Metal oxide reactions at metal oxide surfaces or at metal-metal oxide interfaces are of exceptional significance in areas such as catalysis, micro- and nanoelectronics, chemical sensors, and catalysis. Such reactions are frequently complicated by the presence of high electric fields and/or H2O-containing environments. The focus of this research was to understand (1) the iron oxide growth mechanism on Fe(111) at 300 K and 500 K together with the effect of high electric fields on these iron oxide films, and (2) the growth of alumina films on two faces of Ni3Al single crystal and the interaction of the resulting films with water vapor under non-UHV conditions. These studies were conducted with AES, LEED, and STM. XPS was also employed in the second study. Oxidation of Fe(111) at 300 K resulted in the formation of Fe2O3 and Fe3O4. The substrate is uniformly covered with an oxide film with relatively small oxide islands, i.e. 5-15 nm in width. At 500 K, Fe3O4 is the predominant oxide phase formed, and the growth of oxide is not uniform, but occurs as large islands (100 - 300 nm in width) interspersed with patches of uncovered substrate. Under the stress of STM induced high electric fields, dielectric breakdown of the iron oxide films formed at 300 K occurs at a critical bias voltage of 3.8 ± 0.5 V at varying field strengths. No reproducible result was obtained from the high field stress studies of the iron oxide formed at 500 K. Ni3Al(110) and Ni3Al(111) were oxidized at 900 K and 300 K, respectively. Annealing at 1100 K was required to order the alumina films in both cases. The results demonstrate that the structure of the 7 Å alumina films on Ni3Al(110) is k-like, which is in good agreement with the DFT calculations. Al2O3/Ni3Al(111) (γ'-phase) and Al2O3/Ni3Al(110) (κ-phase) films undergo drastic reorganization and reconstruction, and the eventual loss of all long-range order upon exposure to H2O pressure > 10-5 Torr. Al2O3/Ni3Al(110) film is significantly more sensitive to H2O vapor than the Al2O3/Ni3Al(111) film, and this may be due to the incommensurate nature of the oxide/Ni3Al(110) interface. STM measurements indicate that this effect is pressure- rather than exposure- dependent, and that the oxide instability is initiated at the oxide surface, rather than at the oxide/metal interface. The effect is not associated with formation of a surface hydroxide, yet is specific to H2O (similar O2 exposures have no effect).

Hipótese do estudo: A hipótese do presente estudo é de que o cimento resinoso autoadesivo U200 apresente melhores valores de resistência adesiva entre os substratos zircônia Y-TZP/dentina humana, em comparação com o cimento resinoso convencional C&B Cement, utilizando dois tratamentos de superfície distintos (jateamento com óxido de alumínio e silicatização (Rocatec) na superfície da zircônia; e que o tratamento de superfície influencie positivamente os resultados de resistência adesiva. Objetivos: Avaliar por meio de teste de microcisalhamento a resistência adesiva da zircônia Y-TZP cimentada à dentina humana utilizando diferentes agentes de cimentação e tratamentos de superfície. Método: Foram utilizados 42 molares humanos recém extraídos, incluídos 2/3 de suas raízes em resina acrílica. A superfície oclusal foi desgastada até exposição da dentina média, tratada de acordo com as recomendações dos fabricantes dos cimentos. Quarenta e dois blocos de zircônia Y-TZP (10x10x3mm) foram divididos aleatoriamente em três grupos de acordo com o tratamento de superfície (sem tratamento-controle, jateamento com óxido de alumínio-Al2O3 ou silicatização-Rocatec). Todos os blocos de zircônia foram cimentados seguindo as recomendações dos fabricantes e divididos em seis grupos combinando os diferentes tratamentos de superfície e agentes de cimentação. Os espécimes foram armazenados em água destilada 37C por 24h e após este período foram submetidos ao teste de microcisalhamento em máquina de ensaios universal (Shimadzu AGX) com velocidade constante de 0,5mm/min até ocorrer fratura da interface. Os valores foram obtidos em Mpa e as superfícies de fraturas avaliadas e classificadas em: adesiva, coesiva e mista. As médias dos valores de resistência de união e a porcentagem das fraturas foram calculadas, e os valores submetidos à análise estatística, utilizando os testes Análise de Variância (two way) e pos-hoc teste T de Student, adotando p<0,05. Resultados: Quanto ao agente de cimentação os resultados obtidos para os grupos sem tratamento de superfície o cimento autoadesivo U200 apresentou melhor performance quando comparado ao cimento convencional C&B Cement; os grupos submetidos ao jateamento com Al2O3 e Rocatec não apresentaram diferença estatística entre os cimentos U200 e C&B Cement. Quanto à analise de superfície, os grupos cimentados com C&B e U200 apresentaram predominantemente falhas de natureza mista. Conclusão: Com base nos resultados encontrados no presente estudo foi possível concluir que o tratamento de superfície que melhor influenciou a resistência adesiva foi o jateamento com Al2O3, atendendo melhor os dois agentes de cimentação. Quanto ao agente de cimentação o U200 apresentou os melhores resultados sem tratamento de superfície. O C&B Cement e U200 apresentaram valores semelhantes com a superfície jateada com Al2O3. Para o Rocatec, os cimentos U200 e C&B Cement apresentaram valores semelhantes, entretanto menores do que os valores conseguidos para o Al2O3. / Study hypothesis: The hypothesis of this study is that the resin cement Self Adhesive U200 present best values of bond strength between zirconia substrates Y-TZP / dentin compared to conventional resin cement C & B Cement, using two surface treatments distinct (sandblasting with aluminum and silica coating (Rocatec) oxide on the surface of zirconia, and the surface treatment positively influence the bond strength. Objectives: To assess via microshear test the bond strength of zirconia Y-TZP cemented to dentin human using different cementing agents and surface treatments. Method:. freshly extracted human molars 42, including two thirds of its roots in acrylic resin were used the occlusal surface was worn until the middle dentin exposure, treated according to the recommendations of the cement manufacturers. Forty-two blocks of Y-TZP zirconia (10x10x3mm) were randomly divided into three groups according to the surface treatment (untreated control, blasting with aluminum oxide or silica coating-Al2O3-Rocatec). All zirconia blocks were cemented following the manufacturers recommendations and divided into six groups combining different surface treatments and cementing agents. The specimens were stored in distilled water 37 C for 24 h and after this period underwent microshear test in a universal testing (Shimadzu AGX) machine with constant speed of 0.5 mm / min until fracture occurs interface. The values were obtained in MPa and the fracture surfaces evaluated and classified as: adhesive, cohesive and mixed. The average values of union strength and the percentage of fractures were calculated, and values subjected to statistical analysis using analysis of variance tests (two way) and post-hoc Students t test, considering p <0.05. Results: Regarding the cementing agent the results for the groups without surface treatment U200 self-adhesive cement showed better performance when compared to conventional cement C & B Cement; groups subjected to blasting with Al2O3 and Rocatec showed no statistical difference between the U200 and cements C & B Cement. As for the analysis of surface groups cemented with C & B and U200 were mostly mixed nature of failures. Conclusion: Based on results of this study it was concluded that the surface treatment that best influenced the bond strength was blasting with Al2O3 to better serve the two cementing agents. As the cementing agent U200 showed the best results without surface treatment. The C & B Cement and U200 showed similar values with the surface sandblasted with Al2O3. Rocatec to the U200 and cement Cement B & C showed similar, though lower than the values obtained for Al2O3 values.

We report the experimental observation of hysteresis-free negative capacitance (NC) in thin ferroelectric Hf₀.₅Zr₀.₅O₂ (HZO) films through high-speed pulsed charge-voltage measurements. Hysteretic switching is suppressed by the addition of thin Al₂O₃ layers on top of the HZO to prevent the screening of the polarization. We observe an S-shaped polarization-electric field dependence without hysteresis in agreement with Landau theory, which enables direct extraction of NC modeling parameters for ferroelectric HZO. Hysteresis-free NC is demonstrated down to 100 ns pulse widths limited only by our measurement setup. These results give critical insights into the physics of ferroelectric NC and practical NC device design using ferroelectric HZO.

Mit Fe-Pd-Legierungen nahe der Zusammensetzung Fe70Pd30 kann man aufgrund des thermischen oder magnetischen Formgedächtniseffekts große Dehnungen erzeugen. Daher sind sie für Mikro- und Nanoaktoren sowie Sensoren von großem wissenschaftlichen und technologischen Interesse. Im Vergleich zu Massivmaterial und dünnen Schichten erwartet man für eindimensionale Geometrien wie Nanodrähte deutlich höhere Arbeitsfrequenzen und Dehnungen. Zur Herstellung von Nanodrähten eignet sich die elektrochemische Abscheidung in selbstordnende nanoporöse Membranen als effizienteste Methode gegenüber lithographischen oder physikalischen Methoden. Um den Formgedächtniseffekt auch in Fe-Pd-Nanodrähten mit ca. 30 at.% Pd zu nutzen, werden in dieser Arbeit entsprechende Herstellungsbedingungen wie Elektrolytsystem, Abscheideparameter und Nachbehandlung herausgearbeitet. Die Zusammenhänge zwischen Abscheidebedingungen und Morphologie, lokaler Mikrostruktur, Struktur sowie magnetischen Eigenschaften werden untersucht und bewertet. Es wird gezeigt, dass Fe-Pd-Nanodrähte trotz der Kombination aus edlem und unedlem Metall elektrochemisch hergestellt werden können. Ein komplexierter Fe-Pd-Elektrolyt in Kombination mit optimierten alternierenden Abscheidepotentialen führt reproduzierbar zu durchgehenden, nahezu defektfreien Nanodrähten nahe der Zusammensetzung Fe70Pd30. Mit einer nachträglichen Wärmebehandlung erreicht man eine vollständige Umwandlung der Fe-Pd-Legierung von der kubisch raumzentrierten zur kubisch flächenzentrierten Struktur. Die erfolgreiche Herstellung dieser Nanodrähte stellt eine Schlüsselposition auf dem Weg zu formgedächtnisbasierten Nanoaktoren dar. In dieser Arbeit konnten wichtige Ansatzpunkte zur Strukturkontrolle während der elektrochemischen Abscheidung und somit zur Aktivierung des Formgedächtniseffekts identifiziert werden. / Fe-Pd alloys at about 30 at.% Pd allow obtaining high length changes or strains in the percent range due to thermal or magnetic shape memory effect. They are especially promising candidates for smart and intelligent materials in micro- and nanoactuators as well as sensors. In comparison to bulk materials and thin films the utilization of nanowires promises higher actuation frequencies and strains, which further heighten the scientific and technological interest. Electrodeposition within self-organized nanoporous templates is a very time efficient method to prepare even large arrays of Fe-Pd nanowires of different length and diameter compared to lithographic or physical methods. The aim of this work is to exhibit the preparation conditions such as electrolyte system, deposition parameter and post treatment for shape memory active Fe-Pd nanowires at about 30 at.% Pd. Correlations between morphology, local microstructure, structure and magnetic properties are investigated and evaluated. Fe-Pd nanowires are successfully prepared by electrodeposition despite the combination of noble Pd and less noble Fe metals. The usage of an electrolyte with complexed Fe and Pd ions and an optimized alternating potential deposition regime leads to continuous and almost defect free nanowires close to the composition Fe70Pd30. The complete transition from the bcc to fcc structure of the Fe-Pd alloy is achieved by an additional heat treatment. However, the successful preparation of these nanowires represents a key element towards nanoactuators based on shape memory alloys. Fundamental knowledge about electrochemical preparation of Fe-Pd nanowires is gained. Important starting points towards structure control during deposition and activation of the shape memory effect are identified.

Hocheffiziente Solarzellen beruhen auf der exzellenten Oberflächenpassivierung, die minimale Rekombinationsverluste gewährleistet. Innerhalb des letzten Jahrzehnts wurde Al2O3 in der Photovoltaikindustrie zum bevorzugten Material für p-leitendes Si. Unterschiedliche Abscheidetechnologien erreichten Passivierungen mit effektiven Minoritätsladungsträgerlebensdauern nahe der AUGER–Grenze. Die ausgezeichnete Passivierungswirkung von Al2O3wird zwei Effekten zugeschrieben: Einerseits werden Si−SiO2-grenzflächennahe Rekombinationszentren passiviert, wenn Wasserstoff, beispielsweise aus der Al2O3-Schicht, offene Bindungen absättigt. Bedingt durch die hohe Konzentration intrinsischer negativer Ladungen an der SiO2-Grenzfläche weist Al2O3 andererseits einen charakteristischen Feldeffekt auf. Das resultierende elektrische Feld hält Elektronen von Oberflächenrekombinationszentren fern. Negative Ladungen im Al2O3 werden generell als fest bezeichnet. Allerdings hat Al2O3 zusätzlich eine hohe Dichte an Haftstellen, die von Elektronen besetzt werden können. Die Dichte negativer Ladungen im Al2O3-Passivierungsschichten hängt vom elektrischen Feld und der Bestrahlungsintensität ab. Ziel dieser Arbeit ist die systematische Untersuchung dielektrischer Passivierungsschichtstapel für die Anwendung auf Si-Solarzellen. Der Qualität und Dicke der SiO2-Grenzschicht kommt in diesem Kontext eine besondere Rolle zu, da sie Ladungsträgertunneln ermöglicht. Der Elektronentransport ist eine Funktion der Oxiddicke und das Optimum zwischen Ladungseinfang und -haltung liegt bei etwa 2 nm SiO2. Vier relevante Al2O3-Abscheidetechnologien werden untersucht: Atomlagenabscheidung, Kathodenzerstäubung, Sprühpyrolyse und Rotationsbeschichtung, wobei die erstgenannte dominiert. Es werden Nanolaminate verglichen, die aus Al2O3 und TiO2, HfO2 oder SiO2 mit subnanometerdicken Zwischenschichten bestehen. Während letztgenannte die Oberflächenrekombination nicht vermindern, beeinflussen TiO2- und HfO2-Nanolaminate die Passivierungswirkung. Ein dynamisches Wachstumsmodell, das initiale und stationäre Wachstumsraten der beteiligten Metalloxide berücksichtigt, beschreibt die physikalischen Parameter. Schichtsysteme mit 0,2 % TiO2 oder 7 % HfO2 sind konventionellen Al2O3-Schichten überlegen. In beiden Fällen überwiegt die veränderte Feldeffekt- der chemischen Passivierung, die mit einer Grenzflächenzustandsdichte von maximal 5·1010 eV−1·cm−2 unverändert auf hohem Niveau verbleibt. Die Ladungsdichte beider Schichtsysteme wird entweder über die Änderung ihrer Polarität der festen Ladungen oder der Fähigkeit zum Ladungseinfang bestimmt. Das Tunneln von Elektronen wird durch ein mathematisches Modell erklärt, dass eine bewegliche Ladungsfront innerhalb der Oxidschicht beschreibt. / High-efficiency solar cells rely on excellent passivation of the surface to ensure minimal recombination losses. In the last decade, Al2O3 became the material of choice for p-type Si in the photovoltaic industry. A remarkable surface passivation with effective minority carrier lifetimes close to the AUGER–limit was demonstrated with different deposition techniques. The excellent passivation effect of Al2O3 is attributed to two effects: Firstly, recombination centers at the Si−SiO2 interface get chemically passivated when hydrogen, for instance from the Al2O3 layer, saturates dangling bonds. Secondly, Al2O3 presents an outstanding level of field effect passivation due to its high concentration of intrinsic negative charges close to the SiO2 interface. The generated electrical field effectively repels electrons from surface recombination centers. Negative charges in Al2O3 are generally termed fixed charges. However, Al2O3 incorporates a high density of trap sites, too, that can be occupied by electrons. It was shown that the negative charge density in Al2O3 passivation layers depends on the electrical field and on the illumination intensity. The goal of this work is to systematically investigate dielectric passivation layer stacks for application on Si solar cells. The SiO2 interface quality and thickness plays a major role in this context, enabling or inhibiting carrier tunneling. Since the electron transport is a function of the oxide thickness, the balance between charge trapping and retention is achieved with approximately 2 nm of SiO2. Additionally, four relevant Al2O3 deposition techniques are compared: atomic layer deposition, sputtering, spray pyrolysis and spin–on coating, whereas the former is predominant. Using its flexibility, laminates comprising of Al2O3 and TiO2, HfO2 or SiO2 with subnanometer layers are compared. Although the latter do not show decreased surface recombination, nanolaminates with TiO2 and HfO2 contribute to the passivation. Their physical properties are described with a dynamic growth model that considers initial and steady–state growth rates for the involved metal oxides. Thin films with 0.2 % TiO2 or 7 % HfO2 are superior to conventional Al2O3 layers. In both cases, the modification of the field effect prevails the chemical effect, that is, however, virtually unchanged on a very high level with a density of interface traps of 5·1010 eV−1·cm−2 and below. The density of charges in both systems is changed via modifying either the polarity of intrinsic fixed charges or the ability of trapping charges within the layers. The observations of electron tunneling are explained by means of a mathematical model, describing a charging front, which moves through the dielectric layer.

Selbstreinigende, ultrahydrophobe Oberflächen lassen sich in der Technik vielfältig einsetzen. Das ultrahydrophobe Verhalten beruht einerseits auf einer Rauigkeit im μm-Bereich und andererseits auf der chemischen Zusammensetzung der Oberfläche. Durch den gegebenen Oberflächenaufbau sind derartige Materialien jedoch empfindlich gegen Verschleiß. In diesem Beitrag wird ein Schichtverbund bestehend aus Aluminiumoxid und zwei polymeren Komponenten vorgestellt. Die Aluminiumoxidschicht wird auf dem Wege der anodischen Oxidation erzeugt. Dieses seit langem bekannte Verfahren ermöglicht nicht nur die Oxidation der Aluminiumoberfläche, sondern gestattet es, auch, definierte Oberflächenprofile einzustellen. Durch den gezielten Einbau des hochmolekularen Polymers Chitosan in die mikroprofilierte Aluminiumoxidschicht wurde eine mechanische Stabilisierung der Schicht im Sinne eines anorganisch-organischen Composites erreicht. Außerdem dienten die Amino-Seitengruppen des Chitosans als reaktives Interface für die notwendige chemische Hydrophobierung und als Reaktionszentrum für Vernetzungen, wodurch eine weitere mechanische Stabilisierung bewirkt wird. Der Schichtaufbau hat wesentlichen

Land application of biosolids has become common practice in the United States as an alternative to industrial fertilizers. Although nutrient rich, biosolids have been found to contain high concentrations of emerging contaminants (e.g. pharmaceuticals, personal care products) while containing a significant fraction of inorganic nano-scale colloidal materials such as oxides of iron, titanium, and aluminum. Given their reactivity and small size, there are many questions concerning the potential migration of these nano-sized colloidal materials through the soil column and into our surface and groundwater bodies. Transport of emerging pollutants of concern through the soil column, at minimum, is impacted by colloidal properties (e.g. chemical composition, shape, aggregation kinetics), solution chemistry (e.g. pH, ionic strength, natural organic matter), and water flow velocity. The purpose of this current research was to characterize the long-term transport behavior of aluminum oxide nanoparticles (Al2O3) through a natural porous media with changes in pH, aqueous-phase concentration, pore-water velocity and electrolyte valence. Additionally, deposition rates during the initial stages of deposition were compared to several models developed based on colloid filtration theory and DLVO stability theory. Benchtop column laboratory experiments showed that, under environmentally relevant groundwater conditions, Al2O3 nanoparticles are mobile through saturated porous media. Mobility increased under conditions in which the nanoparticles and porous media were of like charge (pH 9). Changes in linear pore water velocity, under these same high pH conditions, showed similar transport behavior with little mass retained in the system. Deposition is believed to be kinetically controlled at pH 9, as evidenced by the slightly earlier breakthrough as flow rate increased and was further supported by observed concentration effects on the arrival wave following several stop flows. While lower aqueous-phase concentrations resulted in significantly longer breakthrough times, the total mass retained in the system was found to be independent of concentration. Additionally, experimental deposition rate coefficients (kd), used to describe deposition kinetics under "clean bed" conditions, were similar across the aqueous-phase concentrations studied. The use of calcium chloride electrolyte solution in transport studies resulted in enhanced mobility relative to potassium chloride suggesting that changes in groundwater solution chemistry could impact mobility of contaminants associated with biosolids. Predicted deposition rate coefficients, using three different models, were found to under- or over-predict values relative to those experimentally determined values depending on the model. This current research has shown that nanocolloids associated with biosolids, specifically Al2O3, are mobile through saturated porous media. Given the ubiquity of nanocolloidal materials, particularly engineered nanomaterials, coupled with the expected increase in land-application of biosolids, a clear understanding of their transport and fate is prudent to understanding the potential impact these emerging pollutants may have on our surface and groundwater bodies.

No description available.

No description available.

The purpose of this work was to study the synthesis conditions effect on the luminescent and dosimetric properties of aluminum oxide submicron ceramics excited by different types of radiation. We reviewed the research published on the topic of luminescent and dosimetric properties of aluminum oxide and other nanoscale materials. It was found that high-temperature annealing of Al2O3 nanopowder compacts in a vacuum (reducing medium in the presence of carbon) triggers the generation of oxygen vacancies in the oxide, which is confirmed by pulsed cathodoluminescence (PCL) results for the samples under study. It was proved that the samples, when annealed in a vacuum at high temperatures, display maximum thermoluminescence (TL) intensity, which is caused by an increased concentration of oxygen vacancies forming F luminescence center. We obtained a complex of parameters characterizing TL peak at 410 К and thermoluminescence properties and later compared it with the parameters found in references. It was observed that TL peaks intensity at 410 К and 600 K of submicron aluminum oxide depended on the dose of β-irradiation (under 200 Gy) and after electron beams irradiation (under 12 kGy). It was demonstrated that submicron aluminum oxide ceramics would be a promising material to detect ionizing radiation doses in excess of the operating dose range of single crystal α-Al2O3 detectors be more than one order. It was found that the sensitivity of submicron aluminum oxide ceramics after high-dose irradiation returned its initial value when annealed in the atmosphere at the temperature of 600 °C for 1 hour. We analyzed and assessed ecological risks and compliance with safety rules during experimental investigations. / Цель работы – изучение влияния режимов высокотемпературного отжига в восстановительной среде на люминесцентные и дозиметрические свойства субмикронной керамики оксида алюминия. Проведен обзор литературы на тему люминесцентных и дозиметрических свойств оксида алюминия и других наноразмерных материалов. Экспериментально установлено, что высокотемпературный отжиг компактов из нанопорошка в вакууме в сильно-восстановительной среде в присутствии углерода вызывает образование кислородных вакансий в оксиде, что подтверждают спектры импульсной катодолюминесценции исследуемых образцов. Увеличение температуры и времени отжига приводит к росту концентрации центров люминесценции, созданных кислородными вакансиями и, как следствие, увеличению интенсивности термолюминесценции субмикронной керамики оксида алюминия. В результате исследования образцов субмикронной керамики оксида алюминия получен комплекс параметров, характеризующих дозиметрический пик ТЛ (410 К), проведено сравнение найденных параметров с известными литературными данными. Наблюдается зависимость интенсивности пиков ТЛ при 410 К и 600 К синтезированной керамики оксида алюминия от поглощенной дозы β-облучения (до 200 Гр) и при облучении электронными импульсами (до 12 кГр). Установлено, что возврат чувствительности к β-излучению после высокодозного облучения происходит при отжиге в атмосфере при температуре 600 ºС в течение 1 часа. Проведен анализ экологических рисков и соблюдения правил безопасности жизнедеятельности при экспериментальных исследованиях.