Manganese doped ZnS nanoparticles

Nanostructured materials can be defined as those materials whose structural elements - clusters, crystallites or molecules - have dimensions in the 1-100 nm range. The explosion in both academic and industrial interest over the past 20 years arises from the remarkable variations in fundamental electrical, optical and magnetic properties that occur as one progresses from an "infinitely extended" solid to a particle of material consisting of a countable number of atoms. In this work the attention was laid on the optical properties of Mn2+ doped ZnS nanoparticles with respect to a possible application as bio sensor in medical and biological analytics. A synthesis for this type of particles has been developed and the nanocrystals obtained have been investigated in terms of their composition, particle size and optical properties. The particles synthesized were stabilized with the amino acid L-cysteine and showed the typical ZnS:Mn emission spectrum with its orange emission due to the 4T1 –> 6A1 transition within the d-orbitals of the Mn2+ at 585 nm and its blue emission due to recombination over the ZnS band gap from shallow electron traps at 380 nm. The onset of the absorption was blue shifted from 340 nm (bulk) to 310 nm, indicating a quantum size effect. The particle sizes and particle size distributions were determined with methods such as transmission electron microscopy, photon correlation spectroscopy, analytical ultra centrifugation and field flow fractionation. The particle size has also been calculated from the shift in the band gap with the help of the effective mass approximation. The limits of the applied techniques are discussed and the particle size distribution determined to go from 3-20 nm with a first maximum at about 5 nm and a second maximum at about 17 nm. The particles' luminescence quantum yields have been determined between 1.5-2 %. They could be enhanced by a factor of three by coating the particles with a SiO2 shell. The quantum yields showed a strong dependence on the dispersion concentration and Mn2+ content. These effects have been investigated with quantum yield measurements at different temperatures and Mn2+ contents, and lifetime measurements. The lifetime measurements showed decay times in the ns region for the blue and in the μs-ms region for the orange emission, indicating a florescence mechanism for the ZnS and a phosphorescence mechanism for the Mn2+ radiation.

Finite element modeling and experimental study of brittle fracture in tempered martensitic steels for thermonuclear fusion applications

Pablo Federico Mueller

In this work we have studied brittle fracture in high-chromium reduced activation tempered martensitic steels foreseen as structural materials for thermonuclear fusion reactors. Developing the adequate materials that can withstand the severe irradiation conditions of the burning plasma in a future fusion reactor is one of the major challenges to be solved in order to make profit from the great advantages of thermonuclear fusion as an energy source. High-chromium tempered martensitic steels such as F82H and the most advanced version Eurofer97 are among the main candidate materials for structural applications in future fusion power plants due to low irradiation-induced swelling, good mechanical and thermal properties, and reasonably fast radioactive decay. The most concerning drawback of these kind of steels is irradiation embrittlement, which is manifested by a ductile-to-brittle transition temperature shift to higher temperatures after irradiation whose amplitude depends on the irradiation conditions (temperature, neutron flux, neutron fluence, etc). The aim of this work was to study and model brittle fracture in the ductile-brittle transition region of this kind of steels in the as-received unirradiated conditions. It is necessary to be able to transfer laboratory specimen fracture data to real components and structures in order to assess the performance of these steels in the different operating and transient conditions they could find during the operation life of a fusion reactor. In order to do so, the specimen geometry effects and specimen size effects on measured fracture toughness need to be properly understood, taken into account and predicted with an appropriate model. In particular, specimen size effect on measured toughness is a major concern for the nuclear materials research community owing to the limited irradiation volume in current and planed materials irradiation facilities. The main results of this PhD work are summarized below. The microstructure of Eurofer97 and F82H has been characterized and compared by means of optical microscopy, scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy in order to identify microstructural features that could play a role in the measured fracture toughness. Both steels have similar but slightly different chemical composition and final heat-treatments but the prior austenitic grain size measured in F82H is approximately 8 times larger than in Eurofer97. It was shown that the alloying element Tantalum, added to stabilize the austenite grain size, played a different role in both steels. After a careful analysis of the particles present in both steels, it was found that Tantalum in Eurofer97 formed carbides of an average size around 100 nanometers. In contrast in F82H it did not form small carbides but formed big oxide inclusions with a size up to 30 µm. These large particles do not effectively pin the grain boundaries. The different behavior of Tantalum in these steels is believed to be mainly a consequence of the larger content of Oxygen present and the smaller amount of Aluminum in F82H compared to Eurofer97. The Master-Curve ASTM-E1921 standard is a method initially developed to determine the ductile-to-brittle transition reference temperature, T0, in fission reactor ferritic steels from a small number of experiments. In this work the applicability of the Master-Curve method to reduced activation tempered martensitic steels such as Eurofer97 and F82H was studied in detail. Fracture tests with pre-cracked sub-sized compact tension specimens (three different sizes, 0.18T, 0.35T and 0.87T of Eurofer97) were carried out in the temperature range [-196 °C, -40 °C]. The toughness-temperature behavior and scatter were shown to deviate from the ASTM-E1921 standard predictions near the lower shelf. Using the method of maximum likelihood, the athermal component of the Master-Curve was calculated to better fit our fracture toughness data from the lower to the middle transition region. We showed that these Master-Curve adjustments are necessary to make the T0 values obtained near the lower shelf with 0.35T size C(T) specimens consistent with those obtained in the middle transition region with 0.87T C(T) specimens. The ASTM-E1921 specimen size limitations, setting the maximum toughness measurable with a given specimen size, were found to be too lenient for this kind of steels. This problem was especially evident in fracture toughness data of Eurofer97 and F82H obtained in the upper transition temperature range with two different specimen sizes. Thus a more stringent specimen size requirement was proposed to avoid inconsistent transition temperature determinations. A promising local fracture model with the potential of predicting cleavage fracture toughness was studied. Finite element simulations were undertaken for compact specimens, notched specimens and tensile specimens of Eurofer97 steel tested from 20 °C down to -197 °C. Three and two dimensional as well as axisymmetric simulations were run in order to calculate the stress and strain fields at the onset of brittle fracture. For each tested temperature, the calculated load-displacement curves were found to reproduce very well those of the experiments. A local approach fracture criterion was studied. This criterion states that when the maximum principal stress is larger than a critical stress within a critical volume ahead of the crack tip, notch or neck, cleavage is triggered leading to macroscopic fracture of the specimen. It was shown that this model is able to predict the minimum fracture load of the notched specimens with the same values of critical stress and critical volume that were calibrated to predict the lower bound of fracture in compact specimens. This local approach model was also successfully used to predict the strong size effect observed experimentally in pre-cracked compact tension specimens in the upper transition region. The critical fracture stress determined in the standard tensile specimens was found higher than that of the fracture specimens. It was suggested that this difference stems from a significant difference in the stress state between the different specimens (triaxiality). Finally, the comparison between the overall fracture behavior in the transition between F82H and Eurofer97 steels indicated that these two materials are quite similar. A difference in the reference temperature T0 of about 20 °C was found, with a nominal value of -100 °C and -80 °C for F82H and Eurofer97 respectively. However, some excessive scatter in the toughness data was found in F82H with more data points than expected lying below the 1% tolerance bound; this was not observed in Eurofer97. From an engineering point of view, the entire fracture databases of these two steels are encompassed practically by the same lower tolerance bound.

EPFL2009

Process monitoring of alumina nanoparticle synthesis by inductively coupled RF thermal plasma

Jong-Won Shin

Since the first inductively coupled plasma (ICP) torch was developed in the 60's, RF thermal plasmas have found a variety of applications in material processing such as crystal growth, thermal spray coatings, spheroidization and vaporization of refractory materials. In recent decades, inductively coupled thermal plasmas have been used for the synthesis of high purity nanoparticles, thank to their remarkable advantages such as high energy density, variable operating pressures and low product contamination. The formation of nano-sized particles in thermal plasmas particularly using solid refractory precursor is a complex process. Hereby the injected precursor powders are heated by the high temperature of the thermal plasma. The heated powders are vaporized and decomposed into vapor species. During the following cooling, the vapor species are condensed to nano-sized particles. In this synthesis process, characterized by evaporation-condensation, the properties of the synthesized particles such as particle size, size distribution, phases and morphology are affected by various process parameters. Gas pressure, flow rates of the different torch gases, size of the precursor powders and powder loading in the plasma are considered as the influencing process parameters. In order to optimize and control the process for tailor-made nanoparticle synthesis, it is necessary to understand the effects of the process parameters on plasma properties and on the particle-plasma interactions resulting in final properties of the synthesized powders. In the present work, firstly, the enthalpy probe technique, a well-established plasma diagnostic tool for high pressure thermal plasma, has been applied to characterize the inductively coupled Ar-H2 thermal RF plasma used for alumina nanoparticle synthesis at different operating conditions. The plasma enthalpy has been determined, and the plasma temperature under a given gas pressure could subsequently be calculated assuming local thermodynamic equilibrium (LTE), once the gas composition has been determined by mass spectrometry. The gas velocity of the plasma jet could also be obtained by using the Bernoulli equation and stagnation pressure. Secondly, the influence of flow rates of central gas and precursor feed rates on the Al2O3 precursor evaporation has been investigated by process monitoring. Optical emission spectroscopy (OES) and laser light extinction (LE) measurements have been carried out to monitor in-situ the injection of the alumina precursors and to obtain information on the ongoing precursor evaporation. The emission line intensities of the aluminum vapor were used to determine the dependence of process parameters on precursor evaporation. Furthermore, the laser light extinction was used to calculate the number density of non plasma-treated powders, from which the number fraction of evaporated powders could be deduced. The size and morphology of the synthesized particles have been characterized ex-situ. Finally, the influence of quenching conditions on the condensation and formation of the nano-sized alumina particle has been studied by process analysis of the gas phase reactions of alumina. Optical emission spectroscopic was performed at different axial positions to monitor the gas phase reactions of the vaporized particles. Axial profiles of the emission line intensities of the main vapor species of alumina, Al(g) and AlO(g), were compared with the results of the enthalpy probe measurements and the thermal decomposition reactions of alumina found in literature. The results allow explanation of the alumina reactions in the thermal plasma as well as gives indications for the optimal axial position of the quenching gas injection. In addition to the determination of the optimal quenching position, the influence of the flow rates of quenching gas on the nanoparticle formation has been investigated. The synthesis of the submicron alumina using vapor-condensation principle predominantly leads to various thermodynamically metastable crystal structures called transition alumina. Therefore, the occurrence of different transition aluminas is discussed with regards to the flow rates of the quenching gas. The results presented in this thesis show that the synthesis process of the nanoparticle can be described on the basis of experimental results and basic information on the powder materials. The explanation of the influence of process parameters on powder evaporation and nanoparticle formation shows the usefulness of the in-situ plasma process monitoring, and the large potential for optimizing and controlling the nanopowder synthesis process in an inductively coupled RF thermal plasma.

EPFL2006

Contribution to the Production and Characterization of W-Y, W-Y2O3 and W-TiC Materials for Fusion Reactors

Lyubomira Veleva

This PhD Thesis work was aimed at investigating the potentiality of tungsten-base materials as structural materials for the future thermonuclear fusion reactors in attempting to develop reduced activation tungsten-base materials with high strength and sufficient ductility, especially in terms of fracture toughness and ductile-to-brittle transition temperature, on the basis of the following ideas: (1) nano-grained materials are expected to show an improved ductility with respect to normal grain-sized materials, and (2) nano-grained materials and materials reinforced with either oxide or carbide particles are expected to show improved strength and radiation resistance, as (i) the particles should act as obstacles for the propagation of mobile dislocations, (ii) the numerous grain boundaries and interfaces between the matrix and the particles should act as sinks for the irradiation-induced defects, and (iii) the particles should also help stabilizing the numerous grain boundaries upon thermal annealing and/or irradiation. A variety of W-base materials, namely W-(0.3-1.0-2.0)Y2O3, W-(0.3-1.0-2.0)Y and W-(0.3-0.9-1.7)TiC materials (in weight percent), have been successfully produced at the laboratory scale by powder metallurgy techniques including mechanical alloying followed by either cold pressing and sintering or hot isostatic pressing (HIPping). X-ray diffractometry and scanning and transmission electron microscopy observations combined with density and microhardness measurements as well as with tensile, Charpy impact, fracture toughness and non-standard three point bending tests allowed the identification of optimal chemical compositions and manufacturing conditions, among those investigated and on the basis of the experimental devices at disposal. Microscopic investigations showed that the materials produced at the laboratory scale are composed of small grains, with sizes between a few tens and a few hundreds nanometers, and contain a high density of small Y2O3 or TiC particles, with sizes between 1 and 50 nm. In the case of W-Y materials, all the Y transformed into Y2O3 during mechanical alloying, due to the high amount of O (around 1 wt.%) present in the milled powders, which is beneficial for reducing the excess O content in the materials. All materials also contain a residual porosity of a few percents, which is typical of materials compacted by HIPping. Macroscopic investigations showed that the HIPped materials exhibit high strength values and a promising resistance to irradiation but poor fracture properties up to a very high temperature of about 1100 °C, due mostly to air contamination of the mechanically alloyed powders and to residual porosity of the compacted materials. The materials produced entirely at the laboratory scale by mechanical alloying and HIPping are of better quality than a W-2Y material that was produced by mechanical alloying at the laboratory scale and compacted by sintering and forging at the Plansee company (Austria). Further studies should focus on reducing the O content in the mechanically alloyed powders and the residual porosity of the compacted materials. The grain size should be also optimized as well as the size distribution, number density and crystallographic features of the oxide and carbide particles.

EPFL2011