In2O3 microcrystals obtained from rapid calcination in domestic microwave oven

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Bond strength of hard chairside reline resins to a rapid polymerizing denture base resin before and after thermal cycling

Purpose: This study assessed the shear bond strength of 4 hard chairside reline resins (Kooliner, Tokuso Rebase Fast, Duraliner II, Ufi Gel Hard) to a rapid polymerizing denture base resin (QC-20) processed using 2 polymerization cycles (A or B), before and after thermal cycling. Materials and Methods: Cylinders (3.5 mm x 5.0 mm) of the reline resins were bonded to cylinders of QC-20 polymerized using cycle A (boiling water-20 minutes) or B (boiling water; remove heat-20 minutes; boiling water-20 minutes). For each reline resin/polymerization cycle combination, 10 specimens (groups CAt e CBt) were thermally cycled (5 and 55°C; dwell time 30 seconds; 2,000 cycles); the other 10 were tested without thermal cycling (groups CAwt ad CBwt). Shear bond tests (0.5 mm/min) were performed on the specimens and the failure mode was assessed. Data were analyzed by 3-way ANOVA and Newman-Keuls post-hoc test (α=.05). Results: QC-20 resin demonstrated the lowest bond strengths among the reline materials (P<.05) and mainly failed cohesively. Overall, the bond strength of the hard chairside reline resins were similar (10.09±1.40 to 15.17±1.73 MPa) and most of the failures were adhesive/cohesive (mixed mode). However, Ufi Gel Hard bonded to QC-20 polymerized using cycle A and not thermally cycled showed the highest bond strength (P<.001). When Tokuso Rebase Fast and Duraliner II were bonded to QC-20 resin polymerized using cycle A, the bond strength was increased (P=.043) after thermal cycling. Conclusions: QC-20 displayed the lowest bond strength values in all groups. In general, the bond strengths of the hard chairside reline resins were comparable and not affected by polymerization cycle of QC-20 resin and thermal cycling.

SOLUTE-DERIVED THERMAL STABILITY OF NANOCRYSTALLINE ALUMINUM AND PROCESSING FACTOR INFLUENCE ON THE FORMATION OF AL6MN QUASICRYSTALS IN MELT-SPINNING

Thermal stability of nanograined metals can be difficult to attain due to the large driving force for grain growth that arises from the significant boundary area constituted by the nanostructure. Kinetic approaches for stabilization of the nanostructure effective at low homologous temperatures often fail at higher homologous temperatures. Thermodynamic approaches for thermal stabilization may offer higher temperature stability. In this research, modest alloying of aluminum with solute (1 at.% Sc, Yb, or Sr) was examined as a means to thermodynamically stabilize a bulk nanostructure at elevated temperatures. After using melt-spinning and ball-milling to create an extended solid-solution and nanostructure with average grain size on the order of 30-45 nm, 1 h annealing treatments at 673 K (0.72 Tm) , 773 K (0.83 Tm) , and 873 K (0.94 Tm) were applied. The alloys remain nanocrystalline (<100 nm) as measured by Warren-Averbach Fourier analysis of x-ray diffraction peaks and direct observation of TEM dark field micrographs, with the efficacy of stabilization: Sr>Yb>Sc. Disappearance of intermetallic phases in the Sr and Yb alloys in the x-ray diffraction spectra are observed to occur coincident with the stabilization after annealing, suggesting that precipitates dissolve and the boundaries are enriched with solute. Melt-spinning has also been shown to be an effective process to produce a class of ordered, but non-periodic crystals called quasicrystals. However, many of the factors related to the creation of the quasicrystals through melt-spinning are not optimized for specific chemistries and alloy systems. In a related but separate aspect of this research, meltspinning was utilized to create metastable quasicrystalline Al6Mn in an α-Al matrix through rapid solidification of Al-8Mn (by mol) and Al-10Mn (by mol) alloys. Wheel speed of the melt-spinning wheel and orifice diameter of the tube reservoir were varied to determine their effect on the resulting volume proportions of the resultant phases using integrated areas of collected x-ray diffraction spectra. The data were then used to extrapolate parameters for the Al-10Mn alloy which consistently produced Al6Mn quasicrystal with almost complete suppression of the equilibrium Al6Mn orthorhombic phase.

Study of the kinetics and mechanism of rapid self-assembly in block copolymer thin films during solvo-microwave annealing

Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high- lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during "solvo-microwave" annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 degrees C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during "solvo-microwave" annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O-2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.

Modelling and Verification of a Correction Factor to Evaluate the Efficiency of Solar Thermal Collectors with the Rapid Test Method

A new method for the evaluation of the efficiency of parabolic trough collectors, called Rapid Test Method, is investigated at the Solar Institut Jülich. The basic concept is to carry out measurements under stagnation conditions. This allows a fast and inexpensive process due to the fact that no working fluid is required. With this approach, the temperature reached by the inner wall of the receiver is assumed to be the stagnation temperature and hence the average temperature inside the collector. This leads to a systematic error which can be rectified through the introduction of a correction factor. A model of the collector is simulated with COMSOL Multipyisics to study the size of the correction factor depending on collector geometry and working conditions. The resulting values are compared with experimental data obtained at a test rig at the Solar Institut Jülich. These results do not match with the simulated ones. Consequentially, it was not pos-sible to verify the model. The reliability of both the model with COMSOL Multiphysics and of the measurements are analysed. The influence of the correction factor on the rapid test method is also studied, as well as the possibility of neglecting it by measuring the receiver’s inner wall temperature where it receives the least amount of solar rays. The last two chapters analyse the specific heat capacity as a function of pressure and tem-perature and present some considerations about the uncertainties on the efficiency curve obtained with the Rapid Test Method.

Theoretical investigation of thermal tweezers for parallel manipulation of atoms and nanoparticles on surfaces

A major focus of research in nanotechnology is the development of novel, high throughput techniques for fabrication of arbitrarily shaped surface nanostructures of sub 100 nm to atomic scale. A related pursuit is the development of simple and efficient means for parallel manipulation and redistribution of adsorbed atoms, molecules and nanoparticles on surfaces – adparticle manipulation. These techniques will be used for the manufacture of nanoscale surface supported functional devices in nanotechnologies such as quantum computing, molecular electronics and lab-on-achip, as well as for modifying surfaces to obtain novel optical, electronic, chemical, or mechanical properties. A favourable approach to formation of surface nanostructures is self-assembly. In self-assembly, nanostructures are grown by aggregation of individual adparticles that diffuse by thermally activated processes on the surface. The passive nature of this process means it is generally not suited to formation of arbitrarily shaped structures. The self-assembly of nanostructures at arbitrary positions has been demonstrated, though these have typically required a pre-patterning treatment of the surface using sophisticated techniques such as electron beam lithography. On the other hand, a parallel adparticle manipulation technique would be suited for directing the selfassembly process to occur at arbitrary positions, without the need for pre-patterning the surface. There is at present a lack of techniques for parallel manipulation and redistribution of adparticles to arbitrary positions on the surface. This is an issue that needs to be addressed since these techniques can play an important role in nanotechnology. In this thesis, we propose such a technique – thermal tweezers. In thermal tweezers, adparticles are redistributed by localised heating of the surface. This locally enhances surface diffusion of adparticles so that they rapidly diffuse away from the heated regions. Using this technique, the redistribution of adparticles to form a desired pattern is achieved by heating the surface at specific regions. In this project, we have focussed on the holographic implementation of this approach, where the surface is heated by holographic patterns of interfering pulsed laser beams. This implementation is suitable for the formation of arbitrarily shaped structures; the only condition is that the shape can be produced by holographic means. In the simplest case, the laser pulses are linearly polarised and intersect to form an interference pattern that is a modulation of intensity along a single direction. Strong optical absorption at the intensity maxima of the interference pattern results in approximately a sinusoidal variation of the surface temperature along one direction. The main aim of this research project is to investigate the feasibility of the holographic implementation of thermal tweezers as an adparticle manipulation technique. Firstly, we investigate theoretically the surface diffusion of adparticles in the presence of sinusoidal modulation of the surface temperature. Very strong redistribution of adparticles is predicted when there is strong interaction between the adparticle and the surface, and the amplitude of the temperature modulation is ~100 K. We have proposed a thin metallic film deposited on a glass substrate heated by interfering laser beams (optical wavelengths) as a means of generating very large amplitude of surface temperature modulation. Indeed, we predict theoretically by numerical solution of the thermal conduction equation that amplitude of the temperature modulation on the metallic film can be much greater than 100 K when heated by nanosecond pulses with an energy ~1 mJ. The formation of surface nanostructures of less than 100 nm in width is predicted at optical wavelengths in this implementation of thermal tweezers. Furthermore, we propose a simple extension to this technique where spatial phase shift of the temperature modulation effectively doubles or triples the resolution. At the same time, increased resolution is predicted by reducing the wavelength of the laser pulses. In addition, we present two distinctly different, computationally efficient numerical approaches for theoretical investigation of surface diffusion of interacting adparticles – the Monte Carlo Interaction Method (MCIM) and the random potential well method (RPWM). Using each of these approaches we have investigated thermal tweezers for redistribution of both strongly and weakly interacting adparticles. We have predicted that strong interactions between adparticles can increase the effectiveness of thermal tweezers, by demonstrating practically complete adparticle redistribution into the low temperature regions of the surface. This is promising from the point of view of thermal tweezers applied to directed self-assembly of nanostructures. Finally, we present a new and more efficient numerical approach to theoretical investigation of thermal tweezers of non-interacting adparticles. In this approach, the local diffusion coefficient is determined from solution of the Fokker-Planck equation. The diffusion equation is then solved numerically using the finite volume method (FVM) to directly obtain the probability density of adparticle position. We compare predictions of this approach to those of the Ermak algorithm solution of the Langevin equation, and relatively good agreement is shown at intermediate and high friction. In the low friction regime, we predict and investigate the phenomenon of ‘optimal’ friction and describe its occurrence due to very long jumps of adparticles as they diffuse from the hot regions of the surface. Future research directions, both theoretical and experimental are also discussed.

Thermal profile of a near-adiabatic compression process in a cylindrical tube and establishment of critical control elements for repeatable process control

The compressed gas industry and government agencies worldwide utilize "adiabatic compression" testing for qualifying high-pressure valves, regulators, and other related flow control equipment for gaseous oxygen service. This test methodology is known by various terms including adiabatic compression testing, gaseous fluid impact testing, pneumatic impact testing, and BAM testing as the most common terms. The test methodology will be described in greater detail throughout this document but in summary it consists of pressurizing a test article (valve, regulator, etc.) with gaseous oxygen within 15 to 20 milliseconds (ms). Because the driven gas1 and the driving gas2 are rapidly compressed to the final test pressure at the inlet of the test article, they are rapidly heated by the sudden increase in pressure to sufficient temperatures (thermal energies) to sometimes result in ignition of the nonmetallic materials (seals and seats) used within the test article. In general, the more rapid the compression process the more "adiabatic" the pressure surge is presumed to be and the more like an isentropic process the pressure surge has been argued to simulate. Generally speaking, adiabatic compression is widely considered the most efficient ignition mechanism for directly kindling a nonmetallic material in gaseous oxygen and has been implicated in many fire investigations. Because of the ease of ignition of many nonmetallic materials by this heating mechanism, many industry standards prescribe this testing. However, the results between various laboratories conducting the testing have not always been consistent. Research into the test method indicated that the thermal profile achieved (i.e., temperature/time history of the gas) during adiabatic compression testing as required by the prevailing industry standards has not been fully modeled or empirically verified, although attempts have been made. This research evaluated the following questions: 1) Can the rapid compression process required by the industry standards be thermodynamically and fluid dynamically modeled so that predictions of the thermal profiles be made, 2) Can the thermal profiles produced by the rapid compression process be measured in order to validate the thermodynamic and fluid dynamic models; and, estimate the severity of the test, and, 3) Can controlling parameters be recommended so that new guidelines may be established for the industry standards to resolve inconsistencies between various test laboratories conducting tests according to the present standards?

3D thermal mapping of building interiors using an RGB-D and thermal camera

The building sector is the dominant consumer of energy and therefore a major contributor to anthropomorphic climate change. The rapid generation of photorealistic, 3D environment models with incorporated surface temperature data has the potential to improve thermographic monitoring of building energy efficiency. In pursuit of this goal, we propose a system which combines a range sensor with a thermal-infrared camera. Our proposed system can generate dense 3D models of environments with both appearance and temperature information, and is the first such system to be developed using a low-cost RGB-D camera. The proposed pipeline processes depth maps successively, forming an ongoing pose estimate of the depth camera and optimizing a voxel occupancy map. Voxels are assigned 4 channels representing estimates of their true RGB and thermal-infrared intensity values. Poses corresponding to each RGB and thermal-infrared image are estimated through a combination of timestamp-based interpolation and a pre-determined knowledge of the extrinsic calibration of the system. Raycasting is then used to color the voxels to represent both visual appearance using RGB, and an estimate of the surface temperature. The output of the system is a dense 3D model which can simultaneously represent both RGB and thermal-infrared data using one of two alternative representation schemes. Experimental results demonstrate that the system is capable of accurately mapping difficult environments, even in complete darkness.

Fabrication of SiGe rings and holes on Si(001) by flash annealing

We show that SiGe islands are transformed into nanoholes and rings by annealing treatments only and without Si capping. Rings are produced by a rapid flash heating at temperatures higher than the melting point of Ge, whereas nanoholes are produced by several minute annealing. The rings are markedly rich in Si with respect to the pristine islands, suggesting that the evolution path from islands to rings is driven by the selective dissolution of Ge occurring at high temperature.

Study of particulate matter removal mechanism by using non-thermal plasma technology

Numbers of diesel engines in both stationary and mobile applications are increasing nowadays. Diesel engines emit lower Hydrocarbon (HC) and Carbon monoxide (CO) than gasoline engines. However, they can produce more nitrogen oxides (NOx) and have higher particulate matter (PM). On the other hand, emissions standards are getting stringent day by day due to considerable concerns about unregulated pollutants and particularly ultrafine particles deleterious effect on human health. Non-thermal plasma (NTP) treatment of exhaust gas is known as a promising technology for both NOx and PM reduction by introducing plasma inside the exhaust gas. Vehicle exhaust gases undergo chemical changes when exposed to plasma. In this study, the PM removal mechanism using NTP by applying high voltage pulses of up to 20 kVpp with a repetition rate of 10 kHz are investigated. It is found that, voltage increase not necessarily has a positive effect on PM removal in diesel engine emissions.

Rapid aminoacidemia enhances myofibrillar protein synthesis and anabolic intramuscular signaling responses after resistance exercise

Background: Ingestion of whey or casein yields divergent patterns of aminoacidemia that influence whole-body and skeletal muscle myofibrillar protein synthesis (MPS) after exercise. Direct comparisons of the effects of contrasting absorption rates exhibited by these proteins are confounded by their differing amino acid contents. Objective: Our objective was to determine the effect of divergent aminoacidemia by manipulating ingestion patterns of whey protein alone on MPS and anabolic signaling after resistance exercise. Design: In separate trials, 8 healthy men consumed whey protein either as a single bolus (BOLUS; 25-g dose) or as repeated, small, "pulsed" drinks (PULSE; ten 2.5-g drinks every 20 min) to mimic a more slowly digested protein. MPS and phosphorylation of signaling proteins involved in protein synthesis were measured at rest and after resistance exercise. Results: BOLUS increased blood essential amino acid (EAA) concentrations above those of PULSE (162% compared with 53%, P < 0.001) 60 min after exercise, whereas PULSE resulted in a smaller but sustained increase in aminoacidemia that remained elevated above BOLUS amounts later (180-220 min after exercise, P < 0.05). Despite an identical net area under the EAA curve, MPS was elevated to a greater extent after BOLUS than after PULSE early (1-3 h: 95% compared with 42%) and later (3-5 h: 193% compared with 121%) (both P < 0.05). There were greater changes in the phosphorylation of the Akt-mammalian target of rapamycin pathway after BOLUS than after PULSE. Conclusions: Rapid aminoacidemia in the postexercise period enhances MPS and anabolic signaling to a greater extent than an identical amount of protein fed in small pulses that mimic a more slowly digested protein. A pronounced peak aminoacidemia after exercise enhances protein synthesis.

Sterilizing tissue-materials using pulsed power plasma

This paper investigates the potential of pulsed power to sterilize hard and soft tissues and its impact on their physico-mechanical properties. It hypothesizes that pulsed plasma can sterilize both vascular and avascular tissues and the transitive layers in between without deleterious effects on their functional characteristics. Cartilage/bone laminate was chosen as a model to demonstrate the concept, treated at low temperature, at atmospheric pressure, in short durations and in buffered environment using a purposed-built pulsed power unit. Input voltage and time of exposure were assigned as controlling parameters in a full factorial design of experiment to determine physical and mechanical alteration pre- and post-treatment. The results demonstrated that, discharges of 11 kV sterilized samples in 45 s, reducing intrinsic elastic modules from 1.4 ± 0.9 to 0.9 ± 0.6 MPa. There was a decrease of 14.1 % in stiffness and 27.8 % in elastic-strain energy for the top quartile. Mechanical impairment was directly proportional to input voltage (P value < 0.05). Bacterial inactivation was proportional to treatment time for input voltages above 32 V (P < 0.001; R Sq = 0.98). Thermal analysis revealed that helix-coil transition decelerated with exposure time and collagen fibrils were destabilized as denaturation enthalpy reduced by 200 μV. We concluded by presenting a safe operating threshold for pulsed power plasma as a feasible protocol for effective sterilization of connective tissues with varying level of loss in mechanical robustness which we argue to be acceptable in certain medical and tissue engineering application.

Investigation on bioactivity of titanium dioxide thin films fabricated by electron cyclotron resonance plasma aided pulsed laser deposition

Titanium dioxide thin films with a rutile crystallinite size around 20 nm were fabricated by pulsed laser deposition (PLD) aided with an electron cyclotron resonance (ECR) plasma. With annealing treatment, the crystal size of the rutile crystallinite increased to 100 nm. The apatite-forming ability of the films as deposited and after annealing was investigated in a kind of simulated body fluid with ion concentrations nearly equal to those of human blood plasma. The results indicate that ECR aided PLD is an effective way both to fabricate bioactive titanium dioxide thin films and to optimize the bioactivity of titanium dioxide, with both crystal size and defects of the film taken into account.

Reduction of diesel engine exhaust emissions using non-thermal plasma technology

Non-thermal plasma (NTP) is a promising candidate for controlling engine exhaust emissions. Plasma is known as the fourth state of matter, where both electrons and positive ions co-exist. Both gaseous and particle emissions of diesel exhaust undergo chemical changes when they are exposed to plasma. In this project diesel particulate matter (DPM) mitigation from the actual diesel exhaust by using NTP technology has been studied. The effect of plasma, not only on PM mass but also on PM size distribution, physico-chemical structure of PM and PM removal mechanisms, has been investigated. It was found that NTP technology can significantly reduce both PM mass and number. However, under some circumstances particles can be formed by nucleation. Energy required to create the plasma with the current technology is higher than the benchmark set by the commonly used by the automotive industry. Further research will enable the mechanism of particle creation and energy consumption to be optimised.

Performance evaluation of non-thermal plasma on particulate matter, ozone and CO2 correlation for diesel exhaust emission reduction

This study is seeking to investigate the effect of non-thermal plasma technology in the abatement of particulate matter (PM) from the actual diesel exhaust. Ozone (O3) strongly promotes PM oxidation, the main product of which is carbon dioxide (CO2). PM oxidation into the less harmful product (CO2) is the main objective whiles the correlation between PM, O3 and CO2 is considered. A dielectric barrier discharge reactor has been designed with pulsed power technology to produce plasma inside the diesel exhaust. To characterise the system under varied conditions, a range of applied voltages from 11 kVPP to 21kVPP at repetition rates of 2.5, 5, 7.5 and 10 kHz, have been experimentally investigated. The results show that by increasing the applied voltage and repetition rate, higher discharge power and CO2 dissociation can be achieved. The PM removal efficiency of more than 50% has been achieved during the experiments and high concentrations of ozone on the order of a few hundreds of ppm have been observed at high discharge powers. Furthermore, O3, CO2 and PM concentrations at different plasma states have been analysed for time dependence. Based on this analysis, an inverse relationship between ozone concentration and PM removal has been found and the role of ozone in PM removal in plasma treatment of diesel exhaust has been highlighted.