Structural and optical properties of Cu2O crystalline electrodeposited films

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Polymer controlled mineralization of zinc phosphate hydrates and applications in corrosion protection, catalysis and biomedicine

ZUSAMMENFASSUNG Die Tauglichkeit von Hybridmaterialien auf der Basis von Zinkphosphathydrat-Zementen zum Einsatz als korrosionshemmende anorganische Pigmente oder zur prothetischen und konservierenden Knochen- und Zahntherapie wird weltweit empirisch seit den neunziger Jahren intensiv erforscht. In der vorliegenden Arbeit wurden zuerst Referenzproben, d.h. alpha-und beta-Hopeite (Abk. a-,b-ZPT) dank eines hydrothermalen Kristallisationsverfahrens in wässerigem Milieu bei 20°C und 90°C hergestellt. Die Kristallstruktur beider Polymorphe des Zinkphosphattetrahydrats Zn3(PO4)2  4 H2O wurde komplett bestimmt. Einkristall-strukturanalyse zeigt, daß der Hauptunterschied zwischen der alpha-und beta-Form des Zinkphosphattetrahydrats in zwei verschiedenen Anordnungen der Wasserstoffbrücken liegt. Die entsprechenden drei- und zweidimensionalen Anordnungen der Wasserstoffbrücken der a-und b-ZPT induzieren jeweils unterschiedliches thermisches Verhalten beim Aufwärmen. Während die alpha-Form ihr Kristallwasser in zwei definierten Stufen verliert, erzeugt die beta-Form instabile Dehydratationsprodukt. Dieses entspricht zwei unabhängigen, aber nebeneinander ablaufenden Dehydratationsmechanismen: (i) bei niedrigen Heizraten einen zweidimensionalen Johnson-Mehl-Avrami (JMA) Mechanismus auf der (011) Ebene, der einerseits bevorzugt an Kristallkanten stattfindet und anderseits von existierenden Kristalldefekten auf Oberflächen gesteuert wird; (ii) bei hohen Heizraten einem zweidimensionalen Diffusionsmechanismus (D2), der zuerst auf der (101) Ebene und dann auf der (110) Ebene erfolgt. Durch die Betrachtung der ZPT Dehydratation als irreversibele heterogene Festkörperstufenreaktion wurde dank eines „ähnlichen Endprodukt“-Protokolls das Dehydratationsphasendiagramm aufgestellt. Es beschreibt die möglichen Zusammenhänge zwischen den verschiedenen Hydratationszuständen und weist auf die Existenz eines Übergangszustandes um 170°C (d.h. Reaktion b-ZPT  a-ZPT) hin. Daneben wurde auch ein gezieltes chemisches Ätzverfahren mit verdünnten H3PO4- und NH3 Lösungen angewendet, um die ersten Stufe des Herauslösens von Zinkphosphat genau zu untersuchen. Allerdings zeigen alpha- und beta-Hopeite charakteristische hexagonale und kubische Ätzgruben, die sich unter kristallographischer Kontrolle verbreitern. Eine zuverlässige Beschreibung der Oberfächenchemie und Topologie konnte nur durch AFM und FFM Experimente erfolgen. Gleichzeitig konnte in dieser Weise die Oberflächendefektdichte und-verteilung und die Volumenauflösungsrate von a-ZPT und b-ZPT bestimmt werden. Auf einem zweiten Weg wurde eine innovative Strategie zur Herstellung von basischen Zinkphosphatpigmenten erster und zweiter Generation (d.h. NaZnPO4  1H2O und Na2ZnPO4(OH)  2H2O) mit dem Einsatz von einerseits oberflächenmodifizierten Polystyrolatices (z.B. produziert durch ein Miniemulsionspolymerisationsverfahren) und anderseits von Dendrimeren auf der Basis von Polyamidoamid (PAMAM) beschritten. Die erhaltene Zeolithstruktur (ZPO) hat in Abhängigkeit von steigendem Natrium und Wassergehalt unterschiedliche kontrollierte Morphologie: hexagonal, würfelförmig, herzförmig, sechsarmige Sterne, lanzettenförmige Dendrite, usw. Zur quantitativen Evaluierung des Polymereinbaus in der Kristallstruktur wurden carboxylierte fluoreszenzmarkierte Latices eingesetzt. Es zeigt sich, daß Polymeradditive nicht nur das Wachstum bis zu 8 µm.min-1 reduzierten. Trotzdem scheint es auch als starker Nukleationsbeschleuniger zu wirken. Dank der Koordinationschemie (d.h. Bildung eines sechszentrigen Komplexes L-COO-Zn-PO4*H2O mit Ligandenaustausch) konnten zwei einfache Mechanismen zur Wirkung von Latexpartikeln bei der ZPO Kristallisation aufgezeigt werden: (i) ein Intrakorona- und (ii) ein Extrakorona-Keimbildungsmechanismus. Weiterhin wurde die Effizienz eines Kurzzeit- und Langzeitkorrosionschutzes durch maßgeschneiderte ZPO/ZPT Pigmente und kontrollierte Freisetzung von Phosphationen in zwei Näherungen des Auslösungsgleichgewichts abgeschätzt: (i) durch eine Auswaschungs-methode (thermodynamischer Prozess) und (ii) durch eine pH-Impulsmethode (kinetischer Prozess. Besonders deutlich wird der Ausflösungs-Fällungsmechanismus (d.h. der Metamorphismus). Die wesentliche Rolle den Natriumionen bei der Korrosionshemmung wird durch ein passendes zusammensetzungsabhängiges Auflösungsmodell (ZAAM) beschrieben, das mit dem Befund des Salzsprühteste und der Feuchtigkeitskammertests konsistent ist. Schließlich zeigt diese Arbeit das herausragende Potential funktionalisierter Latices (Polymer) bei der kontrollierten Mineralisation zur Herstellung maßgeschneiderter Zinkphosphat Materialien. Solche Hybridmaterialien werden dringend in der Entwicklung umweltfreundlicher Korrosionsschutzpigmente sowie in der Dentalmedizin benötigt.

Optical properties and defect structure of Sr2+ co-doped LaBr3:5%Ce scintillation crystals

Sr2+ co-doped LaBr3:5%Ce scintillators show a record low energy resolution of 2% at 662 keV and a considerably better proportional response compared to standard LaBr3:5%Ce. This paper reports on the optical properties and time response of Sr co-doped LaBr3:5%Ce. Multiple excitation and emission bands were observed in X-ray and optically excited luminescence measurements. Those bands are ascribed to three different Ce3+ sites. The first is the unperturbed site with the same luminescence properties as those of standard LaBr3:Ce. The other two are perturbed sites with red-shifted 4f-5d1 Ce3+ excitation and emission bands, longer Ce3+ decay times, and smaller Stokes shifts. The lowering of the lowest 5d level of Ce3+ was ascribed to larger crystal field interactions at the perturbed sites. Two types of point defects in the LaBr3 matrix were proposed to explain the observed results. No Ce4+ ions were detected in Sr co-doped LaBr3:5%Ce by diffuse reflectance measurements.

Object Kinetic Monte Carlo calculations of irradiated Fe-Cr dilute alloys: The effect of the interaction radius between substitutional Cr and self-interstitial Fe

ObjectKineticMonteCarlo models allow for the study of the evolution of the damage created by irradiation to time scales that are comparable to those achieved experimentally. Therefore, the essential ObjectKineticMonteCarlo parameters can be validated through comparison with experiments. However, this validation is not trivial since a large number of parameters is necessary, including migration energies of point defects and their clusters, binding energies of point defects in clusters, as well as the interactionradii. This is particularly cumbersome when describing an alloy, such as the Fe–Cr system, which is of interest for fusion energy applications. In this work we describe an ObjectKineticMonteCarlo model for Fe–Cr alloys in the dilute limit. The parameters used in the model come either from density functional theory calculations or from empirical interatomic potentials. This model is used to reproduce isochronal resistivity recovery experiments of electron irradiateddiluteFe–Cr alloys performed by Abe and Kuramoto. The comparison between the calculated results and the experiments reveal that an important parameter is the capture radius between substitutionalCr and self-interstitialFe atoms. A parametric study is presented on the effect of the capture radius on the simulated recovery curves.

Estudio de la tolerancia al daño de los materiales y sistemas de pretensado

La mayoría de las estructuras de hormigón pretensadas construidas en los últimos 50 años han demostrado una excelente durabilidad cuando su construcción se realiza atendiendo las recomendaciones de un buen diseño así como una buena ejecución y puesta en obra de la estructura. Este hecho se debe en gran parte al temor que despierta el fenómeno de la corrosión bajo tensión típico de las armaduras de acero de alta resistencia. Menos atención se ha prestado a la susceptibilidad a la corrosión bajo tensión de los anclajes de postensado, posiblemente debido a que se han reportado pocos casos de fallos catastróficos. El concepto de Tolerancia al Daño y la Mecánica de la Fractura en estructuras de Ingeniería Civil ha empezado a incorporarse recientemente en algunas normas de diseño y cálculo de estructuras metálicas, sin embargo, aún está lejos de ser asimilado y empleado habitualmente por los ingenieros en sus cálculos cuando la ocasión lo requiere. Este desconocimiento de los aspectos relacionados con la Tolerancia al Daño genera importantes gastos de mantenimiento y reparación. En este trabajo se ha estudiado la aplicabilidad de los conceptos de la Mecánica de la Fractura a los componentes de los sistemas de postensado empleados en ingeniería civil, empleándolo para analizar la susceptibilidad de las armaduras activas frente a la corrosión bajo tensiones y a la pérdida de capacidad portante de las cabezas de anclajes de postensado debido a la presencia de defectos. Con este objeto se han combinado tanto técnicas experimentales como numéricas. Los defectos superficiales en los alambres de pretensado no se presentan de manera aislada si no que existe una cierta continuidad en la dirección axial así como un elevado número de defectos. Por este motivo se ha optado por un enfoque estadístico, que es más apropiado que el determinístico. El empleo de modelos estadísticos basados en la teoría de valores extremos ha permitido caracterizar el estado superficial en alambres de 5,2 mm de diámetro. Por otro lado la susceptibilidad del alambre frente a la corrosión bajo tensión ha sido evaluada mediante la realización de una campaña de ensayos de acuerdo con la actual normativa que ha permitido caracterizar estadísticamente su comportamiento. A la vista de los resultados ha sido posible evaluar como los parámetros que definen el estado superficial del alambre pueden determinar la durabilidad de la armadura atendiendo a su resistencia frente a la corrosión bajo tensión, evaluada mediante los ensayos que especifica la normativa. En el caso de las cabezas de anclaje de tendones de pretensado, los defectos se presentan de manera aislada y tienen su origen en marcas, arañazos o picaduras de corrosión que pueden producirse durante el proceso de fabricación, transporte, manipulación o puesta en obra. Dada la naturaleza de los defectos, el enfoque determinístico es más apropiado que el estadístico. La evaluación de la importancia de un defecto en un elemento estructural requiere la estimación de la solicitación local que genera el defecto, que permite conocer si el defecto es crítico o si puede llegar a serlo, si es que progresa con el tiempo (por fatiga, corrosión, una combinación de ambas, etc.). En este trabajo los defectos han sido idealizados como grietas, de manera que el análisis quedara del lado de la seguridad. La evaluación de la solicitación local del defecto ha sido calculada mediante el empleo de modelos de elementos finitos de la cabeza de anclaje que simulan las condiciones de trabajo reales de la cabeza de anclaje durante su vida útil. A partir de estos modelos numéricos se ha analizado la influencia en la carga de rotura del anclaje de diversos factores como la geometría del anclaje, las condiciones del apoyo, el material del anclaje, el tamaño del defecto su forma y su posición. Los resultados del análisis numérico han sido contrastados satisfactoriamente mediante la realización de una campaña experimental de modelos a escala de cabezas de anclaje de Polimetil-metacrilato en los que artificialmente se han introducido defectos de diversos tamaños y en distintas posiciones. ABSTRACT Most of the prestressed concrete structures built in the last 50 years have demonstrated an excellent durability when they are constructed in accordance with the rules of good design, detailing and execution. This is particularly true with respect to the feared stress corrosion cracking, which is typical of high strength prestressing steel wires. Less attention, however, has been paid to the stress corrosion cracking susceptibility of anchorages for steel tendons for prestressing concrete, probably due to the low number of reported failure cases. Damage tolerance and fracture mechanics concepts in civil engineering structures have recently started to be incorporated in some design and calculation rules for metallic structures, however it is still far from being assimilated and used by civil engineers in their calculations on a regular basis. This limited knowledge of the damage tolerance basis could lead to significant repair and maintenance costs. This work deals with the applicability of fracture mechanics and damage tolerance concepts to the components of prestressed systems, which are used in civil engineering. Such concepts have been applied to assess the susceptibility of the prestressing steel wires to stress corrosion cracking and the reduction of load bearing capability of anchorage devices due to the presence of defects. For this purpose a combination of experimental work and numerical techniques have been performed. Surface defects in prestressing steel wires are not shown alone, though a certain degree of continuity in the axial direction exist. A significant number of such defects is also observed. Hence a statistical approach was used, which is assumed to be more appropriate than the deterministic approach. The use of statistical methods based in extreme value theories has allowed the characterising of the surface condition of 5.2 mm-diameter wires. On the other hand the stress corrosion cracking susceptibility of the wire has been assessed by means of an experimental testing program in line with the current regulations, which has allowed statistical characterisasion of their performances against stress corrosion cracking. In the light of the test results, it has been possible to evaluate how the surface condition parameters could determine the durability of the active metal armour regarding to its resistance against stress corrosion cracking assessed by means of the current testing regulations. In the case of anchorage devices for steel tendons for prestressing concrete, the damage is presented as point defects originating from dents, scratches or corrosion pits that could be produced during the manufacturing proccess, transport, handling, assembly or use. Due to the nature of these defects, in this case the deterministic approach is more appropriate than the statistical approach. The assessment of the relevancy of defect in a structural component requires the computation of the stress intensity factors, which in turn allow the evaluation of whether the size defect is critical or could become critical with the progress of time (due to fatigue, corrosion or a combination of both effects). In this work the damage is idealised as tiny cracks, a conservative hypothesis. The stress intensity factors have been calculated by means of finite element models of the anchorage representing the real working conditions during its service life. These numeric models were used to assess the impact of some factors on the rupture load of the anchorage, such the anchorage geometry, material, support conditions, defect size, shape and its location. The results from the numerical analysis have been succesfully correlated against the results of the experimental testing program of scaled models of the anchorages in poly-methil methacrylate in which artificial damage in several sizes and locations were introduced.

A molecular dynamics study of swift heavy ion irradiation of amorphous silica: the role of thermal effects

Irradiation with swift heavy ions (SHI), roughly defined as those having atomic masses larger than 15 and energies exceeding 1 MeV/amu, may lead to significant modification of the irradiated material in a nanometric region around the (straight) ion trajectory (latent tracks). In the case of amorphous silica, SHI irradiation originates nano-tracks of higher density than the virgin material (densification). As a result, the refractive index is increased with respect to that of the surroundings. Moreover, track overlapping leads to continuous amorphous layers that present a significant contrast with respect to the pristine substrate. We have recently demonstrated that SHI irradiation produces a large number of point defects, easily detectable by a number of experimental techniques (work presented in the parallel conference ICDIM). The mechanisms of energy transfer from SHI to the target material have their origin in the high electronic excitation induced in the solid. A number of phenomenological approaches have been employed to describe these mechanisms: coulomb explosion, thermal spike, non-radiative exciton decay, bond weakening. However, a detailed microscopic description is missing due to the difficulty of modeling the time evolution of the electronic excitation. In this work we have employed molecular dynamics (MD) calculations to determine whether the irradiation effects are related to the thermal phenomena described by MD (in the ps domain) or to electronic phenomena (sub-ps domain), e.g., exciton localization. We have carried out simulations of up to 100 ps with large boxes (30x30x8 nm3) using a home-modified version of MDCASK that allows us to define a central hot cylinder (ion track) from which heat flows to the surrounding cold bath (unirradiated sample). We observed that once the cylinder has cooled down, the Si and O coordination numbers are 4 and 2, respectively, as in virgin silica. On the other hand, the density of the (cold) cylinder increases with respect to that of silica and, furthermore, the silica network ring size decreases. Both effects are in agreement with the observed densification. In conclusion, purely thermal effects do not explain the generation of point defects upon irradiation, but they do account for the silica densification.

Material requirements for the adoption of unconventional silicon crystal and wafer growth techniques for high-efficiency solar cells

Silicon wafers comprise approximately 40% of crystalline silicon module cost, and represent an area of great technological innovation potential. Paradoxically, unconventional wafer-growth techniques have thus far failed to displace multicrystalline and Czochralski silicon, despite four decades of innovation. One of the shortcomings of most unconventional materials has been a persistent carrier lifetime deficit in comparison to established wafer technologies, which limits the device efficiency potential. In this perspective article, we review a defect-management framework that has proven successful in enabling millisecond lifetimes in kerfless and cast materials. Control of dislocations and slowly diffusing metal point defects during growth, coupled to effective control of fast-diffusing species during cell processing, is critical to enable high cell efficiencies. To accelerate the pace of novel wafer development, we discuss approaches to rapidly evaluate the device efficiency potential of unconventional wafers from injection-dependent lifetime measurements.

Size dependent enhancement of helium ion irradiation tolerance in sputtered Cu/V nanolaminates

We have investigated the evolution of radiation damage and changes in hardness of sputter-deposited Cu/V nanolaminates upon room temperature helium ion irradiation. As the individual layer thickness decreases from 200 to 5 nm, helium bubble density and radiation hardening both decrease. The magnitude of radiation hardening becomes negligible for individual layer thickness of 2.5 nm or less. These observations indicate that nearly immiscible Cu/V interface can effectively absorb radiation-induced point defects and reduce their concentrations.

Unfolding grain size effects in barium titanate ferroelectric ceramics

Grain size effects on the physical properties of polycrystalline ferroelectrics have been extensively studied for decades; however there are still major controversies regarding the dependence of the piezoelectric and ferroelectric properties on the grain size. Dense BaTiO3 ceramics with different grain sizes were fabricated by either conventional sintering or spark plasma sintering using micro- and nano-sized powders. The results show that the grain size effect on the dielectric permittivity is nearly independent of the sintering method and starting powder used. A peak in the permittivity is observed in all the ceramics with a grain size near 1μm and can be attributed to a maximum domain wall density and mobility. The piezoelectric coefficient d33 and remnant polarization Pr show diverse grain size effects depending on the particle size of the starting powder and sintering temperature. This suggests that besides domain wall density, other factors such as back fields and point defects, which influence the domain wall mobility, could be responsible for the different grain size dependence observed in the dielectric and piezoelectric/ferroelectric properties. In cases where point defects are not the dominant contributor, the piezoelectric constant d33 and the remnant polarization Pr increase with increasing grain size.

High On/Off ratio memristive switching of manganite/cuprate bilayer by interfacial magnetoelectricity

Memristive switching serves as the basis for a new generation of electronic devices. Memristors are two-terminal devices in which the current is turned on and off by redistributing point defects, e.g., vacancies, which is difficult to control. Memristors based on alternative mechanisms have been explored, but achieving both the high On/Off ratio and the low switching energy desirable for use in electronics remains a challenge. Here we report memristive switching in a La_(0.7)Ca_(0.3)MnO_(3)/PrBa_(2)Cu_(3)O_(7) bilayer with an On/Off ratio greater than 103 and demonstrate that the phenomenon originates from a new type of interfacial magnetoelectricity. Using results from firstprinciples calculations, we show that an external electric-field induces subtle displacements of the interfacial Mn ions, which switches on/off an interfacial magnetic “dead” layer, resulting in memristive behavior for spin-polarized electron transport across the bilayer. The interfacial nature of the switching entails low energy cost about of a tenth of atto Joule for write/erase a “bit”. Our results indicate new opportunities for manganite/cuprate systems and other transition-metal-oxide junctions in memristive applications.

Rheological behaviour of the mushy zone and its effect on the formation of casting defects during solidification

A new conceptual framework has been developed which explains the formation of shear-related casting defects such as porosity, segregation and tears. The theory relates defect formation to the mechanical behaviour of the partially solidified microstructure when shear stresses are developed during the filling of a casting and by the subsequent feeding processes during solidification. Two transition points, the dendrite coherency point and the maximum packing solid fraction, divide the mushy zone into three regions of different mechanical and feeding behaviours. The response of the mush to shear is related to the presence of these zones during solidification of a casting. The resulting defects are rationalized by considering the governing local shear stress and shear rate, local strength and time available for fluid flow. The design of the casting, the casting process used and the alloy composition all influence the relative importance of shearing on defect formation. (C) 1998 Acta Metallurgica Inc. Published by Elsevier Science Ltd. All rights reserved.

In vivo biological performance of a novel highly bioactive glass-ceramic (Biosilicate (R)): A biomechanical and histomorphometric study in rat tibial defects

This study aimed to investigate bone responses to a novel bioactive fully crystallized glass-ceramic of the quaternary system P(2)O(5)-Na(2)O-CaO-SiO(2) (Biosilicates (R)). Although a previous study demonstrated positive effects of Biosilicate (R) on in vitro bone-like matrix formation, its in vivo effect was not studied yet. Male Wistar rats (n = 40) with tibial defects were used. Four experimental groups were designed to compare this novel biomaterial with a gold standard bioactive material (Bioglass (R) 45S5), unfilled defects and intact controls. A three-point bending test was performed 20 days after the surgical procedure, as well as the histomorphometric analysis in two regions of interest: cortical bone and medullary canal where the particulate biomaterial was implanted. The biomechanical test revealed a significant increase in the maximum load at failure and stiffness in the Biosilicate group (R) (vs. control defects), whose values were similar to uninjured bones. There were no differences in the cortical bone parameters in groups with bone defects, but a great deal of woven bone was present surrounding Biosilicate (R) and Bioglass (R) 45S5 particulate. Although both bioactive materials supported significant higher bone formation; Biosilicate (R) was superior to Bioglass (R) 45S5 in some histomorphometric parameters (bone volume and number of osteoblasts). Regarding bone resorption, Biosilicate (R) group showed significant higher number of osteoclasts per unit of tissue area than defect and intact controls, despite of the non-significant difference in the osteoclastic surface as percentage of bone surface. This study reveals that the fully crystallized Biosilicate (R) has good bone-forming and bone-bonding properties. (C) 2011 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 978: 139-147, 2011.