Applications for nanomaterials in critical technologies

This thesis is devoted to the development, synthesis, properties, and applications of nano materials for critical technologies, including three areas: (1) Microbial contamination of drinking water is a serious problem of global significance. About 51% of the waterborne disease outbreaks in the United States can be attributed to contaminated ground water. Development of metal oxide nanoparticles, as viricidal materials is of technological and fundamental scientific importance. Nanoparticles with high surface areas and ultra small particle sizes have dramatically enhanced efficiency and capacity of virus inactivation, which cannot be achieved by their bulk counterparts. A series of metal oxide nanoparticles, such as iron oxide nanoparticles, zinc oxide nanoparticles and iron oxide-silver nanoparticles, coated on fiber substrates was developed in this research for evaluation of their viricidal activity. We also carried out XRD, TEM, SEM, XPS, surface area measurements, and zeta potential of these nanoparticles. MS2 virus inactivation experiments showed that these metal oxide nanoparticle coated fibers were extremely powerful viricidal materials. Results from this research suggest that zinc oxide nanoparticles with diameter of 3.5 nm, showing an isoelectric point (IEP) at 9.0, were well dispersed on fiberglass. These fibers offer an increase in capacity by orders of magnitude over all other materials. Compared to iron oxide nanoparticles, zinc oxide nanoparticles didn’t show an improvement in inactivation kinetics but inactivation capacities did increase by two orders of magnitude to 99.99%. Furthermore, zinc oxide nanoparticles have higher affinity to viruses than the iron oxide nanoparticles in presence of competing ions. The advantages of zinc oxide depend on high surface charge density, small nanoparticle sizes and capabilities of generating reactive oxygen species. The research at its present stage of development appears to offer the best avenue to remove viruses from water. Without additional chemicals and energy input, this system can be implemented by both points of use (POU) and large-scale use water treatment technology, which will have a significant impact on the water purification industry. (2) A new family of aliphatic polyester lubricants has been developed for use in micro-electromechanical systems (MEMS), specifically for hard disk drives that operate at high spindle speeds (>15000rpm). Our program was initiated to address current problems with spin-off of the perfluoroether (PFPE) lubricants. The new polyester lubricant appears to alleviate spin-off problems and at the same time improves the chemical and thermal stability. This new system provides a low cost alternative to PFPE along with improved adhesion to the substrates. In addition, it displays a much lower viscosity, which may be of importance to stiction related problems. The synthetic route is readily scalable in case additional interest emerges in other areas including small motors. (3) The demand for increased signal transmission speed and device density for the next generation of multilevel integrated circuits has placed stringent demands on materials performance. Currently, integration of the ultra low-k materials in dual Damascene processing requires chemical mechanical polishing (CMP) to planarize the copper. Unfortunately, none of the commercially proposed dielectric candidates display the desired mechanical and thermal properties for successful CMP. A new polydiacetylene thermosetting polymer (DEB-TEB), which displays a low dielectric constant (low-k) of 2.7, was recently developed. This novel material appears to offer the only avenue for designing an ultra low k dielectric (1.85k), which can still display the desired modulus (7.7Gpa) and hardness (2.0Gpa) sufficient to withstand the process of CMP. We focused on further characterization of the thermal properties of spin-on poly (DEB-TEB) ultra-thin film. These include the coefficient of thermal expansion (CTE), biaxial thermal stress, and thermal conductivity. Thus the CTE is 2.0*10-5K-1 in the perpendicular direction and 8.0*10-6 K-1 in the planar direction. The low CTE provides a better match to the Si substrate which minimizes interfacial stress and greatly enhances the reliability of the microprocessors. Initial experiments with oxygen plasma etching suggest a high probability of success for achieving vertical profiles.

Comparison of High Q microresonators operating on a thin plate mode : the Lamé-mode

International audience

The development of planar high-K/III-V p-channel MOSFETs for post-silicon CMOS

Conventional Si complementary-metal-oxide-semiconductor (CMOS) scaling is fast approaching its limits. The extension of the logic device roadmap for future enhancements in transistor performance requires non-Si materials and new device architectures. III-V materials, due to their superior electron transport properties, are well poised to replace Si as the channel material beyond the 10nm technology node to mitigate the performance loss of Si transistors from further reductions in supply voltage to minimise power dissipation in logic circuits. However several key challenges, including a high quality dielectric/III-V gate stack, a low-resistance source/drain (S/D) technology, heterointegration onto a Si platform and a viable III-V p-metal-oxide-semiconductor field-effect-transistor (MOSFET), need to be addressed before III-Vs can be employed in CMOS. This Thesis specifically addressed the development and demonstration of planar III-V p-MOSFETs, to complement the n-MOSFET, thereby enabling an all III-V CMOS technology to be realised. This work explored the application of InGaAs and InGaSb material systems as the channel, in conjunction with Al2O3/metal gate stacks, for p-MOSFET development based on the buried-channel flatband device architecture. The body of work undertaken comprised material development, process module development and integration into a robust fabrication flow for the demonstration of p-channel devices. The parameter space in the design of the device layer structure, based around the III-V channel/barrier material options of In_x≥0.53Ga_1-xAs/In_0.52Al_0.48As and In_x≥0.1Ga_1-xSb/AlSb, was systematically examined to improve hole channel transport. A mobility of 433 cm²/Vs, the highest room temperature hole mobility of any InGaAs quantum-well channel reported to date, was obtained for the In_0.85Ga_0.15As (2.1% strain) structure. S/D ohmic contacts were developed based on thermally annealed Au/Zn/Au metallisation and validated using transmission line model test structures. The effects of metallisation thickness, diffusion barriers and de-oxidation conditions were examined. Contacts to InGaSb-channel structures were found to be sensitive to de-oxidation conditions. A fabrication process, based on a lithographically-aligned double ohmic patterning approach, was realised for deep submicron gate-to-source/drain gap (L_side) scaling to minimise the access resistance, thereby mitigating the effects of parasitic S/D series resistance on transistor performance. The developed process yielded gaps as small as 20nm. For high-k integration on GaSb, ex-situ ammonium sulphide ((NH₄)₂S) treatments, in the range 1%-22%, for 10min at 295K were systematically explored for improving the electrical properties of the Al₂O₃/GaSb interface. Electrical and physical characterisation indicated the 1% treatment to be most effective with interface trap densities in the range of 4 - 10×10¹²cm^-2eV^-1 in the lower half of the bandgap. An extended study, comprising additional immersion times at each sulphide concentration, was further undertaken to determine the surface roughness and the etching nature of the treatments on GaSb. A number of p-MOSFETs based on III-V-channels with the most promising hole transport and integration of the developed process modules were successfully demonstrated in this work. Although the non-inverted InGaAs-channel devices showed good current modulation and switch-off characteristics, several aspects of performance were non-ideal; depletion-mode operation, modest drive current (I_d,sat=1.14mA/mm), double peaked transconductance (g_m=1.06mS/mm), high subthreshold swing (SS=301mV/dec) and high on-resistance (R_on=845kΩ.μm). Despite demonstrating substantial improvement in the on-state metrics of I_d,sat (11×), g_m (5.5×) and R_on (5.6×), inverted devices did not switch-off. Scaling gate-to-source/drain gap (L_side) from 1μm down to 70nm improved I_d,sat (72.4mA/mm) by a factor of 3.6 and gm (25.8mS/mm) by a factor of 4.1 in inverted InGaAs-channel devices. Well-controlled current modulation and good saturation behaviour was observed for InGaSb-channel devices. In the on-state In_0.3Ga_0.7Sb-channel (I_d,sat=49.4mA/mm, g_m=12.3mS/mm, R_on=31.7kΩ.μm) and In_0.4Ga_0.6Sb-channel (I_d,sat=38mA/mm, g_m=11.9mS/mm, R_on=73.5kΩ.μm) devices outperformed the InGaAs-channel devices. However the devices could not be switched off. These findings indicate that III-V p-MOSFETs based on InGaSb as opposed to InGaAs channels are more suited as the p-channel option for post-Si CMOS.

Age estimation in common sole Solea solea larvae: validation of daily increments and evaluation of a pattern recognition technique

Close similarities have been found between the otoliths of sea-caught and laboratory-reared larvae of the common sole Solea solea (L.), given appropriate temperatures and nourishment of the latter. But from hatching to mouth formation. and during metamorphosis, sole otoliths have proven difficult to read because the increments may be less regular and low contrast. In this study, the growth increments in otoliths of larvae reared at 12 degrees C were counted by light microscopy to test the hypothesis of daily deposition, with some results verified using scanning electron microscopy (SEM), and by image analysis in order to compare the reliability of the 2 methods in age estimation. Age was first estimated (in days posthatch) from light micrographs of whole mounted otoliths. Counts were initiated from the increment formed at the time of month opening (Day 4). The average incremental deposition rate was consistent with the daily hypothesis. However, the light-micrograph readings tended to underestimate the mean ages of the larvae. Errors were probably associated with the low-contrast increments: those deposited after the mouth formation during the transition to first feeding, and those deposited from the onset of eye migration (about 20 d posthatch) during metamorphosis. SEM failed to resolve these low-contrast areas accurately because of poor etching. A method using image analysis was applied to a subsample of micrograph-counted otoliths. The image analysis was supported by an algorithm of pattern recognition (Growth Demodulation Algorithm, GDA). On each otolith, the GDA method integrated the growth pattern of these larval otoliths to averaged data from different radial profiles, in order to demodulate the exponential trend of the signal before spectral analysis (Fast Fourier Transformation, FFT). This second method both allowed more precise designation of increments, particularly for low-contrast areas, and more accurate readings but increased error in mean age estimation. The variability is probably due to a still rough perception of otolith increments by the GDA method, counting being achieved through a theoretical exponential pattern and mean estimates being given by FFT. Although this error variability was greater than expected, the method provides for improvement in both speed and accuracy in otolith readings.

Devem as porcelanas serem re-silanizadas após a contaminação?

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Ciências da Saúde, Programa de Pós-Graduação em Ciências da Saúde, 2015.

Análisis teórico del contacto plasma-superficie y sus aplicaciones industriales

Actualmente, la física de plasmas constituye una parte importante de la investigación en física que está siendo desarrollada. Su campo de aplicación varía desde el estudio de plasmas interestelares y cósmicos, como las estrellas, las nebulosas, el medio intergaláctico, etc.; hasta aplicaciones más terrenales como la producción de microchips o los dispositivos de iluminación. Resulta particularmente interesante el estudio del contacto de una superficie metálica con un plasma. Siendo la razón que, la dinámica de la interfase formada entre un plasma imperturbado y una superficie metálica, resulta de gran importancia cuando se trata de estudiar problemas como: la implantación iónica en una oblea de silicio, el grabado por medio de plasmas, la carga de una aeronave cuando atraviesa la ionosfera y la diagnosis de plasmas mediante sondas de Langmuir. El uso de las sondas de Langmuir está extendido a través de multitud de aplicaciones tecnológicas e industriales como método de diagnosis de plasmas. Algunas de estas aplicaciones han sido mencionadas justo en el párrafo anterior. Es más, su uso también es muy popular en la investigación en física de plasmas, por ser una de las pocas técnicas de diagnosis que proporciona información local sobre el plasma. El equipamiento donde es habitualmente implementado varía desde plasmas de laboratorio de baja temperatura hasta plasmas de fusión en dispositivos como tokamaks o stellerators. La geometría más popular de este tipo de sondas es cilíndrica, y la principal magnitud que se usa para diagnosticar el plasma es la corriente recogida por la sonda cuando se encuentra polarizada a un cierto potencial. Existe un interes especial en diagnosticar por medio de la medida de la corriente iónica recogida por la sonda, puesto que produce una perturbación muy pequeña del plasma en comparación con el uso de la corriente electrónica. Dada esta popularidad, no es de extrañar que grandes esfuerzos se hayan realizado en la consecución de un modelo teórico que explique el comportamiento de una sonda de Langmuir inmersa en un plasma. Hay que remontarse a la primera mitad del siglo XX para encontrar las primeras teorías que permiten diagnosticar parámetros del plasma mediante la medida de la corriente iónica recogida por la sonda de Langmuir. Desde entonces, las mejoras en estos modelos y el desarrollo de otros nuevos ha sido una constante en la investigación en física de plasmas. No obstante, todavía no está claro como los iones se aproximan a la superficie de la sonda. Las dos principales, a la par que opuestas, aproximaciones al problema que están ampliamente aceptadas son: la radial y la orbital; siendo el problema que ambas predicen diferentes valores para la corriente iónica. Los experimentos han arrojado resultados de acuerdo con ambas teorías, la radial y la orbital; y lo que es más importante, una transición entre ambos ha sido recientemente observada. La mayoría de los logros conseguidos a la hora de comprender como los iones caen desde el plasma hacia la superficie de la sonda, han sido llevados a cabo en el campo de la dinámica de fluidos o la teoría cinética. Por otra parte, este problema puede ser abordado mediante el uso de simulaciones de partículas. La principal ventaja de las simulaciones de partículas sobre los modelos de fluidos o cinéticos es que proporcionan mucha más información sobre los detalles microscópicos del movimiento de las partículas, además es relativamente fácil introducir interacciones complejas entre las partículas. No obstante, estas ventajas no se obtienen gratuitamente, ya que las simulaciones de partículas requieren grandísimos recursos. Por esta razón, es prácticamente obligatorio el uso de técnicas de procesamiento paralelo en este tipo de simulaciones. El vacío en el conocimiento de las sondas de Langmuir, es el que motiva nuestro trabajo. Nuestra aproximación, y el principal objetivo de este trabajo, ha sido desarrollar una simulación de partículas que nos permita estudiar el problema de una sonda de Langmuir inmersa en un plasma y que está negativamente polarizada con respecto a éste. Dicha simulación nos permitiría estudiar el comportamiento de los iones en los alrededores de una sonda cilíndrica de Langmuir, así como arrojar luz sobre la transición entre las teorías radiales y orbitales que ha sido observada experimentalmente. Justo después de esta sección introductoria, el resto de la tesis está dividido en tres partes tal y como sigue: La primera parte está dedicada a establecer los fundamentos teóricos de las sondas de Langmuir. En primer lugar, se realiza una introducción general al problema y al uso de sondas de Langmuir como método de diagnosis de plasmas. A continuación, se incluye una extensiva revisión bibliográfica sobre las diferentes teorías que proporcionan la corriente iónica recogida por una sonda. La segunda parte está dedicada a explicar los detalles de las simulaciones de partículas que han sido desarrolladas a lo largo de nuestra investigación, así como los resultados obtenidos con las mismas. Esta parte incluye una introducción sobre la teoría que subyace el tipo de simulaciones de partículas y las técnicas de paralelización que han sido usadas en nuestros códigos. El resto de esta parte está dividido en dos capítulos, cada uno de los cuales se ocupa de una de las geometrías consideradas en nuestras simulaciones (plana y cilíndrica). En esta parte discutimos también los descubrimientos realizados relativos a la transición entre el comportamiento radial y orbital de los iones en los alrededores de una sonda cilíndrica de Langmuir. Finalmente, en la tercera parte de la tesis se presenta un resumen del trabajo realizado. En este resumen, se enumeran brevemente los resultados de nuestra investigación y se han incluido algunas conclusiones. Después de esto, se enumeran una serie de perspectivas futuras y extensiones para los códigos desarrollados.

Post-CMOS compatible high-throughput fabrication of AIN-based piezoelectric microcantilevers

A post-complementary metal oxide semiconductor (CMOS) compatible microfabrication process of piezoelectric cantilevers has been developed. The fabrication process is suitable for standard silicon technology and provides low-cost and high-throughput manufacturing. This work reports design, fabrication and characterization of piezoelectric cantilevers based on aluminum nitride (AlN) thin films synthesized at room temperature. The proposed microcantilever system is a sandwich structure composed of chromium (Cr) electrodes and a sputtered AlN film. The key issue for cantilever fabrication is the growth at room temperature of the AlN layer by reactive sputtering, making possible the innovative compatibility of piezoelectric MEMS devices with CMOS circuits already processed. AlN and Cr have been etched by inductively coupled plasma (ICP) dry etching using a BCl3–Cl2–Ar plasma chemistry. As part of the novelty of the post-CMOS micromachining process presented here, a silicon Si (1 0 0) wafer has been used as substrate as well as the sacrificial layer used to release the microcantilevers. In order to achieve this, the Si surface underneath the structure has been wet etched using an HNA (hydrofluoric acid + nitric acid + acetic acid) based solution. X-ray diffraction (XRD) characterization indicated the high crystalline quality of the AlN film. An atomic force microscope (AFM) has been used to determine the Cr electrode surface roughness. The morphology of the fabricated devices has been studied by scanning electron microscope (SEM). The cantilevers have been piezoelectrically actuated and their out-of-plane vibration modes were detected by vibrometry.

Through Wafer 3D Vertical Micro-Coaxial Probe for High Frequency Material Characterization and Millimeter Wave Packaging Systems

This work presents the development of an in-plane vertical micro-coaxial probe using bulk micromachining technique for high frequency material characterization. The coaxial probe was fabricated in a silicon substrate by standard photolithography and a deep reactive ion etching (DRIE) technique. The through-hole structure in the form of a coaxial probe was etched and metalized with a diluted silver paste. A co-planar waveguide configuration was integrated with the design to characterize the probe. The electrical and RF characteristics of the coaxial probe were determined by simulating the probe design in Ansoft’s High Frequency Structure Simulator (HFSS). The reflection coefficient and transducer gain performance of the probe was measured up to 65 GHz using a vector network analyzer (VNA). The probe demonstrated excellent results over a wide frequency band, indicating its ability to integrate with millimeter wave packaging systems as well as characterize unknown materials at high frequencies. The probe was then placed in contact with 3 materials where their unknown permittivities were determined. To accomplish this, the coaxial probe was placed in contact with the material under test and electromagnetic waves were directed to the surface using the VNA, where its reflection coefficient was then determined over a wide frequency band from dc-to -65GHz. Next, the permittivity of each material was deduced from its measured reflection coefficients using a cross ratio invariance coding technique. The permittivity results obtained when measuring the reflection coefficient data were compared to simulated permittivity results and agreed well. These results validate the use of the micro-coaxial probe to characterize the permittivity of unknown materials at high frequencies up to 65GHz.

Large scale fabrication of nitrogen vacancy-embedded diamond nanostructures for single-photon source applications

Some color centers in diamond can serve as quantum bits which can be manipulated with microwave pulses and read out with laser, even at room temperature. However, the photon collection efficiency of bulk diamond is greatly reduced by refraction at the diamond/air interface. To address this issue, we fabricated arrays of diamond nanostructures, differing in both diameter and top end shape, with HSQ and Cr as the etching mask materials, aiming toward large scale fabrication of single-photon sources with enhanced collection efficiency made of nitrogen vacancy (NV) embedded diamond. With a mixture of O2 and CHF3 gas plasma, diamond pillars with diameters down to 45 nm were obtained. The top end shape evolution has been represented with a simple model. The tests of size dependent single-photon properties confirmed an improved single-photon collection efficiency enhancement, larger than tenfold, and a mild decrease of decoherence time with decreasing pillar diameter was observed as expected. These results provide useful information for future applications of nanostructured diamond as a single-photon source.

Self-healing thermal annealing: surface morphological restructuring control of GaN nanorods

With advances in nanolithography and dry etching, top-down methods of nanostructuring have become a widely used tool for improving the efficiency of optoelectronics. These nano dimensions can offer various benefits to the device performance in terms of light extraction and efficiency, but often at the expense of emission color quality. Broadening of the target emission peak and unwanted yellow luminescence are characteristic defect-related effects due to the ion beam etching damage, particularly for III–N based materials. In this article we focus on GaN based nanorods, showing that through thermal annealing the surface roughness and deformities of the crystal structure can be “self-healed”. Correlative electron microscopy and atomic force microscopy show the change from spherical nanorods to faceted hexagonal structures, revealing the temperature-dependent surface morphology faceting evolution. The faceted nanorods were shown to be strain- and defect-free by cathodoluminescence hyperspectral imaging, micro-Raman, and transmission electron microscopy (TEM). In-situ TEM thermal annealing experiments allowed for real time observation of dislocation movements and surface restructuring observed in ex-situ annealing TEM sampling. This thermal annealing investigation gives new insight into the redistribution path of GaN material and dislocation movement post growth, allowing for improved understanding and in turn advances in optoelectronic device processing of compound semiconductors.

Erosão dentária na adolescência

Com o presente trabalho, pretende-se perceber qual a relação do estilo de vida, hábitos alimentares e doenças sistémicas dos adolescentes com a erosão dentária, e quais são as melhores formas de prevenção e tratamento. É na fase da adolescência que começa a haver uma maior preocupação com o corpo e que começam a surgir alguns extremos de consumo alimentar, que podem caracterizar-se em desordens alimentares afetando diretamente a saúde oral, podendo causar erosão dentária. É também na adolescência que a prática de atividade desportiva aumenta, podendo também ter impacto no desenvolvimento desta patologia. A erosão dentária começa com a desmineralização das camadas superficiais do esmalte, podendo evoluir para perda significativa da estrutura dentária. Os ácidos responsáveis pela erosão dentária podem ter origem extrínseca ou intrínseca. Enquanto os fatores extrínsecos estão relacionados com hábitos alimentares e estilo de vida, os fatores intrínsecos podem ser provocados por doenças sistémicas. O fator fundamental da prevenção da erosão dentária é a diminuição da frequência e da severidade do ataque ácido. No entanto, pela sua etiologia multifatorial, muitas vezes este controlo torna-se difícil. Em relação ao tratamento, existem diferentes opções dependendo do grau da lesão, mas um diagnóstico precoce é o fator chave neste processo. É importante referir que a monitorização e o controlo periódico do paciente deverão ser realizados com o objetivo de promover a sua saúde e prevenir o aparecimento de novas lesões.

Development, Evaluation and Optimization of Fabrication Processes for Daylight Guiding Systems Based on Micromirror Arrays

In this work, fabrication processes for daylight guiding systems based on micromirror arrays are developed, evaluated and optimized.Two different approaches are used: At first, nanoimprint lithography is used to fabricate large area micromirrors by means of Substrate Conformal Imprint Lithography (SCIL).Secondly,a new lithography technique is developed using a novel bi-layered photomask to fabricate large area micromirror arrays. The experimental results showing a reproducible stable process, high yield, and is consuming less material, time, cost and effort.

Controlled surface nanotopography and oxygen plasma treatment of PEEK to improve cellular response

Poly(aryl-ether-ether-ketone) (PEEK) is a semi crystalline polymer which exhibits properties that make it an attractive choice for use as an implant material. It displays natural radiolucency, and MRI compatibility, as well as good chemical and sterilization resistance, both of which make it of particular interest in orthopaedic implants. However, PEEK has demonstrated poor cellular adhesion both in vitro and in vivo. This is problematic as implant surfaces that do not develop a layer of adhesive cells are at risk of undergoing fibrous encapsulation, which in turn leads to lack of a strong interface between the implant device and the patient tissue, which can in turn lead to failure of the implant and revision surgery . As incorporating nanotopography into a polymer surface has been demonstrated to be able to direct the differentiation behaviour of stem cells, a possible solution to PEEKs underlying issues with poor cellular response would be to incorporate specific nanoscale topography into the material surface through injection moulding, and then analysing if this is a viable method for addressing PEEKs issues with cellular response. In addition to nanoscale topography, the experimental PEEK surfaces were treated with oxygen plasma to address the underlying cytophobicity of the material. As this type of treatment has been documented to be capable of etching the PEEK surface, experiments were carried out to quantify the effect of this treatment, both on the ability of cells to adhere to the PEEK surface, as well as the effect it has upon the nanotopography present at the PEEK surface. The results demonstrated that there were a range of plasma treatments which would significantly improve the ability of cells to adhere to the PEEK surface without causing unacceptable damage to the nanotopography. Three different types of cells with osteogenic capacity were tested with the PEEK surfaces to gauge the ability of the topography to alter their behaviour: SAOS-2, osteoprogenitors and 271+ MSCs. Due to PEEKs material properties (it is non transparent, exhibits birefringence and is strongly autofluorescent) a number of histological techniques were used to investigate a number of different stages that take place in osteogenesis. The different cell types did display slightly different responses to the topographies. The SAOS-2 cells cultured on surfaces that had been plasma treated for 2 minutes at 200W had statistically significantly higher levels of von Kossa staining on the NSQ surface compared to the planar surface, and the same experiment employing alizarin red staining, showed a statistically significantly lower level of staining on the SQ surface compared to the planar surface. Using primary osteoprogenitor cells designed to look into if whether or not the presence of nanotopography effected the osteogenic response of these cells, we saw a lack of statistically significant difference produced by the surfaces investigated. By utilising HRP based immunostaining, we were able to investigate, in a quantitative fashion, the production of the two osteogenic markers osteopontin and osteocalcin by cells. When stained for osteocalcin, the SQ nanotopography had total percentage of the surface with stained material, average area and average perimeter all statistically significantly lower than the planar surface. For the cells that were stained for osteopontin, the SQ nanotopgraphy had a total percentage of the surface with stained material, average area and average perimeter all highly statistically significantly lower than those of the planar surface. Additionally, for this marker the NSQ nanotopography had average areas and average perimeters that were highly significantly higher than those of the planar surface. There were no significant differences for any of the values investigated for the 271+ MSC’s When plasma treatment was varied, the SAOS-2 cells demonstrated an overall trend i.e. increasing the energy of plasma treatment in turn leads to an increase in the overall percentage of staining. A similar experiment employing stem cells isolated from human bone marrow instead of SAOS-2 cells showed that for polycarbonate surfaces , used as a control, mineralization is statistically significantly higher on the NSQ nanopattern compared to the planar surface, whereas on the PEEK surfaces we observe the opposite trend i.e. the NSQ nanotopography having a statistically significantly lower amount of mineralization compared to the planar surface at the 200W 2min and 30W 1min plasma treatments. The standout trend from the PEEK results in this experiment was that the statistically significant differences on the PEEK substrates were clustered around the lower energy plasma treatments, which could suggest that the plasma treatment disrupted a function of the nanotopograhy which is why, as the energy increases, there are less statistically significant differences between the NSQ nanotopography and the Planar surface This thesis documents the response of a number of different types of cells to specific nanoscale topographies incorporated into the PEEK surface which had been treated with oxygen plasma. It outlines the development of a number of histological methods which measure different aspects of osteogenesis, and were selected to both work with PEEK, and produce quantitative results through the use of Cell Profiler. The methods that have been employed in this body of work would be of interest to other researchers working with this material, as well as those working with similarly autofluorescent materials.

Fracture toughness characterization of aluminium-epoxy adhesive joints reinforced with electrospun Nylon 6,6 nanofibers

The use of adhesives to join two different substrates is an efficient replacement to classic joining technologies such as welding and soldering. One the one hand adhesion has different advantages over those techniques such as an improved stress distribution and the potential weight reduction of the structure; on the other hand, two of the most important drawbacks are a relatively low fracture toughness and the need of an accurate surface preparation. These two aspects will be accurately analysed in the present work: the use of Nylon nanofibers as reinforcement for the adhesive should increase fracture toughness, while a surface preparation method consisting of mechanical and chemical treatments will be developed. After the specimens are produced, they will be tested in mode I fracture using a DCB (Double Beam Cantilever) test, which allows to measure the fracture toughness during crack propagation. At the end of the test, the surfaces of the adherends will be visually observed and SEM (Scanning Electronic Microscope) analysed in order to evaluate if adhesive or cohesive fracture occurred, and thus if surface treatments has been well developed to allow a better adhesive-aluminium joining.

Influence of application mode of universal adhesives on bond strength performances and enzymatic activity of coronal and radicular dentin

Objective: The aims of this thesis were to analyze the application mode of the universal adhesives (UA) and to give instructions for clinical procedures. The etching mode of UA on the bond strength to dentin and on the risk of retention, marginal discoloration, marginal adaptation and post-operative sensitivity (POS) was analyzed by two systematic reviews. Three in vitro studies were conducted: 1) evaporation mode of a UA on coronal dentin; 2) cementation approach on radicular dentin; 3) adhesion of metal brackets to enamel. Materials and methods: Two systematic review were conducted firstly, then in vitro study to investigate the evaporation mode in presence or not of pulpal pressure by means of μTBS, and the enzymatic activity using in situ zymography, at T0 and T6. The cementation of a fiber into radicular dentin with different resin-cements was studied, by push-out bond strength evaluation. Orthodontic brackets were cemented according to 4 adhesive protocols and shear bond strength test was conducted. Two adhesive removal techniques were evaluated, and spectrophotometry was used. Results: The probability of POS occurrence was less in SE. SEE approach seems to perform better than SE. Air-drying resulted in higher μTBS. Suction-evaporation, aging and ER mode increased MMPs activity. Differences in NL expression were present at T0 for fiber post study, and the aging produced an increase in marginal infiltration. Brackets cemented with new universal cement with previous etchant application showed good μTBS values. Conclusion: SEE performed better than SE and TE with UA in terms of uTBS. Evaporating with air-drying is better for UA in terms of uTBS and enzymatic activity. Aging and choice of resin cement for cementation of fiber posts influenced the PBS. Brackets cementation with a new resin- cement seems to offer the highest bond strength and leaves more cement remnants after the bracket removal.