'Enhancement of the crystallization process of TbxFe1-x thin films upon the formation of alpha-Tb phase'

TbxFe1−x thin films deposited by sputtering on Mo were investigated structurally and magnetically. The microstructure consists of TbFe2 nanoparticles embedded in an amorphous matrix, and the Tb content can be correlated with an increase in the volume of these nanoparticles. Similar microstructure and behavior were found when TbFe2 was deposited on glass and on a Pt buffer layer. Nevertheless, thermal treatments promote a different effect, depending on the mechanical stiffness of the buffer layer. The layers deposited on Mo, a rigid material, show crystalline TbFe2 together with α-Tb phase upon thermal treatment. In contrast, TbFe2 does not crystallize properly on Pt, a material with a lower stiffness than Mo. Intermediate results were observed on the film deposited on glass. Experimental results show the impact of the buffer stiffness on the crystallization process. Moreover, the formation of α-Tb appears to be fundamental to crystallized TbFe2 on layers deposited on rigid buffers

Experimental and numerical study of cw green laser crystallization of a-Si:H thin films

Crystallization and grain growth technique of thin film silicon are among the most promising methods for improving efficiency and lowering cost of solar cells. A major advantage of laser crystallization and annealing over conventional heating methods is its ability to limit rapid heating and cooling to thin surface layers. Laser energy is used to heat the amorphous silicon thin film, melting it and changing the microstructure to polycrystalline silicon (poly-Si) as it cools. Depending on the laser density, the vaporization temperature can be reached at the center of the irradiated area. In these cases ablation effects are expected and the annealing process becomes ineffective. The heating process in the a-Si thin film is governed by the general heat transfer equation. The two dimensional non-linear heat transfer equation with a moving heat source is solve numerically using the finite element method (FEM), particularly COMSOL Multiphysics. The numerical model help to establish the density and the process speed range needed to assure the melting and crystallization without damage or ablation of the silicon surface. The samples of a-Si obtained by physical vapour deposition were irradiated with a cw-green laser source (Millennia Prime from Newport-Spectra) that delivers up to 15 W of average power. The morphology of the irradiated area was characterized by confocal laser scanning microscopy (Leica DCM3D) and Scanning Electron Microscopy (SEM Hitachi 3000N). The structural properties were studied by micro-Raman spectroscopy (Renishaw, inVia Raman microscope).

Land cover dynamics and climate change implications on water resources in South Pacific Costa Rica

Water is fundamental to human life and the availability of freshwater is often a constraint on human welfare and economic development. Consequently, the potential effects of global changes on hydrology and water resources are considered among the most severe and vital ones. Water scarcity is one of the main problems in the rural communities of Central America, as a result of an important degradation of catchment areas and the over-exploitation of aquifers. The present Thesis is focused on two critical aspects of global changes over water resources: (1) the potential effects of climate change on water quantity and (2) the impacts of land cover and land use changes on the hydrological processes and water cycle. Costa Rica is among the few developing countries that have recently achieved a land use transition with a net increase in forest cover. Osa Region in South Pacific Costa Rica is an appealing study site to assess water supply management plans and to measure the effects of deforestation, forest transitions and climate change projections reported in the region. Rural Community Water Supply systems (ASADAS) in Osa are dealing with an increasing demand of freshwater due to the growing population and the change in the way of life in the rural livelihoods. Land cover mosaics which have resulted from the above mentioned processes are characterized by the abandonment of marginal farmland with the spread over these former grasslands of high return crops and the expansion of secondary forests due to reforestation initiatives. These land use changes have a significant impact on runoff generation in priority water-supply catchments in the humid tropics, as evidenced by the analysis of the Tinoco Experimental Catchment in the Southern Pacific area of Costa Rica. The monitoring system assesses the effects of the different land uses on the runoff responses and on the general water cycle of the basin. Runoff responses at plot scale are analyzed for secondary forests, oil palm plantations, forest plantations and grasslands. The Oil palm plantation plot presented the highest runoff coefficient (mean RC=32.6%), twice that measured under grasslands (mean RC=15.3%) and 20-fold greater than in secondary forest (mean RC=1.7%). A Thornthwaite-type water balance is proposed to assess the impact of land cover and climate change scenarios over water availability for rural communities in Osa Region. Climate change projections were obtained by the downscaling of BCM2, CNCM3 and ECHAM5 models. Precipitation and temperature were averaged and conveyed by the A1B, A2 and B1 IPCC climate scenario for 2030, 2060 and 2080. Precipitation simulations exhibit a positive increase during the dry season for the three scenarios and a decrease during the rainy season, with the highest magnitude (up to 25%) by the end of the 21st century under scenario B1. Monthly mean temperature simulations increase for the three scenarios throughout the year with a maximum increase during the dry season of 5% under A1B and A2 scenarios and 4% under B1 scenario. The Thornthwaite-type Water Balance model indicates important decreases of water surplus for the three climate scenarios during the rainy season, with a maximum decrease on May, which under A1B scenario drop up to 20%, under A2 up to 40% and under B1 scenario drop up to almost 60%. Land cover scenarios were created taking into account current land cover dynamics of the region. Land cover scenario 1 projects a deforestation situation, with forests decreasing up to 15% due to urbanization of the upper catchment areas; land cover scenario 2 projects a forest recovery situation where forested areas increase due to grassland abandonment on areas with more than 30% of slope. Deforestation scenario projects an annual water surplus decrease of 15% while the reforestation scenario projects a water surplus increase of almost 25%. This water balance analysis indicates that climate scenarios are equal contributors as land cover scenarios to future water resource estimations.

Study of a-Si crystallization dependence on power and irradiation time using a CW green laser

An advantage of laser crystallization over conventional heating methods is its ability to limit rapid heating and cooling to thin surface layers. Laser energy is used to heat the a-Si thin film to change the microstructure to poly-Si. Thin film samples of a-Si were irradiated with a CW-green laser source. Laser irradiated spots were produced by using different laser powers and irradiation times. These parameters are identified as key variables in the crystallization process. The power threshold for crystallization is reduced as the irradiation time is increased. When this threshold is reached the crystalline fraction increases lineally with power for each irradiation time. The experimental results are analysed with the aid of a numerical thermal model and the presence of two crystallization mechanisms are observed: one due to melting and the other due to solid phase transformation.

Anhydrite/aerogel composites for thermal insulation

High performance thermal insulating composite materials can be produced with mineral binders and hydrophobic aerogel particles through a hydrophilization process for the latter with surfactants. The present study is focused on the development of aerogel/calcium sulfate composites by the hydrophilization of hydrophobic silica aerogel particles through a polymer-based surfactant. Its effects on the microstructure and hydration degree are examined as well as their relation to the resulting mechanical and physical properties. Results show that composites with an around 60 % of aerogel by volume can achieve a thermal conductivity <30 mW/m × K. Interestingly, a surfactant addition of 0.1 % by wt% of the water in the mixtures provides better material properties compared to a surfactant wt% addition of 5 %. However, it has been found around 40 % entrained air, affecting the material properties by reducing the binder and aerogel volume fractions within the composites. Moreover, gypsum crystallization starts to be inhibited at aerogel volume fractions >35 %. Towards material optimization, a model for the calculation of thermal conductivity of composites and an equation for the compressive strength are proposed.

Bio-based polymer nanocomposites based on nylon 11 and WS2 inorganic nanotubes

Tungsten disulphide nanotubes (INT-WS2) have been successfully dispersed in a bio-based polyamide matrix (nylon 11) by conventional melt processing. The effect of INT-WS2 content on the morphology, thermal stability, crystallization behaviour and dynamic mechanical properties is investigated. The results indicate that these inorganic nanotubes can be efficiently incorporated into the bio-based polymer matrix without the need for modifiers or surfactants. Additionally, it is found that the non-isothermal crystallization behaviour of nylon 11/INT-WS2 depends on both the cooling rate and INT-WS2 concentration. In particular, crystallization kinetics results demonstrate that the nucleating activity of INTs plays a dominant role in accelerating the crystallization of nylon 11. This fact leads to the appearance of the more-disordered phase at higher temperature. More significantly, it was shown that these INT-WS2 nanocomposites can facilitate a good processability and cost efficiency, and will be of interest for many eco-friendly and medical applications.

Conceptual modelling to assess how the interplay of hydrological connectivity, catchment storage and tracer dynamics controls nonstationary water age estimates

Acknowledgements We would like to gratefully acknowledge the data provided by SEPA, Iain Malcolm. Mark Speed, Susan Waldron and many MSS staff helped with sample collection and lab analysis. We thank the European Research Council (project GA 335910 VEWA) for funding and are grateful for the constructive comments provided by three anonymous reviewers.

Crystallization and identification of an assembly defect of recombinant antenna complexes produced in transgenic tobacco plants

A chimeric Lhcb gene encoding light-harvesting chlorophyll a/b-binding protein (LHCII) was expressed in transgenic tobacco plants. To separate native from recombinant LHCII, the protein was extended by six histidines at its C terminus. Recombinant LHCII was isolated by detergent-mediated monomerization of pure trimers followed by affinity-chromatography on Ni2+-NTA-agarose (NTA is nitrilotriacetic acid). Elution with imidazole yielded recombinant monomers that formed trimers readily after dilution of the detergent without further in vitro manipulations. LHCII subunits showed the typical chlorophyll a/b ratio at all steps of purification indicating no significant loss of pigments. Transgenic tobacco overexpressed amounts of recombinant protein that corresponded to about 0.7% of total LHCII. This yield suggested that expression in planta might be an alternative to the expression of eukaryotic membrane proteins in yeast. Recombinant LHCII was able to form two-dimensional crystals after addition of digalactolipids, which diffracted electrons to 3.6-Å resolution. LHCII carrying a replacement of Arg-21 with Gln accumulated to only 0.004% of total thylakoid proteins. This mutant was monomeric in the photosynthetic membrane probably due to the deletion of the phosphatidylglycerol binding site and was degraded by the plastidic proteolytic system. Exchange of Asn-183 with Leu impaired LHCII biogenesis in a similar way presumably due to the lack of a chlorophyll a binding site.

αβ T cell receptor interactions with syngeneic and allogeneic ligands: Affinity measurements and crystallization

Cellular immunity is mediated by the interaction of an αβ T cell receptor (TCR) with a peptide presented within the context of a major histocompatibility complex (MHC) molecule. Alloreactive T cells have αβ TCRs that can recognize both self- and foreign peptide–MHC (pMHC) complexes, implying that the TCR has significant complementarity with different pMHC. To characterize the molecular basis for alloreactive TCR recognition of pMHC, we have produced a soluble, recombinant form of an alloreactive αβ T cell receptor in Drosophila melanogaster cells. This recombinant TCR, 2C, is expressed as a correctly paired αβ heterodimer, with the chains covalently connected via a disulfide bond in the C-terminal region. The native conformation of the 2C TCR was probed by surface plasmon resonance (SPR) analysis by using conformation-specific monoclonal antibodies, as well as syngeneic and allogeneic pMHC ligands. The 2C interaction with H-2Kb-dEV8, H-2Kbm3-dEV8, H-2Kb-SIYR, and H-2Ld-p2Ca spans a range of affinities from Kd = 10−4 to 10−6M for the syngeneic (H-2Kb) and allogeneic (H-2Kbm3, H-2Ld) ligands. In general, the syngeneic ligands bind with weaker affinities than the allogeneic ligands, consistent with current threshold models of thymic selection and T cell activation. Crystallization of the 2C TCR required proteolytic trimming of the C-terminal residues of the α and β chains. X-ray quality crystals of complexes of 2C with H-2Kb-dEV8, H-2Kbm3-dEV8 and H-2Kb-SIYR have been grown.

Crystal cataracts: Human genetic cataract caused by protein crystallization

Several human genetic cataracts have been linked recently to point mutations in the γD crystallin gene. Here we provide a molecular basis for lens opacity in two genetic cataracts and suggest that the opacity occurs because of the spontaneous crystallization of the mutant proteins. Such crystallization of endogenous proteins leading to pathology is an unusual event. Measurements of the solubility curves of crystals of the Arg-58 to His and Arg-36 to Ser mutants of γD crystallin show that the mutations dramatically lower the solubility of the protein. Furthermore, the crystal nucleation rate of the mutants is enhanced considerably relative to that of the wild-type protein. It should be noted that, although there is a marked difference in phase behavior, there is no significant difference in protein conformation among the three proteins.