Synergetic effects of the Cu/Pt{110} surface alloy: enhanced reactivity of water and carbon monoxide

We have used synchrotron-based high-resolution X-ray photoelectron spectroscopy in combination with ab initio density functional theory calculations to investigate the characteristics of water and CO adsorption on the bimetallic Cu/Pt{110}-(2 x 1) surface at a Cu coverage near 0.5 ML. Cu fills the troughs of the reconstructed clean surface forming nanowires, which are stable up to 830 K. Their presence dramatically influences the adsorption of water and CO. Water adsorption changes from intact to partially dissociated while the desorption temperature of CO on this surface increases by up to 27 K with respect to the clean Pt{110} surface. Ab initio calculations and experimental valence band spectra reveal that the Cu 3d-band is narrowed and shifted upward with respect to bulk Cu surfaces. This and electron donation to surface Pt atoms cause the increase in the bond strength between CO and the Pt surface atoms. The pathway for water dissociation occurs via Cu surface atoms. The heat of adsorption of water bonding to Cu surface atoms was calculated to be 0.82 eV, which is significantly higher than on the clean Pt{110} surface; the activation energy for partial dissociation is 0.53 eV (not corrected for zero point energy).

The builder's complete assistant, or, A library of arts and sciences, absolutely necessary to be understood by builders and workmen in general : viz. I. Arithmetick, vulgar and decimal, in whole numbers and fractions. II. Geometry, lineal, superficial, and solid. III. Architecture, universal. IV. Mensuration. V. Plain trigonometry. VI. Surveying of land, &c. VII. Mechanick powers. VIII. Hydrostaticks : illustrated by above thirteen hundred examples of lines, superficies, solids, mouldings, pedestals, columns, pilasters, entablatures, pediments, imposts, block cornices, rustick quoins, frontispieces, arcades, porticos, &c. : proportioned by modules and minutes, according to Andrea Palladio, and by equal parts : likewise great varieties of trussed roofs, timber bridges, centerings, arches, groins, twisted rails, compartments, obelisks, vases, pedestals for bustos, sun-dials, fonts, &c. and methods for raising heavy bodies by the force of levers, pulleys, axes in peritrochio, screws, and wedges, as also water, by the common pump, crane, etc. : wherein the properties, and pressure of the air on water, &c. are explained : the whole exemplified by 77 large quarto copper-plates /

All of the numbered plates in the atlas are double plates, and thus are counted twice in the adjusted plate count.

Bubble extinction in Hele-Shaw flow with surface tension and kinetic undercooling regularisation

We perform an analytic and numerical study of an inviscid contracting bubble in a two-dimensional Hele-Shaw cell, where the effects of both surface tension and kinetic undercooling on the moving bubble boundary are not neglected. In contrast to expanding bubbles, in which both boundary effects regularise the ill-posedness arising from the viscous (Saffman-Taylor) instability, we show that in contracting bubbles the two boundary effects are in competition, with surface tension stabilising the boundary, and kinetic undercooling destabilising it. This competition leads to interesting bifurcation behaviour in the asymptotic shape of the bubble in the limit it approaches extinction. In this limit, the boundary may tend to become either circular, or approach a line or "slit" of zero thickness, depending on the initial condition and the value of a nondimensional surface tension parameter. We show that over a critical range of surface tension values, both these asymptotic shapes are stable. In this regime there exists a third, unstable branch of limiting self-similar bubble shapes, with an asymptotic aspect ratio (dependent on the surface tension) between zero and one. We support our asymptotic analysis with a numerical scheme that utilises the applicability of complex variable theory to Hele-Shaw flow.

Tailoring surface properties and structure of layered double hydroxides using silanes with different number of functional groups

Four silanes, trimethylchlorosilane (TMCS), dimethyldiethoxylsilane (DMDES), 3-aminopropyltriethoxysilane (APTES) and tetraethoxysilane (TEOS), were adopted to graft layered double hydroxides (LDH) via an induced hydrolysis silylation method (IHS). Fourier transform infrared spectra (FTIR) and 29Si MAS nuclear magnetic resonance spectra (29Si MAS NMR) indicated that APTES and TEOS can be grafted onto LDH surfaces via condensation with hydroxyl groups of LDH, while TMCS and DMDES could only be adsorbed on the LDH surface with a small quantity. A combination of X-ray diffraction patterns (XRD) and 29Si MAS NMR spectra showed that silanes were exclusively present in the external surface and had little influence on the long range order of LDH. The surfactant intercalation experiment indicated that the adsorbed and/or grafted silane could not fix the interlamellar spacing of the LDH. However, they will form crosslink between the particles and affect the further surfactant intercalation in the silylated samples. The replacement of water by ethanol in the tactoids and/or aggregations and the polysiloxane oligomers formed during silylation procedure can dramatically increase the value of BET surface area (SBET) and total pore volumes (Vp) of the products.

The influence of chemical additives on surface charge and hardness of hematite

The zeta potential of high-purity hematite at pH 6 and in a 10−3N NaCl solution has been determined at different concentrations of acetone using the streaming potential technique and the results correlated with the microhardness of the mineral. The zeta potential has been found to decrease as the hardness increases reaching a minimum at 10 cc per litre concentration of acetone when the hardness reaches a maximum. The results have been explained on the basis of competitive adsorption of chloride ions and acetone molecules at low concentrations of acetone and coadsorption of both species above 10 cc per litre concentration. Acetone in distilled water and 10−3N NaCl in distilled water decrease the microhardness of hematite individually between pH 5 to 7 and in combination increase the microhardness reaching a maximum at pH 6.

The Rise and Fall of Water Net (Hydrodictyon reticulatum) in New Zealand

During the late 1980s to early 1990s a range of aquatic habitats in the central North Island of New Zealand were invaded by the filamentous green alga, water net Hydrodictyon reticulatum (Linn. Lagerheim). The alga caused significant economic and recreational impacts at major sites of infestation, but it was also associated with enhanced invertebrate numbers and was the likely cause of an improvement in the trout fishery. The causes of prolific growth of water net and the range of control options pursued are reviewed. The possible causes of its sudden decline in 1995 are considered, including physical factors, increase in grazer pressure, disease, and loss of genetic vigour.

Solubility and Diffusivity of Water in Lunar Basalt, and Chemical Zonation in Olivine-Hosted Melt Inclusions

I report the solubility and diffusivity of water in lunar basalt and an iron-free basaltic analogue at 1 atm and 1350 °C. Such parameters are critical for understanding the degassing histories of lunar pyroclastic glasses. Solubility experiments have been conducted over a range of fO₂ conditions from three log units below to five log units above the iron-wüstite buffer (IW) and over a range of pH₂/pH₂O from 0.03 to 24. Quenched experimental glasses were analyzed by Fourier transform infrared spectroscopy (FTIR) and secondary ionization mass spectrometry (SIMS) and were found to contain up to ~420 ppm water. Results demonstrate that, under the conditions of our experiments: (1) hydroxyl is the only H-bearing species detected by FTIR; (2) the solubility of water is proportional to the square root of pH₂O in the furnace atmosphere and is independent of fO₂ and pH₂/pH₂O; (3) the solubility of water is very similar in both melt compositions; (4) the concentration of H₂ in our iron-free experiments is <3 ppm, even at oxygen fugacities as low as IW-2.3 and pH₂/pH₂O as high as 24; and (5) SIMS analyses of water in iron-rich glasses equilibrated under variable fO₂ conditions can be strongly influenced by matrix effects, even when the concentrations of water in the glasses are low. Our results can be used to constrain the entrapment pressure of the lunar melt inclusions of Hauri et al. (2011).

Diffusion experiments were conducted over a range of fO₂ conditions from IW-2.2 to IW+6.7 and over a range of pH₂/pH₂O from nominally zero to ~10. The water concentrations measured in our quenched experimental glasses by SIMS and FTIR vary from a few ppm to ~430 ppm. Water concentration gradients are well described by models in which the diffusivity of water (D^*_water) is assumed to be constant. The relationship between D^*_water and water concentration is well described by a modified speciation model (Ni et al. 2012) in which both molecular water and hydroxyl are allowed to diffuse. The success of this modified speciation model for describing our results suggests that we have resolved the diffusivity of hydroxyl in basaltic melt for the first time. Best-fit values of D^*_water for our experiments on lunar basalt vary within a factor of ~2 over a range of pH₂/pH₂O from 0.007 to 9.7, a range of fO₂ from IW-2.2 to IW+4.9, and a water concentration range from ~80 ppm to ~280 ppm. The relative insensitivity of our best-fit values of D^*_water to variations in pH₂ suggests that H₂ diffusion was not significant during degassing of the lunar glasses of Saal et al. (2008). D^*_water during dehydration and hydration in H₂/CO₂ gas mixtures are approximately the same, which supports an equilibrium boundary condition for these experiments. However, dehydration experiments into CO₂ and CO/CO₂ gas mixtures leave some scope for the importance of kinetics during dehydration into H-free environments. The value of D^*_water chosen by Saal et al. (2008) for modeling the diffusive degassing of the lunar volcanic glasses is within a factor of three of our measured value in our lunar basaltic melt at 1350 °C.

In Chapter 4 of this thesis, I document significant zonation in major, minor, trace, and volatile elements in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (MgO, FeO, Cr₂O₃, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H₂O, and F, components with a lower concentration in the host olivine than in the melt (Al₂O₃, SiO₂, Na₂O, K₂O, TiO₂, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions concurrent with diffusive propagation of the boundary layer toward the inclusion center.

Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na₂O, K₂O) by coupling to slow diffusing components such as SiO₂ and Al₂O₃. Concentrations of H2O and F decrease towards the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects.

A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150–13,000 °C hr^-1 from the liquidus down to ~1000 °C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1000 °C is 40 s to just over one hour.

Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization.

All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.

Removal of surface states and recovery of band-edge emission in InAs nanowires through surface passivation.

Surface states in semiconductor nanowires (NWs) are detrimental to the NW optical and electronic properties and to their light emission-based applications, due to the large surface-to-volume ratio of NWs and the congregation of defects states near surfaces. In this paper, we demonstrated an effective approach to eliminate surface states in InAs NWs of zinc-blende (ZB) and wurtzite (WZ) structures and a dramatic recovery of band edge emission through surface passivation with organic sulfide octadecylthiol (ODT). Microphotoluminescence (PL) measurements were carried out before and after passivation to study the dominant recombination mechanisms and surface state densities of the NWs. For WZ-NWs, we show that the passivation removed the surface states and recovered the band-edge emission, leading to a factor of ∼19 reduction of PL linewidth. For ZB-NWs, the deep surface states were removed and the PL peaks width became as narrow as ∼250 nm with some remaining emission of near band-edge surface states. The passivated NWs showed excellent stability in atmosphere, water, and heat environments. In particular, no observable changes occurred in the PL features from the passivated NWs exposed in air for more than five months.

Monitoring and simulation of water, heat,and CO2 fluxes in terrestrial ecosystems based on the APEIS-FLUX system

The Integrated Environmental Monitoring (IEM) project, part of the Asia-Pacific Environmental Innovation Strategy (APEIS) project, developed an integrated environmental monitoring system that can be used to detect, monitor, and assess environmental disasters, degradation, and their impacts in the Asia-Pacific region. The system primarily employs data from the moderate resolution imaging spectrometer (MODIS) sensor on the Earth Observation System- (EOS-) Terra/Aqua satellite,as well as those from ground observations at five sites in different ecological systems in China. From the preliminary data analysis on both annual and daily variations of water, heat and CO2 fluxes, we can confirm that this system basically has been working well. The results show that both latent flux and CO2 flux are much greater in the crop field than those in the grassland and the saline desert, whereas the sensible heat flux shows the opposite trend. Different data products from MODIS have very different correspondence, e.g. MODIS-derived land surface temperature has a close correlation with measured ones, but LAI and NPP are quite different from ground measurements, which suggests that the algorithms used to process MODIS data need to be revised by using the local dataset. We are now using the APEIS-FLUX data to develop an integrated model, which can simulate the regional water,heat, and carbon fluxes. Finally, we are expected to use this model to develop more precise high-order MODIS products in Asia-Pacific region.

Chemical composition and reactivity of water on clean and oxygen-covered Pd{111}

The chemical composition and dissociation behaviour of water adsorbed on clean and oxygen pre-covered Pd{111} was studied using high-resolution time-resolved and temperature-programmed X-ray photoelectron spectroscopy. We find that water remains intact at all temperatures up to desorption on the clean surface and at high oxygen coverage(0.69 ML) when a surface oxide is formed. The highest desorption peaks occur at 163 K from the clean surface and at 172 K from the surface oxide. At the intermediate coverage of 0.20 ML oxygen reacts with coadsorbed water at 155 K, to generate a mixed H2O/OH layer exhibiting a (root 3- x root 3)R30 degrees diffraction pattern, which is stable up to 177 K. The measured ratio between intact water and the hydroxyl species in this layer varies between 1.5 and 2 depending on temperature. (C) 2008 Elsevier B.V. All rights reserved.

Downwelling solar irradiance in the biomass burning region of the southern Amazon: Dependence on aerosol intensive optical properties and role of water vapor

The sensitivity of solar irradiance at the surface to the variability of aerosol intensive optical properties is investigated for a site (Alta Floresta) in the southern portion of the Amazon basin using detailed comparisons between measured and modeled irradiances. Apart from aerosol intensive optical properties, specifically single scattering albedo (omega(o lambda)) and asymmetry parameter (g(lambda)), which were assumed constant, all other relevant input to the model were prescribed based on observation. For clean conditions, the differences between observed and modeled irradiances were consistent with instrumental uncertainty. For polluted conditions, the agreement was significantly worse, with a root mean square difference three times larger (23.5 Wm(-2)). Analysis revealed a noteworthy correlation between the irradiance differences (observed minus modeled) and the column water vapor (CWV) for polluted conditions. Positive differences occurred mostly in wet conditions, while the differences became more negative as the atmosphere dried. To explore the hypothesis that the irradiance differences might be linked to the modulation of omega(o lambda) and g(lambda) by humidity, AERONET retrievals of aerosol properties and CWV over the same site were analyzed. The results highlight the potential role of humidity in modifying omega(o lambda) and g(lambda) and suggest that to explain the relationship seen between irradiances differences via aerosols properties the focus has to be on humidity-dependent processes that affect particles chemical composition. Undoubtedly, there is a need to better understand the role of humidity in modifying the properties of smoke aerosols in the southern portion of the Amazon basin.

In Vitro Evaluation of Surface Roughness and Microhardness of Restorative Materials Submitted to Erosive Challenges

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

Influence of air-particle deposition protocols on the surface topography and adhesion of resin cement to zirconia

Objectives: This study evaluated the influence of air-particle abrasion protocols on the surface roughness (SR) of zirconia and the shear bond strength (SBS) of dual-polymerized resin cement to this ceramic. Materials and methods. Sintered zirconia blocks (n = 115) (Lava, 3M ESPE) were embedded in acrylic resin and polished. The specimens were divided according to the 'particle type' (Al: 110 mu m Al2O3; Si: 110 mu m SiO2) and 'pressure' factors (2.5 or 3.5 bar) (n = 3 per group): (a) Control (no air-abrasion); (b) Al2.5; (c) Si2.5; (d) Al3.5; (e) Si3.5. SR (Ra) was measured 3-times from each specimen after 20 s of air-abrasion (distance: 10 mm) using a digital optical profilometer. Surface topography was evaluated under SEM analyses. For the SBS test, 'particle type', 'pressure' and 'thermocycling' (TC) factors were considered (n = 10; n = 10 per group): Control (no air-abrasion); Al2.5; Si2.5; Al3.5; Si3.5; Control(TC); Al2.5(TC); Si2.5(TC); Al3.5(TC); Si3.5(TC). After silane application, resin cement (Panavia F2.0) was bonded and polymerized. Specimens were thermocycled (6.000 cycles, 5-55 degrees C) and subjected to SBS (1 mm/min). Data were analyzed using ANOVA, Tukey's and Dunnett tests (5%). Results. 'Particle' (p = 0.0001) and 'pressure' (p = 0.0001) factors significantly affected the SR. All protocols significantly increased the SR (Al2.5: 0.45 +/- 0.02; Si2.5: 0.39 +/- 0.01; Al3.5: 0.80 +/- 0.01; Si3.5: 0.64 +/- 0.01 mu m) compared to the control group (0.16 +/- 0.01 mu m). For SBS, only 'particle' factor significantly affected the results (p = 0.015). The SiO2 groups presented significantly higher SBS results than Al2O3 (Al2.5: 4.78 +/- 1.86; Si2.5: 7.17 +/- 2.62; Al3.5: 4.97 +/- 3.74; Si3.5: 9.14 +/- 4.09 MPa) and the control group (3.67 +/- 3.0 MPa). All TC specimens presented spontaneous debondings. SEM analysis showed that Al2O3 created damage in zirconia in the form of grooves, different from those observed with SiO2 groups. Conclusions. Air-abrasion with 110 mu m Al2O3 resulted in higher roughness, but air-abrasion protocols with SiO2 promoted better adhesion.