Radiative Relaxation Quantum Yields for Synthetic Eumelanin

We report absolute values for the radiative relaxation quantum yield of synthetic eumelanin as a function of excitation energy. These values were determined by correcting for pump beam attenuation and emission reabsorption in both eumelanin samples and fluorescein standards over a large range of concentrations. Our results confirm that eumelanins are capable of dissipating >99.9% of absorbed UV and visible radiation through nonradiative means. Furthermore, we have found that the radiative quantum yield of synthetic eumelanin is excitation energy dependent. This observation is supported by corrected emission spectra, which also show a clear dependence of both peak position and peak width on excitation energy. Our findings indicate that photoluminescence emission in eumelanins is derived from ensembles of small chemically distinct oligomeric units that can be selectively pumped. This hypothesis lends support to the theory that the basic structural unit of eumelanin is oligomeric rather than heteropolymeric.

Cyclotron effective masses in layered metals

Many layered metals such as quasi-two-dimensional organic molecular crystals show properties consistent with a Fermi-liquid description at low temperatures. The effective masses extracted from the temperature dependence of the magnetic oscillations observed in these materials are in the range, m(c)*/m(e) similar to 1 - 7, suggesting that these systems are strongly correlated. However, the ratio m(c)*/m(e) contains both the renormalization due to the electron-electron interaction and the periodic potential of the lattice. We show that for any quasi-two-dimensional band structure, the cyclotron mass is proportional to the density-of-states at the Fermi energy. Due to Luttinger's theorem, this result is also valid in the presence of interactions. We then evaluate m(c) for several model band structures for the beta, kappa, and theta families of (BEDT-TTF)(2)X, where BEDT-TTF is bis-(ethylenedithia-tetrathiafulvalene) and X is an anion. We find that for kappa-(BEDT-TTF)(2)X, the cyclotron mass of the beta orbit, m(c)*(beta) is close to 2 m(c)*(alpha), where m(c)*(alpha) is the effective mass of the alpha orbit. This result is fairly insensitive to the band-structure details. For a wide range of materials we compare values of the cyclotron mass deduced from band-structure calculations to values deduced from measurements of magnetic oscillations and the specific-heat coefficient gamma.

Aluminium alloys - their physical and mechanical properties: Grain formation in AlSi7Mg0.35 foundry alloy at low superheat

Hypoeutectic AI-Si alloys represent the most widely used alloy system for cast aluminium applications. This system has a unique behaviour with respect to grain formation where an increase in silicon content results in a transition to larger grain sizes after a minimum at an intermediate concentration. As a result of the already large solute content, grain refinement by solute additions is inefficient and nucleant particles from the common aluminium grain refiners are not as effective as in wrought alloys. However, casting conditions, such as a low pouring temperature, that promote the formation of wall crystals tie. crystals nucleated in the thermally undercooled layer at or next to mould walls) are very effective in yielding a small grain size. This paper presents results of an investigation of the effect of low superheat and mould preheat temperature on grain size. It was found that pouring temperature controls the effectiveness of the wall mechanism while mould preheat has little effect until high preheat temperatures at which a large increase in grain size occurs. The observed changes in grain size are explained in terms of the balance between nucleation rate and survival rate of crystal nuclei resulting from changes in superheat and mould temperature.

A numerical study of effect of grain boundaries on elastic and plastic properties in nanocomposite materials

Nanocomposite materials have received considerable attention in recent years due to their novel properties. Grain boundaries are considered to play an important role in nanostructured materials. This work focuses on the finite element analysis of the effect of grain boundaries on the overall mechanical properties of aluminium/alumina composites. A grain boundary is incorporated into the commonly used unit cell model to investigate its effect on material properties. By combining the unit cell model with an indentation model, coupled with experimental indentation measurements, the ''effective'' plastic property of the grain boundary is estimated. In addition, the strengthening mechanism is also discussed based on the Estrin-Mecking model.

Improvement of the electrolytic properties of Y2O3-based materials using a crystallographic index

Y2O3 is a c-type rare earth oxide with a fluorite-related structure. This material has been used to refractory because of its high thermal stability and excellent resistance to hydration. In this study, the effective index was suggested in order to improve the electrolytic properties of Y2O3-based oxide. (CexY1-x)(2)O3+delta (x = 0.25 and 0.3) and [LaaSrbCe0.25Y(1-a-b)](2)O3+delta (a = 0.05, 0.1 and 0.15, b = 0, 0.006 and 0.0125) were prepared as the examples with intermediate and high index, respectively. The specimens with high index value such as (La0.15Ce0.25Y0.60)(2)O-3.25 and (La0.1Sr0.0125Ce0.25Y0.6375)(2)O-3.24 consisted of two phases such as c-type and fluorite, although (Ce0.25Y0.75)(2)O-3.25 with intermediate index value had a single phase of c-type rare earth oxide. Microanalysis indicates that a grain in the (La0.1Sr0.0125Ce0.25Y0.6375)(2)O-3.23(7) sintered body consists of c-type and fluorite phases. An interface between c-type and fluorite phases is coherent in a grain. This suggests that this effective index guides the crystal structure in the specimen to fluorite and the examined composition introduces the interface between c-type and fluorite in the microstructure. The electrochemical properties of specimens including Y2O3 were characterized on the basis of the suggested index. The electrical conductivity of Y2O3-based materials increased with an increase of the index. The apparent activation energy of Y2O3-based materials decreased with increasing index. The ionic transport number of oxygen of the specimens was improved by enhancement of the index, confirming validity of the index. The oxide ionic conductive region of (La0.1Sr0.0125Ce0.25Y0.(6375))(2)O-3.23(7) with high effective index extended up to P-O2 = 10(-18) atm at 800 degreesC, although the specimens with low or intermediate index showed p- or n-type semi-conduction in the same P-O2 region at 800 and 1000 degreesC. These results suggest that the interface between c-type and fluorite phases also contributes to improve the electrolytic properties in the grain. It is concluded that the improvement of electrolytic properties in Y2O3-based materials is attributable to the microstructure with interface between two phases in a grain and the fluorite structure guided by the suggested index. (C) 2001 Published by Elsevier Science B.V.

Precipitation hardening of Cu-Fe-Cr alloys - Part I - Mechanical and electrical properties

This research is part of a project whose scope was to investigate the engineering properties of new non-commercial alloy formulations based on the Cu rich corner of the Cu-Fe-Cr ternary system with the primary aim of exploring the development of a new cost-effective high-strength, high-conductivity copper alloy. The literature indicated that Cu rich Cu-Cr and Cu-Fe alloys have been thoroughly investigated. A number of commercial alloys have been developed and these are used for a variety of applications requiring combinations of high-strength, high-conductivity and resistance to softening. Little evidence was found in the literature that the Cu rich corner of the Cu-Fe-Cr system had previously been investigated for the purpose of developing high-strength, high-conductivity copper alloys resistant to softening. The aim of these present investigations was to explore the possibility that new alloys could be developed that combined the properties of both sets of alloys, ie large precipitation hardening response combined with the ability to stabilise cold worked microstructures to high temperatures while at the same maintain high electrical conductivity. To assess the feasibility of this goal the following alloys were chosen for investigation: Cu-0.7wt%Cr-0.3wt%Fe, Cu-0.7wt%Cr-0.8wt%Fe, Cu-0.7wt%Cr-2.0wt%Fe. This paper reports on the mechanical property investigation which indicated that the Cu-0.7wt%Cr-0.3wt%Fe, and Cu-0.7wt%Cr-2.0wt%Fe alloys were worthy of further investigation. (C) 2001 Kluwer Academic Publishers.

Computation of the linear elastic properties of random porous materials with a wide variety of microstructure

A finite-element method is used to study the elastic properties of random three-dimensional porous materials with highly interconnected pores. We show that Young's modulus, E, is practically independent of Poisson's ratio of the solid phase, nu(s), over the entire solid fraction range, and Poisson's ratio, nu, becomes independent of nu(s) as the percolation threshold is approached. We represent this behaviour of nu in a flow diagram. This interesting but approximate behaviour is very similar to the exactly known behaviour in two-dimensional porous materials. In addition, the behaviour of nu versus nu(s) appears to imply that information in the dilute porosity limit can affect behaviour in the percolation threshold limit. We summarize the finite-element results in terms of simple structure-property relations, instead of tables of data, to make it easier to apply the computational results. Without using accurate numerical computations, one is limited to various effective medium theories and rigorous approximations like bounds and expansions. The accuracy of these equations is unknown for general porous media. To verify a particular theory it is important to check that it predicts both isotropic elastic moduli, i.e. prediction of Young's modulus alone is necessary but not sufficient. The subtleties of Poisson's ratio behaviour actually provide a very effective method for showing differences between the theories and demonstrating their ranges of validity. We find that for moderate- to high-porosity materials, none of the analytical theories is accurate and, at present, numerical techniques must be relied upon.

Influence of nano-structure on electrolytic properties in CeO2 based system

Doped ceria (CeO2) compounds are fluorite type oxides that show oxygen ionic conductivity higher than yttria stabilized zirconia, in oxidizing atmosphere. In order to improve the conductivity, the effective index was suggested to maximize the oxygen ionic conductivity in doped CeO2 based oxides. In addition, the true microstructure of doped CeO2 was observed at atomic scale for conclusion of conduction mechanism. Doped CeO2 had small domains (10-50 nm) with ordered structure in a grain. It is found that the electrolytic properties strongly depended on the nano-structural feature at atomic scale in doped CeO2 electrolyte.

A family of textilinin genes, two of which encode proteins with antihaemorrhagic properties

Two peptides, textilinins 1 and 2, isolated from the venom of the Australian common brown snake, Pseudonaja textilis textilis, are effective in preventing blood loss. To further investigate the potential of textilinins as anti-haemorrhagic agents, we cloned cDNAs encoding these proteins. The isolated full-length cDNA (430 bp in size) was shown to code for a 59 amino acid protein, corresponding in size to the native peptide, plus an additional 24 amino acid propeptide. Six such cDNAs were identified, differing in nucleotide sequence in the coding region but with an identical propeptide. All six sequences predicted peptides containing six conserved cysteines common to Kunitz-type serine protease inhibitors. When expressed as glutathione S-transferase (GST) fusion proteins and released by cleavage with thrombin, only those peptides corresponding to textilinin 1 and 2 were active in inhibiting plasmin with K-i values similar to those of their native counterparts and in binding to plasmin less tightly than aprotinin by two orders of magnitude. Similarly, in the mouse tail vein blood loss model only recombinant textilinin 1 and 2 were effective in reducing blood loss. These recombinant textilinins have potential as therapeutic agents for reducing blood loss in humans, obviating the need for reliance on aprotinin, a bovine product with possible risk of transmissible disease, and compromising the fibrinolytic system in a less irreversible manner.

Electrolytic properties and nanostructural features in the La2O3-CeO2 system

Doped ceria (CeO2) compounds are fluorite-type oxides which show oxide ionic conductivity higher than yttria-stabilized zirconia in oxidizing atmosphere. As a consequence of this, considerable interest has been shown in applications of these materials for low or intermediate temperature operation of solid-oxide fuel cells (SOFCs). In this study, the effective index was suggested to maximize the ionic conductivity in La2O3-CeO2 based oxides. The index considers the fluorite structure, and combines the expected oxygen vacancy level with the ionic radius mismatch between host and dopant cations. Using this approach, the ionic conductivity of this system has been optimized and tested under operating conditions of SOFCs. LaxCe1-xO2-delta (x = 0.125, 0.15, 0.175, and 0.20), (LaxSr1-x)(0.175)Ce0.825O2-delta (x = 0.1, 0.2, and 0.4), and (La1-xSr0.2Bax)(0.175)Ce0.825O2-delta (x 5 0.03, 0.05, and 0.07) were prepared and characterized as the specimens with low, intermediate, and high index, respectively. The ionic conductivity was increased with increasing suggested index. The transmission electron microscopy analysis suggested that partial substitution of alkaline earth elements in place of La into Ce site contributes to a decrease of microdomain size and an improvement of conductivity. (La0.75Sr0.2Ba0.05)(0.175)Ce0.825O1.891 with high index and small microdomains exhibited the highest conductivity, wide ionic domain, and good performance in SOFCs. (C) 2003 The Electrochemical Society.

Numerical study of hydrogenic effective mass theory for an impurity P donor in Si in the presence of an electric field and interfaces

In this paper we examine the effects of varying several experimental parameters in the Kane quantum computer architecture: A-gate voltage, the qubit depth below the silicon oxide barrier, and the back gate depth to explore how these variables affect the electron density of the donor electron. In particular, we calculate the resonance frequency of the donor nuclei as a function of these parameters. To do this we calculated the donor electron wave function variationally using an effective-mass Hamiltonian approach, using a basis of deformed hydrogenic orbitals. This approach was then extended to include the electric-field Hamiltonian and the silicon host geometry. We found that the phosphorous donor electron wave function was very sensitive to all the experimental variables studied in our work, and thus to optimize the operation of these devices it is necessary to control all parameters varied in this paper.

Evidence for energy relaxation via a radiative cascade in surface-passivated PbS quantum dots

Multiple emission peaks have been observed from surface passivated PbS nanocrystals displaying strong quantum confinement. The emission spectra are shown to be strongly dependent on the excited-state parity. We also find that intraband energy relaxation from initial states excited far above the band-edge is nearly three orders of magnitude slower than that found in other nanocrystal quantum dots, providing evidence of inefficient energy relaxation via phonon emission. The initial-state parity dependence of the photoluminescent emission properties suggests that energy relaxation from the higher excited states occurs via a radiative cascade, analogous to energy relaxation in atomic systems. Such radiative cascade emission is possible from ideal zero-dimensional semiconductors, where electronic transitions can be decoupled from phonon modes.

Effects of rock properties on specific cutting energy in linear cutting of sandstones by picks

Specific cutting energy (SE) has been widely used to assess the rock cuttability for mechanical excavation purposes. Some prediction models were developed for SE through correlating rock properties with SE values. However, some of the textural and compositional rock parameters i.e. texture coefficient and feldspar, mafic, and felsic mineral contents were not considered. The present study is to investigate the effects of previously ignored rock parameters along with engineering rock properties on SE. Mineralogical and petrographic analyses, rock mechanics, and linear rock cutting tests were performed on sandstone samples taken from sites around Ankara, Turkey. Relationships between SE and rock properties were evaluated using bivariate correlation and linear regression analyses. The tests and subsequent analyses revealed that the texture coefficient and feldspar content of sandstones affected rock cuttability, evidenced by significant correlations between these parameters and SE at a 90% confidence level. Felsic and mafic mineral contents of sandstones did not exhibit any statistically significant correlation against SE. Cementation coefficient, effective porosity, and pore volume had good correlations against SE. Poisson's ratio, Brazilian tensile strength, Shore scleroscope hardness, Schmidt hammer hardness, dry density, and point load strength index showed very strong linear correlations against SE at confidence levels of 95% and above, all of which were also found suitable to be used in predicting SE individually, depending on the results of regression analysis, ANOVA, Student's t-tests, and R2 values. Poisson's ratio exhibited the highest correlation with SE and seemed to be the most reliable SE prediction tool in sandstones.

Study of optical properties of electropolymerized melanin films by photopyroelectric spectroscopy

Photopyroelectric (PPE) spectroscopy, in the 350-1,075 nm wavelength range, was used to study the optical properties of electropolymerized melanin films on indium tin oxide (ITO) coated glass. The PPE intensity signal as a function of the wavelength lambda, V (n)(lambda) and its phase F (n)(lambda) were independently measured. Using the PPE signal intensity and the thermal and optical properties of the pyroelectric detector, we were able to calculate the optical absorption coefficient beta of melanin in the solid-state. We believe this to be the first such measurement of its kind on this material. Additionally, we found an optical gap in these melanin films at 1.70 eV.

Effects of rock properties on specific cutting energy in linear cutting of sandstones by picks

Specific cutting energy (SE) has been widely used to assess the rock cuttability for mechanical excavation purposes. Some prediction models were developed for SE through correlating rock properties with SE values. However, some of the textural and compositional rock parameters i.e. texture coefficient and feldspar, mafic, and felsic mineral contents were not considered. The present study is to investigate the effects of previously ignored rock parameters along with engineering rock properties on SE. Mineralogical and petrographic analyses, rock mechanics, and linear rock cutting tests were performed on sandstone samples taken from sites around Ankara, Turkey. Relationships between SE and rock properties were evaluated using bivariate correlation and linear regression analyses. The tests and subsequent analyses revealed that the texture coefficient and feldspar content of sandstones affected rock cuttability, evidenced by significant correlations between these parameters and SE at a 90% confidence level. Felsic and mafic mineral contents of sandstones did not exhibit any statistically significant correlation against SE. Cementation coefficient, effective porosity, and pore volume had good correlations against SE. Poisson's ratio, Brazilian tensile strength, Shore scleroscope hardness, Schmidt hammer hardness, dry density, and point load strength index showed very strong linear correlations against SE at confidence levels of 95% and above, all of which were also found suitable to be used in predicting SE individually, depending on the results of regression analysis, ANOVA, Student's t-tests, and R-2 values. Poisson's ratio exhibited the highest correlation with SE and seemed to be the most reliable SE prediction tool in sandstones.