Synthesis and crystal phase evaluation of hydroxylapatite using the rietveld-maximum entropy method

Bioceramic systems based on hydroxylapatite (HAP) are an important class of bioactive materials that may promote bone regeneration. The aim of this research was to evaluate how the stoichiometry of HAP influences its microstructural properties when diagnosed using the combined Rietveld method and Maximum entropy method (MEM). The Rietveld Method (RM) is recognizably a powerful tool used to obtain structural and microstructural information of polycrystalline samples analyzed by x-ray diffraction. Latterly have combined the RM with the maximum entropy method (MEM), with the goal of improve structural refinement results. The MEM provides high resolution maps of electron density and their analysis leave the accurate localization of atoms inside of unit cell. Like that, cycles Rietveld-MEM allow an excellent structural refinement In this work, a hydroxylapatite sample obtained by emulsion method had its structure refined using one cycle Rietveld-MEM with x-ray diffraction data. The indices obtained in initial refinement was Rwp = 7.50%, Re = 6.56%, S - 1.14% e RB = 1.03%. After MEM refinement and electron densities maps analysis to correction of atomics positions, the news indicators of Rietveld refinement quality was Rwp = 7.35%, Re = 6.56%, S = 1.12% and RB = 0.75%. The excellent result obtained to RB shows the efficiency of MEM as auxiliary in the refinement of structure of hydroxylapatite by RM.

Thermoelectric performance of p-type TiCoSb half-Heusler compounds - Intrinsic phase separation and charge carrier concentration optimization as key to high efficiency

The world's rising demand of energy turns the development of sustainable and more efficient technologies for energy production and storage into an inevitable task. Thermoelectric generators, composed of pairs of n-type and p-type semiconducting materials, di¬rectly transform waste heat into useful electricity. The efficiency of a thermoelectric mate¬rial depends on its electronic and lattice properties, summarized in its figure of merit ZT. Desirable are high electrical conductivity and Seebeck coefficients, and low thermal con¬ductivity. Half-Heusler materials are very promising candidates for thermoelectric applications in the medium¬ temperature range such as in industrial and automotive waste heat recovery. The advantage of Heusler compounds are excellent electronic properties and high thermal and mechanical stability, as well as their low toxicity and elemental abundance. Thus, the main obstacle to further enhance their thermoelectric performance is their relatively high thermal conductivity.rn rnIn this work, the thermoelectric properties of the p-type material (Ti/Zr/Hf)CoSb1-xSnx were optimized in a multistep process. The concept of an intrinsic phase separation has recently become a focus of research in the compatible n-type (Ti/Zr/Hf)NiSn system to achieve low thermal conductivities and boost the TE performance. This concept is successfully transferred to the TiCoSb system. The phase separation approach can form a significant alternative to the previous nanostructuring approach via ball milling and hot pressing, saving pro¬cessing time, energy consumption and increasing the thermoelectric efficiency. A fundamental concept to tune the performance of thermoelectric materials is charge carrier concentration optimization. The optimum carrier concentration is reached with a substitution level for Sn of x = 0.15, enhancing the ZT about 40% compared to previous state-of-the-art samples with x = 0.2. The TE performance can be enhanced further by a fine-tuning of the Ti-to-Hf ratio. A correlation of the microstructure and the thermoelectric properties is observed and a record figure of merit ZT = 1.2 at 710°C was reached with the composition Ti0.25Hf0.75CoSb0.85Sn0.15.rnTowards application, the long term stability of the material under actual conditions of operation are an important issue. The impact of such a heat treatment on the structural and thermoelectric properties is investigated. Particularly, the best and most reliable performance is achieved in Ti0.5Hf0.5CoSb0.85Sn0.15, which reached a maximum ZT of 1.1 at 700°C. The intrinsic phase separation and resulting microstructure is stable even after 500 heating and cooling cycles.

High-resolution computer simulation of the dynamics of isoelectric focusing using carrier ampholytes: focusing with concurrent electrophoretic mobilization is an isotachophoretic process

Focusing of four hemoglobins with concurrent electrophoretic mobilization was studied by computer simulation. A dynamic electrophoresis simulator was first used to provide a detailed description of focusing in a 100-carrier component, pH 6-8 gradient using phosphoric acid as anolyte and NaOH as catholyte. These results are compared to an identical simulation except that the catholyte contained both NaOH and NaCl. A stationary, steady-state distribution of carrier components and hemoglobins is produced in the first configuration. In the second, the chloride ion migrates into and through the separation space. It is shown that even under these conditions of chloride ion flux a pH gradient forms. All amphoteric species acquire a slight positive charge upon focusing and the whole pattern is mobilized towards the cathode. The cathodic gradient end is stable whereas the anodic end is gradually degrading due to the continuous accumulation of chloride. The data illustrate that the mobilization is a cationic isotachophoretic process with the sodium ion being the leading cation. The peak height of the hemoglobin zones decreases somewhat upon mobilization, but the zones retain a relatively sharp profile, thus facilitating detection. The electropherograms that would be produced by whole column imaging and by a single detector placed at different locations along the focusing column are presented and show that focusing can be commenced with NaCl present in the catholyte at the beginning of the experiment. However, this may require detector placement on the cathodic side of the catholyte/sample mixture interface.

High-resolution computer simulation of the dynamics of isoelectric focusing: in quest of more realistic input parameters for carrier ampholytes

The impact of the systematic variation of either DeltapK(a) or mobility of 140 biprotic carrier ampholytes on the conductivity profile of a pH 3-10 gradient was studied by dynamic computer simulation. A configuration with the greatest DeltapK(a) in the pH 6-7 range and uniform mobilities produced a conductivity profile consistent with that which is experimentally observed. A similar result was observed when the neutral (pI = 7) ampholyte is assigned the lowest mobility and mobilities of the other carriers are systematically increased as their pI's recede from 7. When equal DeltapK(a) values and mobilities are assigned to all ampholytes a conductivity plateau in the pH 5-9 region is produced which does not reflect what is seen experimentally. The variation in DeltapK(a) values is considered to most accurately reflect the electrochemical parameters of commercially available mixtures of carrier ampholytes. Simulations with unequal mobilities of the cationic and anionic species of the carrier ampholytes show either cathodic (greater mobility of the cationic species) or anodic (greater mobility of the anionic species) drifts of the pH gradient. The simulated cationic drifts compare well to those observed experimentally in a capillary in which the focusing of three dyes was followed by whole column optical imaging. The cathodic drift flattens the acidic portion of the gradient and steepens the basic part. This phenomenon is an additional argument against the notion that focused zones of carrier ampholytes have no electrophoretic flux.

High-resolution dynamic computer simulation analysis of the behavior of sample components with pI values outside the pH gradient established by carrier ampholyte CIEF

The behavior of sample components whose pI values are outside the pH gradient established by 101 hypothetical biprotic carrier ampholytes covering a pH 6-8 range was investigated by computer simulation under constant current conditions with concomitant constant electroosmosis toward the cathode. Data obtained with the sample being applied between zones of carrier ampholytes and on the anodic side of the carrier ampholytes were studied and found to evolve into zone structures comprising three regions between anolyte and catholyte. The focusing region with the pH gradient is bracketed by two isotachopheretic zone structures comprising selected sample and carrier components as isotachophoretic zones. The isotachophoretic structures electrophoretically migrate in opposite direction and their lengths increase with time due to the gradual isotachophoretic decay at the pH gradient edges. Due to electroosmosis, however, the overall pattern is being transported toward the cathode. Sample components whose pI values are outside the established pH gradient are demonstrated to form isotachophoretic zones behind the leading cation of the catholyte (components with pI values larger than 8) and the leading anion of the anolyte (components with pI values smaller than 6). Amphoteric compounds with appropriate pI values or nonamphoteric components can act as isotachophoretic spacer compounds between sample compounds or between the leader and the sample with the highest mobility. The simulation data obtained provide for the first time insight into the dynamics of amphoteric sample components that do not focus within the established pH gradient.

High-resolution in situ oxygen microprofiles, porewater and solid phase geochemistry from the Crimean shelf (Black Sea) from Maria S. Merian cruise MSM15/1

The outer western Crimean shelf of the Black Sea is a natural laboratory to investigate effects of stable oxic versus varying hypoxic conditions on seafloor biogeochemical processes and benthic community structure. Bottom-water oxygen concentrations ranged from normoxic (175 µmol O2/L) and hypoxic (< 63 µmol O2/L) or even anoxic/sulfidic conditions within a few kilometers' distance. Variations in oxygen concentrations between 160 and 10 µmol/L even occurred within hours close to the chemocline at 134 m water depth. Total oxygen uptake, including diffusive as well as fauna-mediated oxygen consumption, decreased from 15 mmol/m**2/d on average in the oxic zone, to 7 mmol/m**2/d on average in the hypoxic zone, correlating with changes in macrobenthos composition. Benthic diffusive oxygen uptake rates, comprising respiration of microorganisms and small meiofauna, were similar in oxic and hypoxic zones (on average 4.5 mmol/m**2/d), but declined to 1.3 mmol/m**2/d in bottom waters with oxygen concentrations below 20 µmol/L. Measurements and modeling of porewater profiles indicated that reoxidation of reduced compounds played only a minor role in diffusive oxygen uptake under the different oxygen conditions, leaving the major fraction to aerobic degradation of organic carbon. Remineralization efficiency decreased from nearly 100 % in the oxic zone, to 50 % in the oxic-hypoxic zone, to 10 % in the hypoxic-anoxic zone. Overall, the faunal remineralization rate was more important, but also more influenced by fluctuating oxygen concentrations, than microbial and geochemical oxidation processes.

Contribución al diseño de lazos de realimentación electrónica para microsistemas electromecánicos (MEMS) resonantes: ruido de fase generado en lazos osciladores por sus realimentaciones

En 1966, D. B. Leeson publicó el artículo titulado “A simple model of feedback oscillator noise spectrum” en el que, mediante una ecuación obtenida de forma heurística y basada en parámetros conocidos de los osciladores, proponía un modelo para estimar el espectro de potencia que cuantifica el Ruido de Fase de estos osciladores. Este Ruido de Fase pone de manifiesto las fluctuaciones aleatorias que se producen en la fase de la señal de salida de cualquier oscilador de frecuencia f_0. Desde entonces, los adelantos tecnológicos han permitido grandes progresos en cuanto a la medida del Ruido de Fase, llegando a encontrar una estrecha “zona plana”, alrededor de f_0, conocida con el nombre de Ensanchamiento de Línea (EL) que Leeson no llegó a observar y que su modelo empírico no recogía. Paralelamente han ido surgiendo teorías que han tratado de explicar el Ruido de Fase con mayor o menor éxito. En esta Tesis se propone una nueva teoría para explicar el espectro de potencia del Ruido de Fase de un oscilador realimentado y basado en resonador L-C (Inductancia-Capacidad). Al igual que otras teorías, la nuestra también relaciona el Ruido de Fase del oscilador con el ruido térmico del circuito que lo implementa pero, a diferencia de aquellas, nuestra teoría se basa en un Modelo Complejo de ruido eléctrico que considera tanto las Fluctuaciones de energía eléctrica asociadas a la susceptancia capacitiva del resonador como las Disipaciones de energía eléctrica asociadas a su inevitable conductancia G=1⁄R, que dan cuenta del contacto térmico entre el resonador y el entorno térmico que le rodea. En concreto, la nueva teoría que proponemos explica tanto la parte del espectro del Ruido de Fase centrada alrededor de la frecuencia portadora f_0 que hemos llamado EL y su posterior caída proporcional a 〖∆f〗^(-2) al alejarnos de f_0, como la zona plana o pedestal que aparece en el espectro de Ruido de Fase lejos de esa f_0. Además, al saber cuantificar el EL y su origen, podemos explicar con facilidad la aparición de zonas del espectro de Ruido de Fase con caída 〖∆f〗^(-3) cercanas a la portadora y que provienen del denominado “exceso de ruido 1⁄f” de dispositivos de Estado Sólido y del ruido “flicker” de espectro 1⁄f^β (0,8≤β≤1,2) que aparece en dispositivos de vacío como las válvulas termoiónicas. Habiendo mostrado que una parte del Ruido de Fase de osciladores L-C realimentados que hemos denominado Ruido de Fase Térmico, se debe al ruido eléctrico de origen térmico de la electrónica que forma ese oscilador, proponemos en esta Tesis una nueva fuente de Ruido de Fase que hemos llamado Ruido de Fase Técnico, que se añadirá al Térmico y que aparecerá cuando el desfase del lazo a la frecuencia de resonancia f_0 del resonador no sea 0° o múltiplo entero de 360° (Condición Barkhausen de Fase, CBF). En estos casos, la modulación aleatoria de ganancia de lazo que realiza el Control Automático de Amplitud en su lucha contra ruidos que traten de variar la amplitud de la señal oscilante del lazo, producirá a su vez una modulación aleatoria de la frecuencia de tal señal que se observará como más Ruido de Fase añadido al Térmico. Para dar una prueba empírica sobre la existencia de esta nueva fuente de Ruido de Fase, se diseñó y construyó un oscilador en torno a un resonador mecánico “grande” para tener un Ruido de Fase Térmico despreciable a efectos prácticos. En este oscilador se midió su Ruido de Fase Técnico tanto en función del valor del desfase añadido al lazo de realimentación para apartarlo de su CBF, como en función de la perturbación de amplitud inyectada para mostrar sin ambigüedad la aparición de este Ruido de Fase Técnico cuando el lazo tiene este fallo técnico: que no cumple la Condición Barkhausen de Fase a la frecuencia de resonancia f_0 del resonador, por lo que oscila a otra frecuencia. ABSTRACT In 1966, D. B. Leeson published the article titled “A simple model of feedback oscillator noise spectrum” in which, by means of an equation obtained heuristically and based on known parameters of the oscillators, a model was proposed to estimate the power spectrum that quantifies the Phase Noise of these oscillators. This Phase Noise reveals the random fluctuations that are produced in the phase of the output signal from any oscillator of frequencyf_0. Since then, technological advances have allowed significant progress regarding the measurement of Phase Noise. This way, the narrow flat region that has been found around f_(0 ), is known as Line Widening (LW). This region that Leeson could not detect at that time does not appear in his empirical model. After Leeson’s work, different theories have appeared trying to explain the Phase Noise of oscillators. This Thesis proposes a new theory that explains the Phase Noise power spectrum of a feedback oscillator around a resonator L-C (Inductance-Capacity). Like other theories, ours also relates the oscillator Phase Noise to the thermal noise of the feedback circuitry, but departing from them, our theory uses a new, Complex Model for electrical noise that considers both Fluctuations of electrical energy associated with the capacitive susceptance of the resonator and Dissipations of electrical energy associated with its unavoidable conductance G=1/R, which accounts for the thermal contact between the resonator and its surrounding environment (thermal bath). More specifically, the new theory we propose explains both the Phase Noise region of the spectrum centered at the carrier frequency f_0 that we have called LW and shows a region falling as 〖∆f〗^(-2) as we depart from f_0, and the flat zone or pedestal that appears in the Phase Noise spectrum far from f_0. Being able to quantify the LW and its origin, we can easily explain the appearance of Phase Noise spectrum zones with 〖∆f〗^(-3) slope near the carrier that come from the so called “1/f excess noise” in Solid-State devices and “flicker noise” with 1⁄f^β (0,8≤β≤1,2) spectrum that appears in vacuum devices such as thermoionic valves. Having shown that the part of the Phase Noise of L-C oscillators that we have called Thermal Phase Noise is due to the electrical noise of the electronics used in the oscillator, this Thesis can propose a new source of Phase Noise that we have called Technical Phase Noise, which will appear when the loop phase shift to the resonance frequency f_0 is not 0° or an integer multiple of 360° (Barkhausen Phase Condition, BPC). This Phase Noise that will add to the Thermal one, comes from the random modulation of the loop gain carried out by the Amplitude Automatic Control fighting against noises trying to change the amplitude of the oscillating signal in the loop. In this case, the BPC failure gives rise to a random modulation of the frequency of the output signal that will be observed as more Phase Noise added to the Thermal one. To give an empirical proof on the existence of this new source of Phase Noise, an oscillator was designed and constructed around a “big” mechanical resonator whose Thermal Phase Noise is negligible for practical effects. The Technical Phase Noise of this oscillator has been measured with regard to the phase lag added to the feedback loop to separate it from its BPC, and with regard to the amplitude disturbance injected to show without ambiguity the appearance of this Technical Phase Noise that appears when the loop has this technical failure: that it does not fulfill the Barkhausen Phase Condition at f_0, the resonance frequency of the resonator and therefore it is oscillating at a frequency other than f_0.

Report on dental education : a response to House Resolution 334, Phase I.

"October 2001"

Organizational, direct and general support, and depot maintenance repair parts and special tools list : air conditioner, floor mounted, air cooled, 60,000 Btu/hr, 208/416V, 50/60 cycle, 3 phase (Carrier Air Conditioning Co. model 76E34-104), FSN 4120-963-4477.

"June 1968."

Operator, organizational, direct and general support, and depot maintenance manual : air conditioner, floor mounting, air-cooled, 60,000 Btu/hr, 208/416 volts, 50/60 cycle, 3 phase, Carrier Air Conditioning Co. model 76E34-104, serial number range 66000001 ....

"November 1966."

Sales manager problem resolution styles:measure development and an examination of their salesperson-related consequences

Personal selling and sales management play a critical role in the short and long term success of the firm, and have thus received substantial academic interest since the 1970s. Sales research has examined the role of the sales manager in some depth, defining a number of key technical and interpersonal roles which sales managers have in influencing sales force effectiveness. However, one aspect of sales management which appears to remain unexplored is that of their resolution of salesperson-related problems. This study represents the first attempt to address this gap by reporting on the conceptual and empirical development of an instrument designed to measure sales managers' problem resolution styles. A comprehensive literature review and qualitative research study identified three key constructs relating to sales managers' problem resolution styles. The three constructs identified were termed; sales manager willingness to respond, sales manager caring, and sales manager aggressiveness. Building on this, existing literature was used to develop a conceptual model of salesperson-specific consequences of the three problem resolution style constructs. The quantitative phase of the study consisted of a mail survey of UK salespeople, achieving a total sample of 140 fully usable responses. Rigorous statistical assessment of the sales manager problem resolution style measures was undertaken, and construct validity examined. Following this, the conceptual model was tested using latent variable path analysis. The results for the model were encouraging overall, and also with regard to the individual hypotheses. Sales manager problem resolution styles were found individually to have significant impacts on the salesperson-specific variables of role ambiguity, emotional exhaustion, job satisfaction, organisational commitment and organisational citizenship behaviours. The findings, theoretical and managerial implications, limitations and directions for future research are discussed.

Rayleigh noise mitigation in DWDM LR-PONs using carrier suppressed subcarrier-amplitude modulated phase shift keying

We demonstrate a novel Rayleigh interferometric noise mitigation scheme for applications in carrier-distributed dense wavelength division multiplexed (DWDM) passive optical networks at 10 Gbit/s using carrier suppressed subcarrier-amplitude modulated phase shift keying modulation. The required optical signal to Rayleigh noise ratio is reduced by 12 dB, while achieving excellent tolerance to dispersion, subcarrier frequency and drive amplitude variations.