The role of aggregates in the thermal stability of Mg-PSZ refractories for vacuum induction melting

Mg-PSZ refractories used as vacuum induction melting crucibles are particle-reinforced composites with aggregate and matrix phases comprising fused zirconia. Three commercial varieties were cycled eight times to service temperatures and their microstructural and thermomechanical evolution investigated, with focus placed on the aggregate populations. Two refractories, with large aggregates of similar size, were found to retain stiffness after cycling but in the refractory containing aggregates with high stabiliser levels, reaction between the stabiliser and Al and Si impurities produced secondary phases. Volume changes accompanying formation of these phases, and subsequent thermal expansion mismatches, led to aggregate break-up with consequent reductions in refractory toughness and strength. Secondary phases developed only rarely in the aggregates (with lower levels of stabiliser) of the second refractory. These aggregates remained intact and the refractory retained its toughness and strength. A third refractory contained small, unstabilised aggregates in a stabilised matrix and the strain mismatches that ensued during polymorphic transformation damaged microstructural interfaces. Refractory stiffness halved within eight cycles and toughness and strength were lost. All three refractories displayed R-curve behaviour and quasi-stable fracture curves were observed during bend tests. The study shows that when using fused zirconia aggregates to design refractories, engineers need to i) limit stabiliser concentrations - a difference of just ±1 wt% Mg (in the presence of impurity elements) may determine whether secondary phase formation occurs and ii) eliminate alumina and silica impurities when possible through substitution of zircon sand with baddeleyite as the source for fused zirconia.Open Acces

Comparison of Algorithms for Baseline Correction of LIBS Spectra for Quantifying Total Carbon in Brazilian Soils

LIBS is a promising and versatile technique for multi-element analysis that usually takes less than a minute and requires minimal sample preparation and no reagents. Despite the recent advances in elemental quantification, the LIBS still faces issues regarding the baseline produced by background radiation, which adds non-linear interference to the emission lines. In order to create a calibration model to quantify elements using LIBS spectra, the baseline has to be properly corrected. In this paper, we compared the performance of three filters to remove random noise and five methods to correct the baseline of LIBS spectra for the quantification of total carbon in soil samples. All combinations of filters and methods were tested, and their parameters were optimized to result in the best correlation between the corrected spectra and the carbon content in a training sample set. Then all combinations with the optimized parameters were compared with a separate test sample set. A combination of Savitzky-Golay filter and 4S Peak Filling method resulted in the best correction: Pearson's correlation coefficient of 0.93 with root mean square error of 0.21. The result was better than using a linear regression model with the carbon emission line 193.04 nm (correlation of 0.91 with error of 0.26). The procedure proposed here opens a new possibility to correct the baseline of LIBS spectra and to create multivariate methods based on the a given spectral range.Comment: 13 pages, 5 figure

Laser Induced Incandescence and Laser Induced Breakdown Spectroscopy based Sensor Development

In this doctoral dissertation, two laser-based sensors were evaluated for different applications. Laser Induced Incandescence (LII) is a technique which can provide nonintrusive quantitative measurement of soot and it provides a unique diagnostic tool to characterize engine performance. Since LII is linearly proportional to the soot volume fraction, it can provide in situ, real time measurement of soot volume fraction with high temporal and spatial resolution. LII has the capability to characterize soot formation during combustion. The soot volume fraction from both flames and a soot generator was investigated with LII. The effects of experimental parameters, such as laser fluence, gate delay, gate width and various laser beam focusing, on LII signal was studied. Laser Induced Breakdown Spectroscopy (LIBS), a diagnostic tool for in situ elemental analysis, has been evaluated for on-line, simultaneous, multi-species impurity monitoring in hydrogen. LIBS spectra with different impurity levels of nitrogen, argon, and oxygen were recorded and the intensity of the spectral lines of Ar, O, N, and H observed were used to form calibration plots for impurities in hydrogen measurements. An ungated detection method for LIBS has been developed and applied to equivalence ratio measurements of CH4/air and biofuel/air. LIBS has also been used to quantitatively analyze the composition of a slurry sample. The quenching effect of water in slurry samples causes low LIBS signal quality with poor sensitivity. Univariate and multivariate calibration was performed on LIBS spectra of dried slurry samples for elemental analysis of Mg, Si and Fe. Calibration results show that the dried slurry samples give good correlation between spectral intensity and elemental concentration

Substituent effects on absorption spectra of pH indicators: an experimental and computational study of sulfonphthaleine dyes

Sulfonphthaleine dyes are an important class of pH indicators, finding applications in novel (textile) sensors. In this paper, we present a combined experimental and theoretical study to elucidate the halochromic behaviour of a large set of sulfonphthaleine compounds. Starting from an experimental analysis consisting of UV-Vis spectroscopy, the pH region and the absorption wavelengths related to the colour shift are obtained and pK(a) values are derived. The effect of the substituents on the pH region can be traced back to their electron donating/withdrawing properties. Time-Dependent Density Functional Theory (TD-DFT) is able to adequately produce the trend in experimental wavelengths. Proton affinities are used to assess the effect of substituents on the pH region. The combination of theory and experiment is able to give a better understanding of the pH sensitivity; the methodology in this work will be useful in future dye design and is applicable to other dye classes as well. (C) 2013 Elsevier Ltd. All rights reserved

Spherulite formation in obsidian lavas in the Aeolian Islands, Italy

The authors wish to gratefully acknowledge Andy Tindle (The Open University) for assistance with EMP analyses, and Richard Darton and David Evans (Keele University) for assistance with XRD and Prof Alun Vaughan and Nicola Freebody (University of Southampton) with Raman analyses. LAB is grateful to Sophie Blanchard for support with MATLAB. The authors acknowledge support from Keele University, and grants from the Mineralogical Society (UK and Ireland) and Volcanic and Magmatic Studies Group. The authors thank Silvio Mollo and Francesca Forni for their detailed and helpful comments.Peer reviewedPublisher PD

The EVA spectral descriptor

The EVA descriptor is derived from fundamental IR- and Raman range molecular vibrational frequencies. EVA is sensitive to 3D structure but has an advantage over field-based 3D-QSAR methods inasmuch as it is invariant to both translation and rotation of the structures concerned and thus structural superposition is not required. The latter property and the demonstration of the effectiveness of the descriptor for QSAR means that EVA has been the subject of a great deal of interest from the modelling community. This review describes the derivation of the descriptor, details its main parameters and how to apply them, and provides an overview of the validation that has been done with the descriptor. A recent enhancement to the technique is described which involves the localised adjustment of variance in such a way that enhanced internal and external predictivity may be obtained. Despite the statistical quality of EVA QSAR models the main draw-back to the descriptor at present is the difficulty associated with back-tracking from a PLS model to an EVA pharmacophore. Brief comment is made on the use of the EVA descriptor for diversity studies and the similarity searching of chemical structure databases

Doctor of Philosophy

dissertationModern medicine would benefi t from the pursuit of new, more speci fic and easier to implement diagnosis tools. In recent years, Raman scattering, surface-enhanced Raman scattering and fluorescence spectroscopy have proven to be successful diagnostic techniques for a wide range of diseases including atherosclerosis, kidney stones, bone diseases, diabetes, and a wide collection of neoplasms. Optical spectroscopy has several advantages over more traditional diagnostic methods (i.e., histopathology, quantitative PCR, etc.) such as faster data analysis, nonspecifi c sample preparation, nonspecifi c labels/reagents/antibodies usage requirements, and immediate on-site implementation. In the present work, label-free in vitro fluorescence and surface enhanced Raman scattering (SERS) spectroscopy have been used to di fferentiate between blood cells of patients aff ected with myeloproliferative neoplasms (MPN) and those of healthy subjects. The SERS technique has also been applied to hemoglobin variants as well as to serum obtained from patients affected with chronic heart failure who positively or negatively responded to the seasonal influenza vaccine. We found that spectral ratios of the background fluorescence intensity that accompanies the SERS spectra of granulocytes serve as excellent markers for the presence of MPNs. In addition, we also found expression dysregulation of two hypoxia induced factor regulated genes, which correlates with our results obtained by SERS spectroscopy assay in MPN patients and supports the presence of the Warburg e ffect in MPNs. We hypothesize that SERS measures metabolic change in granulocytes through two possible mechanisms: (i) Changes in dielectric properties of the environment surrounding the silver-cell interface; and (ii) changes in flavinadenine dinucleotide concentrations, which in turn changes the relative contribution of the auto uorescence to the emission spectrum. These hypotheses are supported by SERS measurement of 2-deoxy-D-glucose incubated granulocytes, where the emission spectra show a similar behavior as observed in the SERS spectra of controls and patients. Using SERS spectroscopy in combination with multivariate analysis (e.g., principal component analysis) and classi fication algorithms (e.g., support vector machines), we are able to distinguish among hemoglobin variants S, C and E and traits FS and FE, as well as seasonal infuenza vaccine responders and nonresponders within a population of patients su ffering from chronic heart failure. The results presented here may have an extraordinary impact on the diagnostics of patients having Myeloproliferative Neoplasms, as well as on the health care management of patients aff ected with hemoglobinopathies and chronic heart failure

Carrier relaxation, pseudogap, and superconducting gap in high-Tc cuprates: A Raman scattering study

We describe results of electronic Raman-scattering experiments in differently doped single crystals of Y-123 and Bi-2212. The comparison of AF insulating and metallic samples suggests that at least the low-energy part of the spectra originates predominantly from excitations of free carriers. We therefore propose an analysis of the data in terms of a memory function approach. Dynamical scattering rates and mass-enhancement factors for the carriers are obtained. In B2g symmetry the Raman data compare well to the results obtained from ordinary and optical transport. For underdoped materials the dc scattering rates in B1g symmetry become temperature independent and considerably larger than in B2g symmetry. This increasing anisotropy is accompanied by a loss of spectral weight in B2g symmetry in the range between the superconducting transition at Tc and a characteristic temperature T* of order room temperature which compares well with the pseudogap temperature found in other experiments. The energy range affected by the pseudogap is doping and temperature independent. The integrated spectral loss is approximately 25% in underdoped samples and becomes much weaker towards higher carrier concentration. In underdoped samples, superconductivity related features in the spectra can be observed only in B2g symmetry. The peak frequencies scale with Tc. We do not find a direct relation between the pseudogap and the superconducting gap.Comment: RevTeX, 21 pages, 24 gif figures. For PostScript with embedded eps figures, see http://www.wmi.badw-muenchen.de/~opel/k2.htm