing in Tokyo: A discrete choice analysis}. Regional Studies , {38}:{27--42}, {2004}. Y. Tramblay, A. Saint-Hilaire, T. B. M. J. Ouarda, F. Moatar, and B Hecht. Estimation of local extreme suspended sediment concentrations in california rivers. Science of the Total Environment , 408:4221--

Effect of constraint on ductile crack growth and ductile-brittle fracture transition of a carbon steel

Ductile-brittle fracture transition was investigated using compact tension (CT) specimens from -70oC to 40oC for a carbon steel. Large deformation finite element analysis has been carried out to simulate the stable crack growth in the compact tension (CT, a/W=0.6), three point-point bend (SE(B), a/W=0.1) and centre-cracked tension (M(T), a/W=0.5) specimens. Experimental crack tip opening displacement (CTOD) resistance curve was employed as the crack growth criterion. Ductile tearing is sensitive to constraint and tearing modulus increases with reduced constraint level. The finite element analysis shows that path-dependence of J-integral occurs from the very beginning of crack growth and ductile crack growth elevates the opening stress on the remaining ligament. Cleavage may occur after some ductile crack growth due to the increase of opening stress. For both stationary and growing cracks, the magnitude of opening stress increases with increasing in-plane constraint. The ductile-brittle transition takes place when the opening stress ahead of the crack tip reaches the local cleavage stress as the in-plane constraint of the specimen increases.

Numerical optimization of soft-mold aided co-curing process of advanced grid-stiffened composite structures

The co-curing process for advanced grid-stiffened (AGS) composite structure is a promising manufacturing process, which could reduce the manufacturing cost, augment the advantages and improve the performance of AGS composite structure. An improved method named soft-mold aided co-curing process which replaces the expansion molds by a whole rubber mold is adopted in this paper. This co-curing process is capable to co-cure a typical AGS composite structure with the manufacturer’s recommended cure cycle (MRCC). Numerical models are developed to evaluate the variation of temperature and the degree of cure in AGS composite structure during the soft-mold aided co-curing process. The simulation results were validated by experimental results obtained from embedded temperature sensors. Based on the validated modeling framework, the cycle of cure can be optimized by reducing more than half the time of MRCC while obtaining a reliable degree of cure. The shape and size effects of AGS composite structure on the distribution of temperature and degree of cure are also investigated to provide insights for the optimization of soft-mold aided co-curing process.

High Lithium Storage in Mixed Crystallographic Phase Nanotubes of Titania and Carbon-Titania

Morphology and electrochemical performance of mixed crystallographic phase titania nanotubes for prospective application as anode in rechargeable lithium ion batteries are discussed. Hydrothermally grown nanotubes of titania (TiO2) and carbon-titania (C-TiO2) comprise a mixture of both anatase and TiO2 (B) crystallographic phases. The first cycle capacity (at Current rate = 10 mAg(-1)) for bare TiO2 nanotubes was 355 mAhg(-1) (approximately 1.06 Li), which is higher than both the theoretical capacity (335 mAhg(-1)) and the reported values for pure anatase and TiO2 (B) nanotubes. Higher capacity is attributed to it combination of the presence of mixed crystallographic phases of titania and trivial size effects. The surface area of bare TiO2 nanotubes was very high at 340 m(2) g(-1). C-TiO2 nanotubes showed a slightly lower first-cycle specific capacity of 307 mAhg(-1), but the irreversible capacity loss in the first cycle decreased by half compared to bare TiO2 nanotubes. The C-TiO2 nanotubes also showed a better rate capability, that is, higher capacities compared to bare TiO2 nanotubes in the Current range 0.1-2 Ag-1. Enhanced rate capability in the case of C-TiO2 is attributed to the efficient percolation of electrons as well its to the decrease in the anatase phase.

Spatial correlation in grain misorientation distribution

Grain misorientation was studied in relation to the nearest neighbor's mutual distance using electron back-scattered diffraction measurements. The misorientation correlation function was defined as the probability density for the occurrence of a certain misorientation between pairs of grains separated by a certain distance. Scale-invariant spatial correlation between neighbor grains was manifested by a power law dependence of the preferred misorientation vs. inter-granular distance in various materials after diverse strain paths. The obtained negative scaling exponents were in the range of -2 +/- 0.3 for high-angle grain boundaries. The exponent decreased in the presence of low-angle grain boundaries or dynamic recrystallization, indicating faster decay of correlations. The correlations vanished in annealed materials. The results were interpreted in terms of lattice incompatibility and continuity conditions at the interface between neighboring grains. Grain-size effects on texture development, as well as the implications of such spatial correlations on texture modeling, were discussed.

Elastic Properties of Alkali Phosphomolybdate Glasses

Ultrasonic velocities at 10 MHz have been measured in two series of lithium, sodium, and potassium phosphomolybdate glasses with two fixed P2O5 concentrations. Elastic moduli, Poisson's ratio, and Debye temperature have been calculated. The composition dependence of most of the properties of lithium glasses exhibits a trend opposite to that of potassium glasses. Properties of sodium glasses lie between the other two alkali systems. Alkali oxide modification is suggested to be accompanied by ring reformation in lithium and sodium glasses. Ring size effects have been shown to account for all of the composition dependence.

Tuning the interfacial properties of supported metal nanoclusters

Nanoclusters are objects made up of several to thousands of atoms and form a transitional state of matter between single atoms and bulk materials. Due to their large surface-to-volume ratio, nanoclusters exhibit exciting and yet poorly studied size dependent properties. When deposited directly on bare metal surfaces, the interaction of the cluster with the substrate leads to alteration of the cluster properties, making it less or even non-functional. Surfaces modified with self-assembled monolayers (SAMs) were shown to form an interesting alternative platform, because of the possibility to control wettability by decreasing the surface reactivity and to add functionalities to pre-formed nanoclusters. In this thesis, the underlying size effects and the influence of the nanocluster environment are investigated. The emphasis is on the structural and magnetic properties of nanoclusters and their interaction with thiol SAMs. We report, for the first time, a ferromagnetic-like spin-glass behaviour of uncapped nanosized Au islands tens of nanometres in size. The flattening kinetics of the nanocluster deposition on thiol SAMs are shown to be mediated mainly by the thiol terminal group, as well as the deposition energy and the particle size distribution. On the other hand, a new mechanism for the penetration of the deposited nanoclusters through the monolayers is presented, which is fundamentally different from those reported for atom deposition on alkanethiols. The impinging cluster is shown to compress the thiol layer against the Au surface and subsequently intercalate at the thiol-Au interface. The compressed thiols try then to straighten and push the cluster away from the surface. Depending on the cluster size, this restoring force may or may not enable a covalent cluster-surface bond formation, giving rise to various cluster-surface binding patterns. Compression and straightening of the thiol molecules pinpoint the elastic nature of the SAMs, which has been investigated in this thesis using nanoindentation. The nanoindenation method has been applied to SAMs of varied tail groups, giving insight into the mechanical properties of thiol modified metal surfaces.

Interfacial shear rheology of highly confined glassy polymers

We present results on interfacial shear rheology measurements on Langmuir monolayers of two different polymers, poly(vinyl acetate) and poly(methyl methacrylate) as a function of surface concentration and temperature. While for the high glass transition poly(methyl methacrylate) polymer we find a systematic transition from a viscous dominated regime to an elastic dominated regime as surface concentration is increased, monolayers of the low glass transition polymer, poly(vinyl acetate), remain viscous even at very high surface concentrations. We further interpret the results in terms of the soft glassy rheology model of Sollich et al. P. Sollich, F. C. Lequeux, P. Hebraud and M. E. Cates, Phys. Rev. Lett., 1997, 78, 2020-2023] and provide evidence of possible reduction in glass transition temperatures in both poly(methyl methacrylate) and poly(vinyl acetate) monolayers due to finite size effects.

Role of multicritical points in addressing some key problems concerning condensed matter science

We illustrate the potential of using higher order critical points in the deeper understanding of several interesting problems of condensed matter science, e.g. critical adsorption, finite size effects, morphology of critical fluctuations, reversible aggregation of colloids, dynamics of the ordering process, etc.

X-ray photoelectron spectroscopic investigations of Cu-Ni, Au-Ag, Ni-Pd, and Cu-Pd bimetallic clusters

Core-level binding energies of the component metals in bimetallic clusters of various compositions in the Ni-Cu, Au-Ag, Ni-Pd, and Cu-Pd systems have been measured as functions of coverage or cluster size, after having characterized the clusters with respect to sizes and compositions. The core-level binding energy shifts, relative to the bulk metals, at large coverages or cluster size, Delta E(a), are found to be identical to those of bulk alloys. By substracting the Delta E(a) values from the observed binding energy shifts, Delta E, we obtain the shifts, Delta E(c), due to cluster size. The Delta E(c) values in all the alloy systems increase with the decrease in cluster size. These results establish the additivity of the binding energy shifts due to alloying and cluster size effects in bimetallic clusters.

Backward switching phenomenon from field forced ferroelectric to antiferroelectric phases in antiferroelectric PbZrO3 thin films

Antiferroelectric materials (example: lead zirconate and modified lead zirconate stannate), in which a field-induced ferroelectric phase transition is feasible due to a small free energy difference between the ferroelectric and the antiferroelectric phases, are proven to be very good candidates for applications involving actuation and high charge storage devices. The property of reverse switching from the field-induced ferroelectric to antiferroelectric phases is studied as a function of temperature, applied electric field, and sample thickness in antiferroelectric lead zirconate thin films deposited by pulsed excimer laser ablation. The maximum released charge density was 22 μC/cm2 from a stored charge density of 36 μC/cm2 in a 0.55 μ thick lead zirconate thin film. This indicated that more than 60% of the stored charge could be released in less than 7 ns at room temperature for a field of 200 kV/cm. The content of net released charge was found to increase with increasing field strength, whereas with increasing temperature the released charge was found to decrease. Thickness-dependent studies on lead zirconate thin films showed that size effects relating to extrinsic and intrinsic pinning mechanisms controlled the released and induced charges through the intrinsic switching time. These results proved that antiferroelectric PZ thin films could be utilized in high-speed charge decoupling capacitors in microelectronics applications.