Processing of high entropy carbide based ceramics

Please click Additional Files below to see the full abstract

Quaternary Ammonium Silane-Functionalized, Methacrylate Resin Composition With Antimicrobial Activities and Self-Repair Potential

The design of antimicrobial polymers to address healthcare issues and minimize environmental problems is an important endeavor with both fundamental and practical implications. Quaternary ammonium silane-functionalized methacrylate (QAMS) represents an example of antimicrobial macromonomers synthesized by a sol–gel chemical route; these compounds possess flexible Si–O–Si bonds. In present work, a partially hydrolyzed QAMS co-polymerized with 2,2-[4(2-hydroxy 3-methacryloxypropoxy)-phenyl]propane is introduced. This methacrylate resin was shown to possess desirable mechanical properties with both a high degree of conversion and minimal polymerization shrinkage. The kill-on-contact microbiocidal activities of this resin were demonstrated using single-species biofilms of Streptococcus mutans (ATCC 36558), Actinomyces naeslundii (ATCC 12104) and Candida albicans (ATCC 90028). Improved mechanical properties after hydration provided the proof-of-concept that QAMS-incorporated resin exhibits self-repair potential via water-induced condensation of organic modified silicate (ormosil) phases within the polymerized resin matrix

O ensino da leitura e da escrita no 1º ano de escolaridade: os resultados dos alunos em leitura

Tese de Doutoramento em Psicologia Aplicada, Área de especialidade Psicologia EducacionalO presente estudo teve como objetivo caracterizar as práticas de ensino da linguagem escrita em Portugal e perceber o seu impacto na aquisição da leitura no final do 1º ano de escolaridade. A primeira etapa deste estudo correspondeu a um estudo descritivo e comparativo com o realizado por Fijalkow (2003) em França. A partir da resposta a um questionário de 883 professores foi possível verificar que os professores dos dois países se aproximam no que diz respeito aos aspetos metodológicos do ensino da leitura e à avaliação da leitura e da escrita dos alunos. Contudo, os professores portugueses dizem utilizar com maior frequência do que os professores franceses, atividades a partir de livros infantis, outros materiais para além do manual e diferentes propostas de escrita. Na segunda etapa deste estudo, o questionário utilizado foi validado através da sua estrutura fatorial e foram utilizados os fatores revelados para a realização de uma análise hierárquica de clusters. Esta análise revelou três grupos de professores: a) um grupo de professores que centra as suas práticas no ensino do código da linguagem escrita (unidades curtas); b) um grupo que realça a construção de significado na interação com o material escrito (unidades longas); c) e um grupo de professores que reúne nas suas práticas características de ambos os grupos referidos anteriormente (unidades diversificadas). A terceira etapa realizada diz respeito à validação das respostas do questionário através da observação de sala de aula. Foram selecionados 5% dos professores de cada um dos três grupos constituídos (N=42). Cada professor foi observado duas vezes durante 60 minutos em situações escolhidas por si como situações privilegiadas para o ensino da linguagem escrita. Através da utilização de uma grelha de observação que divide as atividades desenvolvidas em atividades que remetem para o código ou para o significado, foi possível confirmar as respostas ao questionário para 55% dos professores participantes. No sentido de perceber o impacto das práticas dos professores na aquisição da leitura dos alunos foram selecionados os professores cujas observações foram coincidentes com as respostas ao questionário e avaliados os seus alunos com recurso a três provas de leitura: leitura de palavras isoladas, decisão lexical e compreensão. Participaram 461 alunos distribuídos pelos três grupos referidos anteriormente. Através da realização de uma MANCOVA, controlando a escolaridade das mães dos alunos, verificou-se que os alunos do grupo unidades diversificadas obtêm melhores resultados em todas as provas do que os alunos dos outros dois grupos. Foi ainda possível constatar que não existiram diferenças de desempenho entre os alunos do grupo unidades curtas e os alunos do grupo unidades longas.ABSTRACT: The present study aimed to characterize the teaching practices of written language and understand its impact on reading acquisition by the end of 1st grade. The first step of this study was a descriptive and comparative study to the one conducted by Fijalkow (2003) in France. Based on questionnaire answers of 883 teachers, we found that teachers from both countries have similar approaches regarding methodological aspects of teaching of reading and students’ assessment of reading and writing abilities. However, Portuguese teachers stated that they use more frequently activities from children's literature, other materials besides the manual and different writing proposals than French teachers. In the second step of the study, the questionnaire was validated through its factorial structure and the factors disclosed were used to perform a hierarchical cluster analysis. This analysis revealed three groups of teachers: a) a group of teachers who focus its practices in teaching the code of written language (short units), b) a group that emphasizes the construction of meaning in interaction with the written material (long units), c) and a group of teachers who gathered in their practices characteristics of both groups mentioned above (diversified units). The third step concerns the validation of the questionnaire answers through classroom observation. 5% of the teachers in each of the three groups were selected (N=42). Each teacher was observed twice during 60 minutes in situations identified by them as privileged situations for teaching written language. Using an observation grid which divides the activities conducted in code-activities or the meaning-activities it was possible to confirm questionnaire answers for 55% of the participating teachers. In order to understand the impact of teachers’ practices in students reading acquisition, teachers whose observations were coincident with the questionnaire answers were selected and their students were evaluated using three reading tests: single words reading, lexical decision task and comprehension task. Participants were 461 students distributed through the three groups previously mentioned. By conducting a MANCOVA, controlling mothers’ education level, we concluded that students in the diversified unit group obtain better results in all reading tests than students from the other groups. It was also possible to confirm that there were no differences in performance between students of the short units group and students of the long units group.Tese de Doutoramento em Psicologia Aplicada, Área de especialidade Psicologia EducacionalApoio financeiro da Fundação para a Ciência e Tecnologia (SFRH/BD/64630/2009

APPLICATION OF NANOSCOPIC DYNAMIC MECHANICAL ANALYSIS FOR EVALUATING THE MECHANICAL BEHAVIOR OF HARD TISSUES AND BONDED INTERFACES

In this study Dynamic Mechanical Anlaysis (DMA) was applied to dentin, the macro hybrid layer and intact hybrid layers of the bonded dental restorative interface using nanoindentation. Both intertubular and peritubular dentin were evaluated by DMA using discrete and scanning mode nanoindentation. The complex (E*), loss (E), and storage (E') moduli were quantified over a range of indentation loads and scanning frequencies. The storage modulus of the peritubular cuff (22.19 GPa0.05). A model bonded interface (i.e. the macro hybrid) was evaluated using scanning DMA. A new approach for hydrating samples using ethylene glycol solution was developed and then applied to identify the importance of hydration on the measured properties. Fully hydrated samples exhibited mean values of E*, E' and E of 3.54 GPa, 3.42 GPa and 0.86 GPa, respectively, whereas fully dehydrated samples exhibited values of 4.01 GPa, 3.88 GPa and 0.94 GPa, respectively. There were significant differences in the complex modulus (p0.05). A dynamic loading frequency of 100 Hz and scanning frequency of 0.2 Hz were identified to provide the most reliable results in scanning the collagen-based systems. Lastly, the optimal testing parameters obtained from studying the macro hybrid layer were used to evaluate intact resin-dentin bonded interfaces. The property maps clearly distinguished variations in properties as a function of the constituents. It was identified that scanning based nanoDMA is a potent tool for evaluating mechanical properties of the hybrid layer but testing parameters and maintenance of the hydration are critical to the interpretation of apparent mechanical behavior

APPLICATION OF NANOSCOPIC DYNAMIC MECHANICAL ANALYSIS FOR EVALUATING THE MECHANICAL BEHAVIOR OF HARD TISSUES AND BONDED INTERFACES

In this study Dynamic Mechanical Anlaysis (DMA) was applied to dentin, the macro hybrid layer and intact hybrid layers of the bonded dental restorative interface using nanoindentation. Both intertubular and peritubular dentin were evaluated by DMA using discrete and scanning mode nanoindentation. The complex (E*), loss (E), and storage (E') moduli were quantified over a range of indentation loads and scanning frequencies. The storage modulus of the peritubular cuff (22.19 GPa0.05). A model bonded interface (i.e. the macro hybrid) was evaluated using scanning DMA. A new approach for hydrating samples using ethylene glycol solution was developed and then applied to identify the importance of hydration on the measured properties. Fully hydrated samples exhibited mean values of E*, E' and E of 3.54 GPa, 3.42 GPa and 0.86 GPa, respectively, whereas fully dehydrated samples exhibited values of 4.01 GPa, 3.88 GPa and 0.94 GPa, respectively. There were significant differences in the complex modulus (p0.05). A dynamic loading frequency of 100 Hz and scanning frequency of 0.2 Hz were identified to provide the most reliable results in scanning the collagen-based systems. Lastly, the optimal testing parameters obtained from studying the macro hybrid layer were used to evaluate intact resin-dentin bonded interfaces. The property maps clearly distinguished variations in properties as a function of the constituents. It was identified that scanning based nanoDMA is a potent tool for evaluating mechanical properties of the hybrid layer but testing parameters and maintenance of the hydration are critical to the interpretation of apparent mechanical behavior

Effect of Hf alloying on magnetic, structural, and magnetostrictive properties in FeCo films for magnetoelectric heterostructure devices

Materials with high magnetoelectric coupling are attractive for use in engineered multiferroic heterostructures with applications such as ultra-low power magnetic sensors, parametric inductors, and non-volatile random-access memory devices. Iron–cobalt alloys exhibit both high magnetostriction and high saturation magnetization that are required for achieving significantly higher magnetoelectric coupling. We report on sputter-deposited (Fe0.5Co0.5)1−xHfx (x = 0 – 0.14) alloy thin films and the beneficial influence of Hafnium alloying on the magnetic and magnetostrictive properties. We found that co-sputtering Hf results in the realization of the peening mechanism that drives film stress from highly tensile to slightly compressive. Scanning electron microscopy and x-ray diffraction along with vibrating sample magnetometry show reduction in coercivity with Hf alloying that is correlated with reduced grain size and low film stress. We demonstrate a crossover from tensile to compressive stress at x ∼ 0.09 while maintaining a high magnetostriction of 50 ppm and a low coercive field of 1.1 Oe. These characteristics appear to be related to the amorphous nature of the film at higher Hf alloying

Below the Hall–Petch Limit in Nanocrystalline Ceramics

Reducing the grain size of metals and ceramics can significantly increase strength and hardness, a phenomenon described by the Hall–Petch relationship. The many studies on the Hall–Petch relationship in metals reveal that when the grain size is reduced to tens of nanometers, this relationship breaks down. However, experimental data for nanocrystalline ceramics are scarce, and the existence of a breakdown is controversial. Here we show the Hall–Petch breakdown in nanocrystalline ceramics by performing indentation studies on fully dense nanocrystalline ceramics fabricated with grain sizes ranging from 3.6 to 37.5 nm. A maximum hardness occurs at a grain size of 18.4 nm, and a negative (or inverse) Hall–Petch relationship reduces the hardness as the grain size is decreased to around 5 nm. At the smallest grain sizes, the hardness plateaus and becomes insensitive to grain size change. Strain rate studies show that the primary mechanism behind the breakdown, negative, and plateau behavior is not diffusion-based. We find that a decrease in density and an increase in dissipative energy below the breakdown correlate with increasing grain boundary volume fraction as the grain size is reduced. The behavior below the breakdown is consistent with structural changes, such as increasing triple-junction volume fraction. Grain- and indent-size-dependent fracture behavior further supports local structural changes that corroborate current theories of nanocrack formation at triple junctions. The synergistic grain size dependencies of hardness, elasticity, energy dissipation, and nanostructure of nanocrystalline ceramics point to an opportunity to use the grain size to tune the strength and dissipative properties

Biomimetic Silicification of Demineralized Hierarchical Collagenous Tissues

Unlike man-made composite materials, natural biominerals containing composites usually demonstrate different levels of sophisticated hierarchical structures which are responsible for their mechanical properties and other metabolic functions. However, the complex spatial organizations of the organic–inorganic phases are far beyond what they achieved by contemporary engineering techniques. Here, we demonstrate that carbonated apatite present in collagen matrices derived from fish scale and bovine bone may be replaced by amorphous silica, using an approach that simulates what is utilized by phylogenetically ancient glass sponges. The structural hierarchy of these collagen-based biomaterials is replicated by the infiltration and condensation of fluidic polymer-stabilized silicic acid precursors within the intrafibrillar milieu of type I collagen fibrils. This facile biomimetic silicification strategy may be used for fabricating silica-based, three-dimensional functional materials with specific morphological and hierarchical requirements