The purpose of this work is the deposition of films in order to increase the corrosion resistance of AISI 304 steel, which is a material used to construct the reactors for bioethanol production. This deposition inhibits the permeation of corrosive species to the film-metal interface. Thin films were prepared by radio-frequency plasma enhanced chemical vapor deposition (RF-PECVD) method using plasmas of hexamethyldisiloxane/argon/oxygen mixtures excited by signals of different powers. The plasma was generated by the application of RF power of 13.56 MHz to the sample holder while keeping grounded the topmost electrode and the chamber walls. The effect of the RF power on the properties of the samples was investigated by perfilometry, X-ray photoelectron spectroscopy (XPS), contact angle, and electrochemical impedance spectroscopy (EIS). The results of the corrosion resistance tests of the AISI 304 steel were interpreted in terms of the energy delivered to the growing layer by plasma excitation power.

In recent years, platinum-based single crystalline nanoalloys as nanoscale catalysts, such as Pt-M (M = Ni, Co, Fe..etc.), have exhibited improved catalytic performance due to the increase in the surface-to-volume ratio. Some Pt-M nanopolyhedra such as nanocubes and nano-octahedra have been reported with enhanced activity when being used as electrocatalysts. In order to further establish a correlation between the exposed nanocrystal facets (shapes) and their corresponding activities, a pursuit of shape-controlled nanocatalyst synthesis is essential. Although PtPb nanoalloys have been prepared using solution-based methods, few studies have highlighted their catalytic activity as a function of the nanocrystal shape. This work focuses on a modified polyol synthesis technique and an adjustment of the Pb-metal precursor, which serves as a “buffer” in the nucleation stage of the shape-controlled nanoalloy development. Using this developed synthetic strategy, shape-controlled hexagonally close-packed PtPb nanoalloys can be prepared in a one-pot synthesis without additional post-treatment. The as-prepared PtPb nanocrystals demonstrate an improved anode electrocatalytic performance.

The second half of the twentieth century saw a dramatic shift in lithium chemicals production from traditional pegmatite sources to brines. Today, the bulk of lithium carbonate, which serves as the raw material for various downstream lithium chemicals, including lithium metal for the lithium batteries, is produced from the brines of the Salar de Atacama, Chile, the Salar del Hombre Muerto, Argentina and Clayton Valley Nevada, U.S.A. There is minor production in Tibet and the People’s Republic of China (PRC). Australian spodumene concentrates are converted to lithium carbonate in the PRC.

The resurgence in the potential development of electric cars has resulted in the increased exploration for and identification of potential new lithium brine operations and the reassessment of some pegmatite deposits.

A number of predictions for a potentially large electric car market scenario have raised questions on the availability of sufficient lithium resources. However, since the original 1976 report on global lithium resources by the National Academies of Sciences and Engineering, newly identified deposits have almost quadrupled the total potentially available lithium resources. Based on the best predictions, the lithium supply is more than adequate to meet the demand for electric cars well into the 21st century.

Roll-to-roll deposition techniques for the fabrication of chalcopyrite solar cells are of major interest and are a promising alternative to state of the art vacuum processes. However, for roll-to-roll processes the preparation of precursor materials like nanoparticle inks is a crucial point. In this work a study on the preparation technique of copper-indium intermetallic nanoparticles was conducted. The preparation of the nanoparticles is based on the chemical reduction of copper and indium cations with sodium borohydride. Different parameters are discussed regarding their influence on (1) size and shape of the nanoparticles, (2) Cu/In ratio within the synthesised nanoparticles and (3) yield of the synthesis. Results show a strong dependency of the Cu/In ratio of the nanoparticles and the yield of the synthesis on the synthesis parameters. The influence of different parameters like (a) the ratio of metal cations to BH4- anions, (b) the Cu2+/In3+ cation ratio within the precursor solution and (c) the dropping rate of the copper-indium precursor solution are discussed. The Cu/In ratio within the nanoparticles can mainly be controlled by the Cu2+/In3+ cation ratio and the dropping rate of the copper-indium precursor solution. The yield of the synthesis shows saturation behaviour depending on the ratio of metal cations to BH4- anions. Shape and size of the nanoparticles are independent of the varied parameters.

Papers in the Appendix were published in electronic format as Volume 1534

Bone tissue engineering typically involves the use of porous, bioresorbable scaffolds to serve as temporary, three-dimensional scaffolds to guide cell attachment, differentiation, proliferation, and subsequent tissue regeneration. In this study we developed a composite membrane scaffold by phase inversion technique by using biodegradable polyester, Polycaprolactone (PCL), with hydroxyapatite (HA) in order to develop novel controlled nanostructured biomaterials for bone tissue engineering applications.After preparation, membrane scaffolds were characterized in order to evaluate its morphological, physico-chemical and mechanical properties and then used for the cell culture.

Our experimental design consists to apply the knowledge of natural bone tissue remodelling in an in vitro membrane biohybrid system. We used human mesenchymal stem cells for culture in the membrane scaffolds inducing the differentiation in osteoblasts and human monocytes to trigger osteoclastogenesis. Osteoclastic resorption of the scaffold material would lead to subsequent induction of osteoblasts and faster bone formation with mesenchymal stem cells. Our results show that osteoblasts and osteoclasts were successfully differentiated in the developed PCL-HA membrane scaffold. This membrane system will lead to insights in the creation of a controllable osteoinductive microenvironment based on the specific properties (e.g. basic composition, surface chemistry, architecture) and on the function (resorption coupled to proliferation and differentiation) of defined cellular systems.

The theoretically-predicted enhancement of metal-graphene contacts using the “end-contacted” configuration is studied. Graphene edges at the source/drain regions are created via a CMOS process compatible metal-assisted etching technique. The on-resistance of a graphene device with cobalt-etched-graphene contacts shows 6 times improvement compared to pristine graphene device. Apart from that, four-point contacted graphene devices with nickel-etched-graphene contacts were fabricated and tested under ambient conditions. The proposed graphene devices exhibit contact resistance as low as 14 Ωμm, with an average of 90 Ωμm. Thus, forming metal-etched-graphene contacts is a promising method to obtain low-contact resistance metal contacts to graphene.

In the framework of the study of long-term storage of the spent nuclear fuel, polycrystalline UO2 samples have been implanted with He ions. The thin implanted layer, close to the free surface is subjected to elastic stresses which are studied by x-ray diffraction (micro Laue diffraction) and a mechanical modeling. A simple expression of the displacement gradient tensor has been evidenced; it concerns only three terms (ε3, ε4 and ε5) which strongly evolve with considered grain orientations. Finally, we show that results obtained with micro diffraction are in very good agreement with conventional x-ray diffraction measurements done in laboratory at macro scale.

The electronic properties of ThO2 single crystals were studied using x-ray photoemission spectroscopy (XPS). The XPS results show that the Th 4f core level is in an oxidation state that is consistent with that expected for Th in ThO2. The effective Debye temperature is estimated from the temperature dependent photoemission intensities of the Th 4f core level over the temperature range of 290 to 360 K. A Debye temperature of 468±32 K has been determined.

In order to develop NiMnGa/polymer composite materials, a production of single-crystal-like NiMnGa particles is important and should be developed for better quality. Although mechanical pulverization is a promising method by utilizing intrinsic intergranular brittleness of NiMnGa polycrystalline ingots, the amount of lattice defects introduced during mechanical crushing needs to be minimized. This must be achieved by enhancement of intergranular brittleness of NiMnGa particles. In this study, the effect of Bi addition on the compressive fracture behavior of polycrystalline Ni50Mn28Ga22 was investigated where Bi was expected to be segregated to the grain boundaries in NiMnGa, similar to Bi segregation to the grain boundaries in Ni. It was found that only intergranular fracture was observed in Ni50Mn28Ga22 polycrystals with 0.3 at.% Bi addition, although a mixture of intergranular and transgranular fracture was observed in Bi-free Ni50Mn28Ga22 polycrystal. Microalloying of Bi into NiMnGa enhances intergranular embrittlement. A number of spherical particles of Bi were confirmed on the fractured surface of Bi-doped NiMnGa polycrystals. The formation of Bi particles is a proof of the grain boundary segregation of Bi in NiMnGa.

In nonaqueous emulsion, moisture-sensitive polymerizations are performed in order to generate nanoparticles, which are not accessible by common aqueous emulsion polymerization. A nonaqueous emulsion, consisting of two immiscible aprotic organic solvents, is stabilized by amphiphilic block copolymers, such as PIb-PEO or PIb-PMMA copolymer, and lead to formation of nanosized dispersed droplets. They act as dispersed “nanoreactors” for the one-step synthesis of poly(urethane) nanoparticles in a polyadditon reaction as well as poly(L-lactide) nanoparticles through ring-opening polymerization, catalyzed by a moisture-sensitive catalyst. The well-dispersed particles possess average diameters below 100 nm and have narrow size distributions owing to the long-term stability of the dispersed droplets in the continuous phase.

The fabrication of a thin film optoelectronic device involves the exposure of the transparent conductive oxide (TCO) to a high process temperature. Indium gallium zinc oxide (InGaZnO4 or IGZO) is a well known TCO with high optical transparency, moderate conductivity and high mobility. However, its electrical properties deteriorate after subsequent high temperature processes in air atmosphere. On the other hand indium tin oxide (ITO) has higher conductivity than IGZO and better thermal stability. Therefore, IGZO/ITO bilayers have been deposited on glass by radio frequency magnetron sputtering at room temperature and subsequently annealed at high temperatures in order to study their thermal stability. In the present work, a-IGZO layers with a thickness ranging from 10 nm to 100 nm were deposited over a 50 nm thick ITO layer. Results are compared with those from a single IGZO layered thin film without the ITO bottom layer. The structural, optical and electrical properties of the multilayers are studied with the use of scanning electron microscopy, UV–Vis spectroscopy and Hall measurement. An IGZO optimal thickness of 50 nm is found to improve the bilayer thermal stability at temperatures upto 400 °C keeping good opto-electrical properties. The sheet resistance for the optimized IGZO/ITO composite films is about 22 Ohm/sq, and the transmittance in the visible range is about 90%. The composite shows an excellent mobility above 40 cm2 /V-s and thus can be potentially applied as channel layer in thin film transistors (TFTs)

An Al 5083 alloy with a bimodal grain size has been previously synthesized using a low-temperature milling process and consolidation via cold isostatic pressing (CIP). This material has been shown to exhibit greatly improved strength when compared to conventional aluminum alloys. Additionally, this material has shown sensitivity to test conditions. In this work, we studied the effects of temperature on the strain rate sensitivity of this material by examining its elastic and plastic properties though uniaxial tension tests conducted under a variety of conditions at temperatures up to 473 K. Serrated stress-strain curves were observed, indicating dynamic strain aging. Strain rate sensitivity was found to depend non-monotonically on the test temperature.

A personal view of ferroelectrics and multiferroics research is given with suggestions for future work, emphasizing nano-dynamics.

The structural, electronic and magnetic properties of functional Ni-Mn-(Ga, In, Sn) and Pt-Ni-(Ga, Sn) alloys are studied by first-principles and Monte Carlo tools. The ab initio calculations give a basic understanding of the underlying physics which is associated with the complex magnetic behavior arising from the competition of ferro- and antiferromagnetic interactions for excess Mn atoms in the unit cell. We show that the resulting complex magnetic ordering is the driving mechanism of structural transformations and multifunctional properties of Heusler alloys associated with magnetic shape-memory, magnetocaloric and elastocaloric effects. The thermodynamic properties can be calculated by using the ab initio magnetic exchange parameters in finite-temperature Monte Carlo simulations. Entropy and specific heat changes associated with the magnetic changes and emergence of microstructure across the magnetostructural transition are pointed out. We show how to optimize the functional properties by tuning the compositional changes, for example, a magnetic shape-memory effect of more than 14% can be achieved in Pt-Ni-Mn-Ga alloys. The theoretical studies are accompanied by experimental investigations.

The modelling of of silicon gate-all-around nanowire transistors by non-equilibrium Green function methods requires the computation of self-energies for inelastic electron-phonon interactions. It is shown that many approximations designed to reduce numerical complexityto these self-energies in fact fail because they do not satisfy appropriate causality conditions. Four familiar approximations are discussed and their failures resolved. It is also shown that a condition for the spectral density sum rule to hold (and hence accurate density of states in energy) depends on a simple causality condition.

The lifetime performance and reliability of photovoltaic (PV) modules are critical factors in their successful deployment. Interfaces in thin film PV, such as that between the transparent conductive oxide (TCO) electrode and the absorber layer, are frequently an avenue for degradation; this degradation is promoted by exposure to environmental stressors such as irradiance, heat and humidity. Understanding and suppressing TCO degradation is critical to improving stability and extending the lifetime. Commercially available indium tin oxide (ITO), fluorine doped tin oxide (FTO) and aluminum doped zinc oxide (AZO) were exposed to damp heat (DH), ASTM G154 cycle 4, and modified ASTM G154 for up to 1000 hours. The TCOs’ electrical and optical properties and surface energies were determined before and after each exposure and their relative degradation classified. Data demonstrate that AZO degraded most rapidly of all the TCOs, whereas ITO and FTO degraded at lower to non-quantifiable rates. One approach to suppress degradation could be to use interfacial layers (IFLs), including organofunctional silane layers, to modify the TCO. We modified the TCO surfaces using a variety of organofunctional silanes, and determined a range of surface energies could be obtained without affecting the electrical and optical properties of the TCO. Degradation studies of TCOs with a silane layer were also conducted. We found that an inhomogeneous silane layer was able to delay the resistivity increase for ITO in DH.

The enhancement of the plasmonic signatures, indicated by the shifting of the localized surface plasmon resonances, of three-dimensional, hollow, gold nanocages with respect to substrate nature and cage density is reported. The effect of substrate nature was investigated using absorbance, reflection, and transmission by ultraviolet-visible and near-infrared spectrophotometry. The gold nanocages were deposited on substrates as monolayers primarily by Langmuir-Blodgett technique. The density of the deposited monolayers and the nature of the surface of the substrates were determined using AFM and SEM/TEM imaging. The position of the LSPR signatures, primarily the dipolar plasmonic resonances, with respect to changing environment and nanostructure characteristics determined the tuneability of the plasmonic enhancements.