Fluorination of Boron-Doped Diamond Film Electrodes for Minimization of Perchlorate Formation.

PubMed

Gayen, Pralay; Chaplin, Brian P

2017-08-23

This research investigated the effects of surface fluorination on both rates of organic compound oxidation (phenol and terephthalic acid (TA)) and ClO 4 - formation at boron-doped diamond (BDD) film anodes at 22 °C. Different fluorination methods (i.e., electrochemical oxidation with perfluorooctanoic acid (PFOA), radio frequency plasma, and silanization) were used to incorporate fluorinated moieties on the BDD surface, which was confirmed by X-ray photoelectron spectroscopy (XPS). The silanization method was found to be the most effective fluorination method using a 1H,1H,2H,2H-perfluorodecyltrichlorosilane precursor to form a self-assembled monolayer (SAM) on the oxygenated BDD surface. The ClO 4 - formation decreased from rates of 0.45 ± 0.03 mmol m -2 min -1 during 1 mM NaClO 3 oxidation and 0.28 ± 0.01 mmol m -2 min -1 during 10 mM NaCl oxidation on the BDD electrode to below detectable levels (<0.12 μmoles m -2 min -1 ) for the BDD electrode functionalized by a 1H,1H,2H,2H-perfluorodecyltrichlorosilane SAM. These decreases in rates corresponded to 99.94 and 99.85% decreases in selectivity for ClO 4 - formation during the electrolysis of 10 mM NaCl and 1 mM NaClO 3 electrolytes, respectively. By contrast, the oxidation rates of phenol were reduced by only 16.3% in the NaCl electrolyte and 61% in a nonreactive 0.1 M KH 2 PO 4 electrolyte. Cyclic voltammetry with Fe(CN) 6 3-/4- and Fe 3+/2+ redox couples indicated that the long fluorinated chains created a blocking layer on the BDD surface that inhibited charge transfer via steric hindrance and hydrophobic effects. The surface coverages and thicknesses of the fluorinated films controlled the charge transfer rates, which was confirmed by estimates of film thicknesses using XPS and density functional theory simulations. The aliphatic silanized electrode also showed very high stability during OH • production. Perchlorate formation rates were below the detection limit (<0.12 μmoles m -2 min -1 ) for up to 10 consecutive NaClO 3 oxidation experiments.

Monte Carlo simulation to investigate the formation of molecular hydrogen and its deuterated forms

NASA Astrophysics Data System (ADS)

Sahu, Dipen; Das, Ankan; Majumdar, Liton; Chakrabarti, Sandip K.

2015-07-01

H2 is the most abundant interstellar species, and its deuterated forms (HD and D2) are also present in high abundance. The high abundance of these molecules could be explained by considering the chemistry that occurs on interstellar dust. Because of its simplicity, the rate equation method is widely used to study the formation of grain-surface species. However, because the recombination efficiency for the formation of any surface species is highly dependent on various physical and chemical parameters, the Monte Carlo method is best suited for addressing the randomness of the processes. We perform Monte Carlo simulations to study the formation of H2, HD and D2 on interstellar ice. The adsorption energies of surface species are the key inputs for the formation of any species on interstellar dusts, but the binding energies of deuterated species have yet to be determined with certainty. A zero-point energy correction exists between hydrogenated and deuterated species, which should be considered during modeling of the chemistry on interstellar dusts. Following some previous studies, we consider various sets of adsorption energies to investigate the formation of these species under diverse physical conditions. As expected, notable differences in these two approaches (rate equation method and Monte Carlo method) are observed for the production of these simple molecules on interstellar ice. We introduce two factors, namely, Sf and β , to explain these discrepancies: Sf is a scaling factor, which can be used to correlate the discrepancies between the rate equation and Monte Carlo methods, and β indicates the formation efficiency under various conditions. Higher values of β indicate a lower production efficiency. We observed that β increases with a decrease in the rate of accretion from the gas phase to the grain phase.

Determining the folding and unfolding rate constants of nucleic acids by biosensor. Application to telomere G-quadruplex.

PubMed

Zhao, Yong; Kan, Zhong-yuan; Zeng, Zhi-xiong; Hao, Yu-hua; Chen, Hua; Tan, Zheng

2004-10-20

Nucleic acid molecules may fold into secondary structures, and the formation of such structures is involved in many biological processes and technical applications. The folding and unfolding rate constants define the kinetics of conformation interconversion and the stability of these structures and is important in realizing their functions. We developed a method to determine these kinetic parameters using an optical biosensor based on surface plasmon resonance. The folding and unfolding of a nucleic acid is coupled with a hybridization reaction by immobilization of the target nucleic acid on a sensor chip surface and injection of a complementary probe nucleic acid over the sensor chip surface. By monitoring the time course of duplex formation, both the folding and unfolding rate constants for the target nucleic acid and the association and dissociation rate constants for the target-probe duplex can all be derived from the same measurement. We applied this method to determine the folding and unfolding rate constants of the G-quadruplex of human telomere sequence (TTAGGG)(4) and its association and dissociation rate constants with the complementary strand (CCCTAA)(4). The results show that both the folding and unfolding occur on the time scale of minutes at physiological concentration of K(+). We speculate that this property might be important for telomere elongation. A complete set of the kinetic parameters for both of the structures allows us to study the competition between the formation of the quadruplex and the duplex. Calculations indicate that the formation of both the quadruplex and the duplex is strand concentration-dependent, and the quadruplex can be efficiently formed at low strand concentration. This property may provide the basis for the formation of the quadruplex in vivo in the presence of a complementary strand.

Altered bone turnover during spaceflight

NASA Technical Reports Server (NTRS)

Turner, R. T.; Morey, E. R.; Liu, C.; Baylink, D. J.

1982-01-01

Modifications in calcium metabolism during spaceflight were studied, using parameters that reflect bone turnover. Bone formation rate, medullary area, bone length, bone density, pore size distribution, and differential bone cell number were evaluated in growing rate both immediately after and 25 days after orbital spaceflights aboard the Soviet biological satellites Cosmos 782 and 936. The primary effect of space flight on bone turnover was a reversible inhibition of bone formation at the periosteal surface. A simultaneous increase in the length of the periosteal arrest line suggests that bone formation ceased along corresponding portions of that surface. Possible reasons include increased secretion of glucocorticoids and mechanical unloading of the skeleton due to near-weightlessness, while starvation and immobilization are excluded as causes.

A GAS-PHASE FORMATION ROUTE TO INTERSTELLAR TRANS-METHYL FORMATE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cole, Callie A.; Wehres, Nadine; Yang Zhibo

2012-07-20

The abundance of methyl formate in the interstellar medium has previously been underpredicted by chemical models. Additionally, grain surface chemistry cannot account for the relative abundance of the cis- and trans-conformers of methyl formate, and the trans-conformer is not even formed at detectable abundance on these surfaces. This highlights the importance of studying formation pathways to methyl formate in the gas phase. The rate constant and branching fractions are reported for the gas-phase reaction between protonated methanol and formic acid to form protonated trans-methyl formate and water as well as adduct ion: Rate constants were experimentally determined using a flowingmore » afterglow-selected ion flow tube apparatus at 300 K and a pressure of 530 mTorr helium. The results indicate a moderate overall rate constant of (3.19 {+-} 0.39) Multiplication-Sign 10{sup -10} cm{sup 3} s{sup -1} ({+-} 1{sigma}) and an average branching fraction of 0.05 {+-} 0.04 for protonated trans-methyl formate and 0.95 {+-} 0.04 for the adduct ion. These experimental results are reinforced by ab initio calculations at the MP2(full)/aug-cc-pVTZ level of theory to examine the reaction coordinate and complement previous density functional theory calculations. This study underscores the need for continued observational studies of trans-methyl formate and for the exploration of other gas-phase formation routes to complex organic molecules.« less

[The effects of surface morphology of calcium phosphate ceramics on apatite formation in dynamic SBF].

PubMed

Duan, Yourong; Lü, Wanxin; Wang, Chaoyuan; Chen, Jiyong; Zhang, Xingdong

2002-06-01

Bone-like apatite formation on the surface of calcium phosphate ceramics has been believed to be the prerequisite of new bone growth on ceramics and to be related to the osteoinductivity of the material. The research of the factors effecting bone-like apatite formation is a great help in understanding the mechanism of osteoinduction. This paper is aimed to a comparative study of in vitro formation of bone-like apatite on the surface of dense and rough calcium phosphate ceramics with SBF flowing at different rates. The results showed that the rough surface was beneficial to the formation of bone-like apatite, and the apatite formed faster in 1.5 SBF than in SBF. Rough surface, namely, larger surface area, increased the dissolution of Ca2+ and HPO4(2-) and higher concentration of Ca2+ and HPO4(2-) ions of SBF and was in turn advantageous to the accumulation of Ca2+, HPO4(2-), PO4(3-) near the ceramic surface. Local supersaturating concentration of Ca2+, HPO4(2-), PO4(3-) near sample surface was essential to nucleation of apatite on the surface of sample.

Mechanism of Benzene Tribopolymerization on the RuO2 (110) Surface

NASA Astrophysics Data System (ADS)

Yang, J.; Qi, Y.; Kim, H. D.; Rappe, A. M.

2018-04-01

A tribopolymer formed on the contacts of microelectromechanical and nanoelectromechanical system (MEMS-NEMS) devices is a major concern hampering their practical use in information technology. Conductive metal oxides, such as RuO2 and ReO3 , have been regarded as promising candidate materials for MEMS-NEMS contacts due to their conductivity, hardness, and relatively chemically inert surfaces. However, recent experimental works demonstrate that trace amounts of a polymer could still form on RuO2 surfaces. We demonstrate the mechanism of this class of unexpected tribopolymer formation by conducting density-functional-theory-based computational compression experiments with benzene as the contamination gas. First, mechanical force during compression changes the benzene molecules from slightly physisorbed to strongly chemisorbed. Further compression causes deformation and chemical linkage of the benzene molecules. Finally, the two contacts detach, with one having a complex organic molecule attached and the other a more reactive surface. The complex organic molecule, which has an oxabicyclic segment, can be viewed as the rudiment of a tribopolymer, and the more reactive surface can trigger the next adsorption-reaction-tribopolymer formation cycle. Based on these results, we also predict tribopolymer formation rates by using transition-state theory and the second-order rate law. We promote a deeper understanding of tribopolymer formation (especially on metal oxides) and provide strategies for suppressing tribopolymerization.

Morphogenesis at the inflorescence shoot apex of Anagallis arvensis: surface geometry and growth in comparison with the vegetative shoot.

PubMed

Kwiatkowska, Dorota; Routier-Kierzkowska, Anne-Lise

2009-01-01

Quantitative analysis of geometry and surface growth based on the sequential replica method is used to compare morphogenesis at the shoot apex of Anagallis arvensis in the reproductive and vegetative phases of development. Formation of three types of lateral organs takes place at the Anagallis shoot apical meristem (SAM): vegetative leaf primordia are formed during the vegetative phase and leaf-like bracts and flower primordia during the reproductive phase. Although the shapes of all the three types of primordia are very similar during their early developmental stages, areal growth rates and anisotropy of apex surface growth accompanying formation of leaf or bract primordia are profoundly different from those during formation of flower primordia. This provides an example of different modes of de novo formation of a given shape. Moreover, growth accompanying the formation of the boundary between the SAM and flower primordium is entirely different from growth at the adaxial leaf or bract primordium boundary. In the latter, areal growth rates at the future boundary are the lowest of all the apex surface, while in the former they are relatively very high. The direction of maximal growth rate is latitudinal (along the future boundary) in the case of leaf or bract primordium but meridional (across the boundary) in the case of flower. The replica method does not enable direct analysis of growth in the direction perpendicular to the apex surface (anticlinal direction). Nevertheless, the reconstructed surfaces of consecutive replicas taken from an individual apex allow general directions of SAM surface bulging accompanying primordium formation to be recognized. Precise alignment of consecutive reconstructions shows that the direction of initial bulging during the leaf or bract formation is nearly parallel to the shoot axis (upward bulging), while in the case of flower it is perpendicular to the axis (lateral bulging). In future, such 3D reconstructions can be used to assess displacement velocity fields so that growth in the anticlinal direction can be assessed. In terms of self-perpetuation, the inflorescence SAM of Anagallis differs from the SAM in the vegetative phase in that the centrally located region of slow growth is less distinct in the inflorescence SAM. Moreover, the position of this slowly growing zone with respect to cells is not stable in the course of the meristem ontogeny.

Kinetics of Surface-Mediated Fibrillization of Amyloid-β (12-28) Peptides.

PubMed

Lin, Yi-Chih; Li, Chen; Fakhraai, Zahra

2018-04-17

Surfaces or interfaces are considered to be key factors in facilitating the formation of amyloid fibrils under physiological conditions. In this report, we study the kinetics of the surface-mediated fibrillization (SMF) of an amyloid-β fragment (Aβ 12-28 ) on mica. We employ a spin-coating-based drying procedure to control the exposure time of the substrate to a low-concentration peptide solution and then monitor the fibril growth as a function of time via atomic force microscopy (AFM). The evolution of surface-mediated fibril growth is quantitatively characterized in terms of the length histogram of imaged fibrils and their surface concentration. A two-dimensional (2D) kinetic model is proposed to numerically simulate the length evolution of surface-mediated fibrils by assuming a diffusion-limited aggregation (DLA) process along with size-dependent rate constants. We find that both monomer and fibril diffusion on the surface are required to obtain length histograms as a function of time that resemble those observed in experiments. The best-fit simulated data can accurately describe the key features of experimental length histograms and suggests that the mobility of loosely bound amyloid species is crucial in regulating the kinetics of SMF. We determine that the mobility exponent for the size dependence of the DLA rate constants is α = 0.55 ± 0.05, which suggests that the diffusion of loosely bound surface fibrils roughly depends on the inverse of the square root of their size. These studies elucidate the influence of deposition rate and surface diffusion on the formation of amyloid fibrils through SMF. The method used here can be broadly adopted to study the diffusion and aggregation of peptides or proteins on various surfaces to investigate the role of chemical interactions in two-dimensional fibril formation and diffusion.

Surface Mediated Self-Assembly of Amyloid Peptides

NASA Astrophysics Data System (ADS)

Fakhraai, Zahra

2015-03-01

Amyloid fibrils have been considered as causative agents in many neurodegenerative diseases, including Alzheimer's disease, Parkinson's disease, type II diabetes and amyloidosis. Amyloid fibrils form when proteins or peptides misfold into one dimensional crystals of stacked beta-sheets. In solution, amyloid fibrils form through a nucleation and growth mechanism. The rate limiting nucleation step requires a critical concentration much larger than those measured in physiological conditions. As such the exact origins of the seeds or oligomers that result in the formation of fully mature fibrils in the body remain topic intense studies. It has been suggested that surfaces and interfaces can enhance the fibrillization rate. However, studies of the mechanism and kinetics of the surface-mediated fibrillization are technologically challenging due to the small size of the oligomer and protofibril species. Using smart sample preparation technique to dry the samples after various incubation times we are able to study the kinetics of fibril formation both in solution and in the vicinity of various surfaces using high-resolution atomic force microscopy. These studies elucidate the role of surfaces in catalyzing amyloid peptide formation through a nucleation-free process. The nucleation free self-assembly is rapid and requires much smaller concentrations of peptides or proteins. We show that this process resembles diffusion limited aggregation and is governed by the peptide adhesion rate, two -dimensional diffusion of the peptides on the surface, and preferential interactions between the peptides. These studies suggest an alternative pathway for amyloid formation may exist, which could lead to new criteria for disease prevention and alternative therapies. Research was partially supported by a seed grant from the National Institute of Aging of the National Institutes of Health (NIH) under Award Number P30AG010124 (PI: John Trojanowski) and the University of Pennsylvania.

Evaluation of the amount of nanoparticles emitted in welding fume from stainless steel using different shielding gases.

PubMed

Pacheco, R P; Gomes, J F; Miranda, R M; Quintino, M L

2017-05-01

The primary objective of this study was to correlate the emission of macro and nanoparticles released during the process of metal inert gas/metal active gas (MIG/MAG) of stainless steel with different gas mixtures. Using different gas mixtures with different heat inputs, it was possible to determine fume formation rates and surface areas of nanoparticles with alveolar lung deposition capacity. It was found, how the various transfer modes and the type of gas protection, in particular, the percentage of active elements in the chemical composition of the gas, affect the amount of fumes generated and also the generation of nanoparticles with a high capacity of deposition. The spray transfer mode always shows higher values of nanoparticles surface area, unlike the fume formation rates. Among the tested mixtures 82%Ar + 18%CO 2 generates higher emissions of nanoparticles as well as fume formation rates.

In situ monitoring of laser-induced periodic surface structures formation on polymer films by grazing incidence small-angle X-ray scattering.

PubMed

Rebollar, Esther; Rueda, Daniel R; Martín-Fabiani, Ignacio; Rodríguez-Rodríguez, Álvaro; García-Gutiérrez, Mari-Cruz; Portale, Giuseppe; Castillejo, Marta; Ezquerra, Tiberio A

2015-04-07

The formation of laser-induced periodic surface structures (LIPSS) on model spin-coated polymer films has been followed in situ by grazing incidence small-angle X-ray scattering (GISAXS) using synchrotron radiation. The samples were irradiated at different repetition rates ranging from 1 up to 10 Hz by using the fourth harmonic of a Nd:YAG laser (266 nm) with pulses of 8 ns. Simultaneously, GISAXS patterns were acquired during laser irradiation. The variation of both the GISAXS signal with the number of pulses and the LIPSS period with laser irradiation time is revealing key kinetic aspects of the nanostructure formation process. By considering LIPSS as one-dimensional paracrystalline lattice and using a correlation found between the paracrystalline disorder parameter, g, and the number of reflections observed in the GISAXS patterns, the variation of the structural order of LIPSS can be assessed. The role of the laser repetition rate in the nanostructure formation has been clarified. For high pulse repetition rates (i.e., 10 Hz), LIPSS evolve in time to reach the expected period matching the wavelength of the irradiating laser. For lower pulse repetition rates LIPSS formation is less effective, and the period of the ripples never reaches the wavelength value. Results support and provide information on the existence of a feedback mechanism for LIPSS formation in polymer films.

Optical and thermal properties in ultrafast laser surface nanostructuring on biodegradable polymer

NASA Astrophysics Data System (ADS)

Yada, Shuhei; Terakawa, Mitsuhiro

2015-03-01

We investigate the effect of optical and thermal properties in laser-induced periodic surface structures (LIPSS) formation on a poly-L-lactic acid (PLLA), a biodegradable polymer. Surface properties of biomaterials are known to be one of the key factors in tissue engineering. Methods to process biomaterial surfaces have been studied widely to enhance cell adhesive and anisotropic properties. LIPSS formation has advantages in a dry processing which is able to process complex-shaped surfaces without using a toxic chemical component. LIPSS, however, was difficult to be formed on PLLA due to its thermal and optical properties compared to other polymers. To obtain new perspectives in effect of these properties above, LIPSS formation dependences on wavelength, pulse duration and repetition rate have been studied. At 800 nm of incident wavelength, high-spatial frequency LIPSS (HSFL) was formed after applying 10000 femtosecond pulses at 1.0 J/cm2 in laser fluence. At 400 nm of the wavelength, HSFL was formed at fluences higher than 0.20 J/cm2 with more than 3000 pulses. Since LIPSS was less formed with lower repetition rate, certain heat accumulation may be required for LIPSS formation. With the pulse duration of 2.0 ps, higher laser fluence as well as number of pulses compared to the case of 120 fs was necessary. This indicates that multiphoton absorption process is essential for LIPSS formation. Study on biodegradation modification was also performed.

Recombination of H atoms on the dust in fusion plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bakhtiyari-Ramezani, M., E-mail: mahdiyeh.bakhtiyari@gmail.com; Alinejad, N., E-mail: nalinezhad@aeoi.org.ir; Mahmoodi, J., E-mail: mahmoodi@qom.ac.ir

2015-07-15

We survey a model for theoretical study of the interaction of hydrogen and dust surface and apply our results for dusty plasmas to fusion devices. In this model, considering the mobility of ad-atoms from one physisorbed, or chemisorbed site, to other one by thermal diffusion, we describe the formation of H{sub 2} on grain surfaces. Finally, we calculate the formation rate on the high temperature dust surfaces for a range of temperature and density in typical conditions of divertor of tokamak.

Composition, morphology and surface recombination rate of HCl-isopropanol treated and vacuum annealed InAs(1 1 1)A surfaces

NASA Astrophysics Data System (ADS)

Kesler, V. G.; Seleznev, V. A.; Kovchavtsev, A. P.; Guzev, A. A.

2010-05-01

X-ray photoelectron spectroscopy and atomic force microscopy were used to examine the chemical composition and surface morphology of InAs(1 1 1)A surface chemically etched in isopropanol-hydrochloric acid solution (HCl-iPA) and subsequently annealed in vacuum in the temperature range 200-500 °C. Etching for 2-30 min resulted in the formation of "pits" and "hillocks" on the sample surface, respectively 1-2 nm deep and high, with lateral dimensions 50-100 nm. The observed local formations, whose density was up to 3 × 10 8 cm -2, entirely vanished from the surface after the samples were vacuum-annealed at temperatures above 300 °C. Using a direct method, electron beam microanalysis, we have determined that the defects of the hillock type includes oxygen and excessive As, while the "pits" proved to be identical in their chemical composition to InAs. Vacuum anneals were found to cause a decrease in As surface concentration relative to In on InAs surface, with a concomitant rise of surface recombination rate.

What FIREs Up Star Formation: the Emergence of the Kennicutt-Schmidt Law from Feedback

NASA Astrophysics Data System (ADS)

Orr, Matthew E.; Hayward, Christopher C.; Hopkins, Philip F.; Chan, T. K.; Faucher-Giguère, Claude-André; Feldmann, Robert; Kereš, Dušan; Murray, Norman; Quataert, Eliot

2018-05-01

We present an analysis of the global and spatially-resolved Kennicutt-Schmidt (KS) star formation relation in the FIRE (Feedback In Realistic Environments) suite of cosmological simulations, including halos with z = 0 masses ranging from 1010 - 1013 M⊙. We show that the KS relation emerges and is robustly maintained due to the effects of feedback on local scales regulating star-forming gas, independent of the particular small-scale star formation prescriptions employed. We demonstrate that the time-averaged KS relation is relatively independent of redshift and spatial averaging scale, and that the star formation rate surface density is weakly dependent on metallicity and inversely dependent on orbital dynamical time. At constant star formation rate surface density, the `Cold & Dense' gas surface density (gas with T < 300 K and n > 10 cm-3, used as a proxy for the molecular gas surface density) of the simulated galaxies is ˜0.5 dex less than observed at ˜kpc scales. This discrepancy may arise from underestimates of the local column density at the particle-scale for the purposes of shielding in the simulations. Finally, we show that on scales larger than individual giant molecular clouds, the primary condition that determines whether star formation occurs is whether a patch of the galactic disk is thermally Toomre-unstable (not whether it is self-shielding): once a patch can no longer be thermally stabilized against fragmentation, it collapses, becomes self-shielding, cools, and forms stars, regardless of epoch or environment.

Star Formation-Driven Winds in the Early Universe

NASA Astrophysics Data System (ADS)

Peek, Matthew; Lundgren, Britt; Brammer, Gabriel

2018-01-01

Measuring the extent of star formation-driven winds from galaxies in the early universe is crucial for understanding of how galaxies evolve over cosmic time. Using WFC3/IR grism data from the Hubble Space Telescope (HST), we have measured the star formation rates and star formation rate surface densities of several hundred galaxies at redshift (z) = 1, when the universe was roughly half its present age. The galaxies we examine are also probed by background quasars, whose spectra provide information about the extent of metal-enriched gas in their halos. We use a computational pipeline to measure the density of the star formation in each galaxy and correlate these measurements with detections of Mg II absorption in nearby quasar spectra from the Sloan Digital Sky Survey. Our preliminary results support a model in which galaxies with high SFR surface densities drive metal-enriched gas out of the disk and into these galaxies’ extended halos, where that gas is detected in the spectra of more distant quasars.

The SAMI Galaxy Survey: Publicly Available Spatially Resolved Emission Line Data Products

NASA Astrophysics Data System (ADS)

Medling, Anne; Green, Andrew W.; Ho, I.-Ting; Groves, Brent; Croom, Scott; SAMI Galaxy Survey Team

2017-01-01

The SAMI Galaxy Survey is collecting optical integral field spectroscopy of up to 3400 nearby (z<0.1) galaxies with a range of stellar masses and in a range of environments. The first public data release contains nearly 800 galaxies from the Galaxy And Mass Assembly (GAMA) Survey. In addition to releasing the reduced data cubes, we also provide emission line fits (flux and kinematic maps of strong emission lines including Halpha and Hbeta, [OII]3726,29, [OIII]4959,5007, [OI]6300, [NII]6548,83, and [SII]6716,31), extinction maps, star formation classification masks, and star formation rate maps. We give an overview of the data available for your favorite emission line science and present a few early science results. For example, a sample of edge-on disk galaxies show enhanced extraplanar emission related to SF-driven outflows, which are correlated with a bursty star formation history and higher star formation rate surface densities. Interestingly, the star formation rate surface densities of these wind hosts are 5-100 times lower than the canonical threshold for driving winds (0.1 MSun/yr/kpc2), indicating that galactic winds may be more important in normal star-forming galaxies than previously thought.

Co-adsorption of oxygen and formic acid on rutile TiO2 (110) studied by infrared reflection-absorption spectroscopy

NASA Astrophysics Data System (ADS)

Mattsson, Andreas; Österlund, Lars

2017-09-01

Adsorption of formic acid and co-adsorption with oxygen have been investigated on the rutile TiO2(110) surface using p- and s-polarized infrared reflection-absorption spectroscopy (IRRAS) at O2 exposures between 45 L to 8100 L and at temperatures between 273 K and 343 K. On the clean surface formic acid dissociates into a formate ion (formate) and a proton. Formate binds to two five-fold coordinated Ti atoms in the troughs along the [001] direction, and the proton binds to neighboring bridging O atoms. Exposure of adsorbed formate to O2 leads to a decrease in the asymmetric νas(OCO) band at 1532 cm-1 and to the concomitant formation of a new vibration band at 1516 cm-1. From the s-and p-polarized IRRAS measurements performed at different O2 exposures, surface pre-treatments and substrate temperatures, and by comparisons with previous reports, we conclude that the new species is a bidentate surface hydrogen carbonate, which is formed by reaction between formate and oxygen adatoms on the surface. The σv reflection plane of the surface hydrogen carbonate molecule is oriented along the [001] direction, i.e. the same direction as the adsorbed formate molecule. On the clean TiO2(110) surface exposed to O2 prior to formic acid adsorption, similar results are obtained. The reaction rate to form surface hydrogen carbonate from formate is found to follow first-order kinetics, with an apparent activation energy of Er=0.25 eV.

Monte Carlo kinetics simulations of ice-mantle formation on interstellar grains

NASA Astrophysics Data System (ADS)

Garrod, Robin

2015-08-01

The majority of interstellar dust-grain chemical kinetics models use rate equations, or alternative population-based simulation methods, to trace the time-dependent formation of grain-surface molecules and ice mantles. Such methods are efficient, but are incapable of considering explicitly the morphologies of the dust grains, the structure of the ices formed thereon, or the influence of local surface composition on the chemistry.A new Monte Carlo chemical kinetics model, MIMICK, is presented here, whose prototype results were published recently (Garrod 2013, ApJ, 778, 158). The model calculates the strengths and positions of the potential mimima on the surface, on the fly, according to the individual pair-wise (van der Waals) bonds between surface species, allowing the structure of the ice to build up naturally as surface diffusion and chemistry occur. The prototype model considered contributions to a surface particle's potential only from contiguous (or "bonded") neighbors; the full model considers contributions from surface constituents from short to long range. Simulations are conducted on a fully 3-D user-generated dust-grain with amorphous surface characteristics. The chemical network has also been extended from the simple water system previously published, and now includes 33 chemical species and 55 reactions. This allows the major interstellar ice components to be simulated, such as water, methane, ammonia and methanol, as well as a small selection of more complex molecules, including methyl formate (HCOOCH3).The new model results indicate that the porosity of interstellar ices are dependent on multiple variables, including gas density, the dust temperature, and the relative accretion rates of key gas-phase species. The results presented also have implications for the formation of complex organic molecules on dust-grain surfaces at very low temperatures.

Improvement and formation of UV-induced damage on LBO crystal surface during long-term high-power third-harmonic generation.

PubMed

Hong, Hailong; Liu, Qiang; Huang, Lei; Gong, Mali

2013-03-25

We demonstrate the improvement and formation of UV-induced damage on LBO crystal output surface during long-term (130 h) high-power (20 W) high-repetition-rate (80 kHz) third-harmonic generation. The output surface was super-polished (RMS surface roughness <0.6 nm) to sub-nanometer scale super smooth roughness. The surface lifetime has been improved more than 20-fold compared with the as-polished ones (RMS surface roughness 4.0~8.0 nm). The damage could be attributed to the consequence of thermal effects resulted from impurity absorptions. Simultaneously, it was verified that the impurities originated in part from the UV-induced deposition.

The Effects of Sugars on the Biofilm Formation of Escherichia coli 185p on Stainless Steel and Polyethylene Terephthalate Surfaces in a Laboratory Model.

PubMed

Khangholi, Mahdi; Jamalli, Ailar

2016-09-01

Bacteria utilize various methods in order to live in protection from adverse environmental conditions. One such method involves biofilm formation; however, this formation is dependent on many factors. The type and concentration of substances such as sugars that are present in an environment can be effective facilitators of biofilm formation. First, the physico-chemical properties of the bacteria and the target surface were studied via the MATS and contact angle measurement methods. Additionally, adhesion to different surfaces in the presence of various concentrations of sugars was compared in order to evaluate the effect of these factors on the biofilm formation of Escherichia coli , which represents a major food contaminant . Results showed that the presence of sugars has no effect on the bacterial growth rate; all three concentrations of sugars were hydrophilic and demonstrated a high affinity toward binding to the surfaces. The impact of sugars and other factors on biofilm formation can vary depending on the type of bacteria present.

Mechano-Electrochemical Interaction Gives Rise to Strain Relaxation in Sn Electrodes

DOE PAGES

Barai, Pallab; Huang, Bo; Dillon, Shen J.; ...

2016-01-01

Tin (Sn) anode active particles were electrochemically lithiated during simultaneous imaging in a scanning electron microscope. Relationships among the reaction mechanism, active particle local strain rate, particle size, and microcrack formation are elucidated to demonstrate the importance of strain relaxation due to mechano-electrochemical interaction in Sn-based electrodes under electrochemical cycling. At low rates of operation, due to significant creep relaxation, large Sn active particles, of size 1 μm, exhibit no significant surface crack formation. Microcrack formation within Sn active particles occurs due to two different mechanisms: (i)large concentration gradient induced stress at the two-phase interface, and (ii) high volume expansionmore » induced stress at the surface of the active particles. From the present study, it can be concluded that majority of the microcracks evolve at or near the particle surface due to high volume expansion induced tension. Concentration gradient induced damage prevails near the center of the active particle, though significantly smaller in magnitude. Comparison with experimental results indicates that at operating conditions of C/2, even 500 nm sized Sn active particles remain free from surface crack formation, which emphasizes the importance of creep relaxation. A phase map has been developed to demonstrate the preferred mechano-electrochemical window of operation of Sn-based electrodes.« less

Non-linear hydroxyl radical formation rate in dispersions containing mixtures of pyrite and chalcopyrite particles

NASA Astrophysics Data System (ADS)

Kaur, Jasmeet; Schoonen, Martin A.

2017-06-01

The formation of hydroxyl radicals was studied in mixed pyrite-chalcopyrite dispersions in water using the conversion rate of adenine as a proxy for hydroxyl radical formation rate. Experiments were conducted as a function of pH, presence of phosphate buffer, surface loading, and pyrite-to-chalcopyrite ratio. The results indicate that hydroxyl radical formation rate in mixed systems is non-linear with respect to the rates in the pure endmember dispersions. The only exception is a set of experiments in which phosphate buffer is used. In the presence of phosphate buffer, the hydroxyl radical formation is suppressed in mixtures and the rate is close to that predicted based on the reaction kinetics of the pure endmembers. The non-linear hydroxyl radical formation in dispersions containing mixtures of pyrite and chalcopyrite is likely the result of two complementary processes. One is the fact that pyrite and chalcopyrite form a galvanic couple. In this arrangement, chalcopyrite oxidation is accelerated, while pyrite passes electrons withdrawn from chalcopyrite to molecular oxygen, the oxidant. The incomplete reduction of molecular oxygen leads to the formation of hydrogen peroxide and hydroxyl radical. The galvanic coupling appears to be augmented by the fact that chalcopyrite generates a significant amount of hydrogen peroxide upon dispersal in water. This hydrogen peroxide is then available for conversion to hydroxyl radical, which appears to be facilitated by pyrite as chalcopyrite itself produces only minor amounts of hydroxyl radical. In essence, pyrite is a ;co-factor; that facilitates the conversion of hydrogen peroxide to hydroxyl radical. This conversion reaction is a surface-mediated reaction. Given that hydroxyl radical is one of the most reactive species in nature, the formation of hydroxyl radicals in aqueous systems containing chalcopyrite and pyrite has implications for the stability of organic molecules, biomolecules, the viability of microbes, and exposure to dust containing the two metal sulfides may present a health burden.

Star-Formation Histories of MUSCEL Galaxies

NASA Astrophysics Data System (ADS)

Young, Jason; Kuzio de Naray, Rachel; Xuesong Wang, Sharon

2018-01-01

The MUSCEL program (MUltiwavelength observations of the Structure, Chemistry and Evolution of LSB galaxies) uses combined ground-based/space-based data to determine the spatially resolved star-formation histories of low surface brightness (LSB) galaxies. LSB galaxies are paradoxical in that they are gas rich but have low star-formation rates. Here we present our observations and fitting technique, and the derived histories for select MUSCEL galaxies. It is our aim to use these histories in tandem with velocity fields and metallicity profiles to determine the physical mechanism(s) that give these faint galaxies low star-formation rates despite ample gas supplies.

3rd hand smoking; heterogeneous oxidation of nicotine and secondary aerosol formation in the indoor environment

NASA Astrophysics Data System (ADS)

Petrick, Lauren; Dubowski, Yael

2010-05-01

Tobacco smoking is well known as a significant source of primary indoor air pollutants. However, only recently has it been recognized that the impact of Tobacco smoking may continue even after the cigarette has been extinguished (i.e., third hand smoke) due to the effect of indoor surfaces. These surfaces may affect the fate of tobacco smoke in the form of secondary reactions and pollutants, including secondary organic aerosol (SOA) formation. Fourier Transform Infrared spectrometry with Attenuated Total Reflection (FTIR-ATR) in tandem with a Scanning Mobility Particle Sizing (SMPS) system was used to monitor the ozonation of cellulose sorbed nicotine and resulting SOA formation. SOA formation began at onset of ozone introduction ([O3] = 60 ± 5 ppb) with a size distribution of dp ≤ 25 nm, and was determined to be a result of heterogeneous reaction (opposed to homogeneous). SOA yield from reacted surface nicotine was on the order of 10 %. Simultaneous to SOA monitoring, FTIR-ATR spectra showed surface changes in the nicotine film as the reaction progressed, revealing a pseudo first-order surface reaction rate of 0.0026 ± 0.0008 min-1. Identified surface oxidation products included: cotinine, myosmine, methylnicotinamide and nicotyrine. Surface reaction rate was found to be partially inhibited at high relative humidity. Given the toxicity of some of the identified products (e.g., cotinine has shown potential mutagenicity and teratogenicity) and that small particles may contribute to adverse health effects, the present study indicates that exposure to 3rd hand smoke ozonation products may pose additional health risks.

Soil erosion in mountainous areas: how far can we go?

NASA Astrophysics Data System (ADS)

Egli, Markus

2017-04-01

Erosion is the counter part of soil formation, is a natural process and cannot be completely impeded. With respect to soil protection, the term of tolerable soil erosion, having several definitions, has been created. Tolerable erosion is often equalled to soil formation or production. It is therefore crucial that we know the rates of soil formation when discussing sustainability of soil use and management. Natural rates of soil formation or production are determined by mineral weathering or transformation of parent material into soil, dust deposition and organic matter incorporation. In mountain areas where soil depth is a main limiting factor for soil productivity, the use and management of soils must consider how to preserve them from excessive depth loss and consequent degradation of their physical, chemical and biological properties. Even under natural conditions, landscape surfaces and soils are known to evolve in complex, non-linear ways over time. As a result, soil production and erosion change substantially with time. The fact that soil erosion and soil production processes are discontinuous over time is an aspect that is in most cases completely neglected. To conserve a given situation, tolerable values should take these dynamics into account. Measurements of long and short-term physical erosion rates, total denudation, weathering rates and soil production have recently become much more widely available through cosmogenic and fallout nuclide techniques. In addition to this, soil chronosequences deliver a precious insight into the temporal aspect of soil formation and production. Examples from mountainous and alpine areas demonstrate that soil production rates strongly vary as a function of time (with young soils and eroded surfaces having distinctly higher rates than old soils). Extensive erosion promotes rejuvenation of the surface and, therefore, accelerates chemical weathering and soil production - the resulting soil thickness will however be shallow. The comparison of soil production and erosion rates indicates that the present-day management of grassland soils in several alpine and mountain regions will lead in the long-term to very shallow soils (showing the characteristics of young soils). Shallow soils go along with high 'tolerable' erosion rates. It is, however, strongly doubtful whether this matches the deeper sense of sustainability.

Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

NASA Technical Reports Server (NTRS)

Ota, K.; Conger, W. L.

1977-01-01

The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

Interaction between aggrading geomorphic surfaces and the formation of a late pleistocene paleosol in the palouse loess of eastern Washington state

NASA Astrophysics Data System (ADS)

McDonald, Eric V.; Busacca, Alan J.

1990-09-01

Variable rates of loess deposition contributed to dramatic regional variation in a soil-stratigraphic unit, the Washtucna Soil, in the Palouse loess deposits in the Channeled Scabland of eastern Washington state. Throughout most of the Channeled Scabland, the morphology of the Washtucna Soil is that of a single buried soil, but it bifurcates into two well-developed and pedologically distinct buried soils in areas immediately downwind of the major source of loessial sediment. Regional loess stratigraphy confirms that the two well-developed soils formed during the same interval of time during which only one soil formed in areas that are distal to loess source areas. The variable and perhaps rapid rates of soil formation suggested by the stratigraphy resulted from an interaction between variable rates of loess deposition and the formation of superimposed calcic soils. Petrocalcic horizons with weak Stage IV morphology formed as the zone of carbonate accumulation moved up into former A and cambic horizons that had been profusely burrowed by cicadas. The development of cicada burrows in one phase of soil development that were subsequently engulfed by pedogenic carbonate under a rising land surface seems to have greatly accelerated the development of the petrocalcic horizons. Accelerated rates of formation of the petrocalcic horizons occurred when extrinsic (pulses of loess deposition) and intrinsic (engulfment of burrowed horizons) thresholds were exceeded. Stratigraphic evidence suggests that the soil formation that accompanied the rise in the land surface due to additional loess deposition may have occurred during the late Wisconsin glaciation when giant glacial outburst floods in the channeled Scabland triggered a new cycle of loess deposition.

Ion beam microtexturing of surfaces

NASA Technical Reports Server (NTRS)

Robinson, R. S.

1981-01-01

Some recent work in surface microtecturing by ion beam sputtering is described. The texturing is accomplished by deposition of an impurity onto a substrate while simultaneously bombarding it with an ion beam. A summary of the theory regarding surface diffusion of impurities and the initiation of cone formation is provided. A detailed experimental study of the time-development of individual sputter cones is described. A quasi-liquid coating was observed that apparently reduces the sputter rate of the body of a cone compared to the bulk material. Experimental measurements of surface diffusion activation energies are presented for a variety of substrate-seed combinations and range from about 0.3 eV to 1.2 eV. Observations of apparent crystal structure in sputter cones are discussed. Measurements of the critical temperature for cone formation are also given along with a correlation of critical temperature with substrate sputter rate.

Evaluation of Advanced Reactive Surface Area Estimates for Improved Prediction of Mineral Reaction Rates in Porous Media

NASA Astrophysics Data System (ADS)

Beckingham, L. E.; Mitnick, E. H.; Zhang, S.; Voltolini, M.; Yang, L.; Steefel, C. I.; Swift, A.; Cole, D. R.; Sheets, J.; Kneafsey, T. J.; Landrot, G.; Anovitz, L. M.; Mito, S.; Xue, Z.; Ajo Franklin, J. B.; DePaolo, D.

2015-12-01

CO2 sequestration in deep sedimentary formations is a promising means of reducing atmospheric CO2 emissions but the rate and extent of mineral trapping remains difficult to predict. Reactive transport models provide predictions of mineral trapping based on laboratory mineral reaction rates, which have been shown to have large discrepancies with field rates. This, in part, may be due to poor quantification of mineral reactive surface area in natural porous media. Common estimates of mineral reactive surface area are ad hoc and typically based on grain size, adjusted several orders of magnitude to account for surface roughness and reactivity. This results in orders of magnitude discrepancies in estimated surface areas that directly translate into orders of magnitude discrepancies in model predictions. Additionally, natural systems can be highly heterogeneous and contain abundant nano- and micro-porosity, which can limit connected porosity and access to mineral surfaces. In this study, mineral-specific accessible surface areas are computed for a sample from the reservoir formation at the Nagaoka pilot CO2 injection site (Japan). Accessible mineral surface areas are determined from a multi-scale image analysis including X-ray microCT, SEM QEMSCAN, XRD, SANS, and SEM-FIB. Powder and flow-through column laboratory experiments are performed and the evolution of solutes in the aqueous phase is tracked. Continuum-scale reactive transport models are used to evaluate the impact of reactive surface area on predictions of experimental reaction rates. Evaluated reactive surface areas include geometric and specific surface areas (eg. BET) in addition to their reactive-site weighted counterparts. The most accurate predictions of observed powder mineral dissolution rates were obtained through use of grain-size specific surface areas computed from a BET-based correlation. Effectively, this surface area reflects the grain-fluid contact area, or accessible surface area, in the powder dissolution experiment. In the model of the flow-through column experiment, the accessible mineral surface area, computed from the multi-scale image analysis, is evaluated in addition to the traditional surface area estimates.

The production of oxidants in Europa's surface.

PubMed

Johnson, R E; Quickenden, T I; Cooper, P D; McKinley, A J; Freeman, C G

2003-01-01

The oxidants produced by radiolysis and photolysis in the icy surface of Europa may be necessary to sustain carbon-based biochemistry in Europa's putative subsurface ocean. Because the subduction of oxidants to the ocean presents considerable thermodynamic challenges, we examine the formation of oxygen and related species in Europa's surface ice with the goal of characterizing the chemical state of the irradiated material. Relevant spectral observations of Europa and the laboratory data on the production of oxygen and related species are first summarized. Since the laboratory data are incomplete, we examine the rate equations for formation of oxygen and its chemical precursors by radiolysis and photolysis. Measurements and simple rate equations are suggested that can be used to characterize the production of oxidants in Europa's surface material and the chemical environment produced by radiolysis. Possible precursor molecules and the role of radical trapping are examined. The possibility of oxygen reactions on grain surfaces in Europa's regolith is discussed, and the earlier estimates of the supply of O(2) to the atmosphere are increased.

Modification of molybdenum surface by low-energy oxygen implantation at room temperature

NASA Astrophysics Data System (ADS)

Kavre Piltaver, Ivna; Jelovica Badovinac, Ivana; Peter, Robert; Saric, Iva; Petravic, Mladen

2017-12-01

We have studied the initial stages of oxide formation on molybdenum surfaces under 1 keV O2+ ion bombardment at room temperature (RT), using x-ray photoelectron spectroscopy around Mo 3d or O 1s core-levels and the valence band photoemission. The results are compared with the oxidation mechanism of thermally oxidized Mo at RT. The thermal oxidation reveals the formation of a very thin MoO2 layer that prevents any further adsorption of oxygen at higher oxygen doses. Oxygen implantation is more efficient in creating thicker oxide films with the simultaneous formation of several oxide compounds. The oxidation rates of MoO2 and Mo2O5 follow the parabolic growth rate consistent with the mass transport driven by diffusion of either neutral or singly and doubly charged oxygen interstitials. The oxidation of MoO3, which occurs at a later oxidation stage, follows the logarithmic rate driven by the diffusion of cations in an electric field.

PLATELET ADHESION TO POLYURETHANE UREA UNDER PULSATILE FLOW CONDITIONS

PubMed Central

Navitsky, Michael A.; Taylor, Joshua O.; Smith, Alexander B.; Slattery, Margaret J.; Deutsch, Steven; Siedlecki, Christopher A.; Manning, Keefe B.

2014-01-01

Platelet adhesion to a polyurethane urea surface is a precursor to thrombus formation within blood-contacting cardiovascular devices, and platelets have been found to adhere strongly to polyurethane surfaces below a shear rate of approximately 500 s−1. The aim of the current work is to determine platelet adhesion properties to the polyurethane urea surface as a function of time varying shear exposure. A rotating disk system is used to study the influence of steady and pulsatile flow conditions (e.g. cardiac inflow and sawtooth waveforms) for platelet adhesion to the biomaterial surface. All experiments retain the same root mean square angular rotation velocity (29.63 rad/s) and waveform period. The disk is rotated in platelet rich bovine plasma for two hours with adhesion quantified by confocal microscopy measurements of immunofluorescently labeled bovine platelets. Platelet adhesion under pulsating flow is found to exponentially decay with increasing shear rate. Adhesion levels are found to depend upon peak platelet flux and shear rate regardless of rotational waveform. In combination with flow measurements, these results may be useful for predicting regions susceptible to thrombus formation within ventricular assist devices. PMID:24721222

Contact activation of blood coagulation on a defined kaolin/collagen surface in a microfluidic assay.

PubMed

Zhu, Shu; Diamond, Scott L

2014-12-01

Generation of active Factor XII (FXIIa) triggers blood clotting on artificial surfaces and may also enhance intravascular thrombosis. We developed a patterned kaolin (0 to 0.3 pg/μm(2))/type 1 collagen fibril surface for controlled microfluidic clotting assays. Perfusion of whole blood (treated only with a low level of 4 μg/mL of the XIIa inhibitor, corn trypsin inhibitor) drove platelet deposition followed by fibrin formation. At venous wall shear rate (100 s(-1)), kaolin accelerated onset of fibrin formation by ~100 sec when compared to collagen alone (250 sec vs. 350 sec), with little effect on platelet deposition. Even with kaolin present, arterial wall shear rate (1000 s(-1)) delayed and suppressed fibrin formation compared to venous wall shear rate. A comparison of surfaces for extrinsic activation (tissue factor TF/collagen) versus contact activation (kaolin/collagen) that each generated equal platelet deposition at 100 s(-1) revealed: (1) TF surfaces promoted much faster fibrin onset (at 100 sec) and more endpoint fibrin at 600 sec at either 100 s(-1) or 1000 s(-1), and (2) kaolin and TF surfaces had a similar sensitivity for reduced fibrin deposition at 1000 s(-1) (compared to fibrin formed at 100 s(-1)) despite differing coagulation triggers. Anti-platelet drugs inhibiting P2Y1, P2Y12, cyclooxygenase-1 or activating IP-receptor or guanylate cyclase reduced platelet and fibrin deposition on kaolin/collagen. Since FXIIa or FXIa inhibition may offer safe antithrombotic therapy, especially for biomaterial thrombosis, these defined collagen/kaolin surfaces may prove useful in drug screening tests or in clinical diagnostic assays of blood under flow conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Formation of Micro-Scale Gas Pockets From Underwater Wall Orifices

NASA Astrophysics Data System (ADS)

Pereira, Francisco A.; Gharib, Morteza

2012-11-01

Our experiments examine the formation of micro-scale gas pockets from orifices on walls with hydrophilic and hydrophobic wetting properties. Bubble injection is operated in a liquid at rest at constant flow rate and in a quasi-static regime, and the mechanism of bubble growth is investigated through high speed recordings. The growth dynamics is studied in terms of orifice size, surface wetting properties and buoyancy sign. The bubble formation is characterized by an explosive growth, with a pressure wave that causes the bubble to take highly transient shapes in its very initial stages, before stabilizing as a sphere and growing at a relatively slow rate. In case of positive buoyancy, the bubble elongates with the formation of a neck before detaching from the wall. When buoyancy acts towards the wall, the bubble attaches to the wall and expands laterally with a moving contact line. In presence of hydrophobic surfaces, the bubble attaches immediately to the wall irrespective of buoyancy direction and takes a hemispherical shape, expanding radially along the surface. A force balance is outlined to explain the different figures. The work was performed by FAP while on leave from CNR-INSEAN, and is supported by the Office of Naval Research (ONR).

Critical rate of electrolyte circulation for preventing zinc dendrite formation in a zinc-bromine redox flow battery

NASA Astrophysics Data System (ADS)

Yang, Hyeon Sun; Park, Jong Ho; Ra, Ho Won; Jin, Chang-Soo; Yang, Jung Hoon

2016-09-01

In a zinc-bromine redox flow battery, a nonaqueous and dense polybromide phase formed because of bromide oxidation in the positive electrolyte during charging. This formation led to complicated two-phase flow on the electrode surface. The polybromide and aqueous phases led to different kinetics of the Br/Br- redox reaction; poor mixing of the two phases caused uneven redox kinetics on the electrode surface. As the Br/Br- redox reaction was coupled with the zinc deposition reaction, the uneven redox reaction on the positive electrode was accompanied by nonuniform zinc deposition and zinc dendrite formation, which degraded battery stability. A single-flow cell was operated at varying electrolyte circulation rates and current densities. Zinc dendrite formation was observed after cell disassembly following charge-discharge testing. In addition, the flow behavior in the positive compartment was observed by using a transparent version of the cell. At low rate of electrolyte circulation, the polybromide phase clearly separated from the aqueous phase and accumulated at the bottom of the flow frame. In the corresponding area on the negative electrode, a large amount of zinc dendrites was observed after charge-discharge testing. Therefore, a minimum circulation rate should be considered to avoid poor mixing of the positive electrolyte.

Tridax procumbens flavonoids: a prospective bioactive compound increased osteoblast differentiation and trabecular bone formation.

PubMed

Al Mamun, Md Abdullah; Hosen, Mohammad Jakir; Khatun, Amina; Alam, M Masihul; Al-Bari, Md Abdul Alim

2017-09-08

The Tridax procumbens extracts (TPE) are known for their ethno-medicinal properties to increase osteogenic functioning in mesenchymal stem cells. Recently, we found that the T. procumbens flavonoids (TPF) significantly suppressed the RANKL-induced osteoclasts differentiation and bone resorption. The TPF also promoted osteoblasts differentiation and bone formation demonstrated by increasing bone formation markers in cultured mouse primary osteoblasts. However, the effects of the TPF on in vivo bone formation remain unclear. In this study, we investigated the effects of the TPF on in vivo bone formation, injected the TPF (20 mg/kg) twice a day in the low calcium diet mice and killed them after 21 day. Radiographic and histomorphometric analyses were performed on the dissected bones to determine the anabolic effects of the TPF. Bone mineral density and bone mineral content of the TPF-treated mice were significantly increased compared to the control mice. Bone formation-related indices like osteoblast number, osteoblast surface, bone volume, mineralizing surface, mineral apposition rate and bone formation rate were significantly increased in the TPF-treated mice compared to the control mice. Our findings point towards the stimulation of bone formation by TPF, suggested that the TPF could be a potential natural anabolic agent to treat patients with bone loss-associated diseases such as osteoporosis.

Integrated loessite-paleokarst depositional system, early Pennsylvanian Molas Formation, Paradox Basin, southwestern Colorado, U.S.A.

NASA Astrophysics Data System (ADS)

Evans, James E.; Reed, Jason M.

2007-03-01

Mississippian paleokarst served as a dust trap for the oldest known Paleozoic loessite in North America. The early Pennsylvanian Molas Formation consists of loessite facies (sorted, angular, coarse-grained quartz siltstone), infiltration facies (loess redeposited as cave sediments within paleokarst features of the underlying Mississippian Leadville Limestone), colluvium facies (loess infiltrated into colluvium surrounding paleokarst towers) and fluvial facies (siltstone-rich, fluvial channel and floodplain deposits with paleosols). The depositional system evolved from an initial phase of infiltration and colluvium facies that were spatially and temporally related to the paleokarst surface, to loessite facies that mantled the paleotopography, and to fluvial facies that were intercalated with marine-deltaic rocks of the overlying Pennsylvanian Hermosa Formation. This sequence is interpreted as a response to the modification of the dust-trapping ability of the paleokarst surface. Loess was initially eroded from the surface, transported and redeposited in the subsurface by the karst paleohydrologic system, maintaining the dust-trapping ability of the paleotopographic surface. Later, the paleotopographic surface was buried when loess accumulation rates exceeded the transport capacity of the karst paleohydrologic system. These changes could have occurred because of (1) increased dust input rates in western Pangaea, (2) rising base levels and/or (3) porosity loss due to deposition within paleokarst passageways.

Atomic-level spatial distributions of dopants on silicon surfaces: toward a microscopic understanding of surface chemical reactivity

NASA Astrophysics Data System (ADS)

Hamers, Robert J.; Wang, Yajun; Shan, Jun

1996-11-01

We have investigated the interaction of phosphine (PH 3) and diborane (B 2H 6) with the Si(001) surface using scanning tunneling microscopy, infrared spectroscopy, and ab initio molecular orbital calculations. Experiment and theory show that the formation of PSi heterodimers is energetically favorable compared with formation of PP dimers. The stability of the heterodimers arises from a large strain energy associated with formation of PP dimers. At moderate P coverages, the formation of PSi heterodimers leaves the surface with few locations where there are two adjacent reactive sites. This in turn modifies the chemical reactivity toward species such as PH 3, which require only one site to adsorb but require two adjacent sites to dissociate. Boron on Si(001) strongly segregates into localized regions of high boron concentration, separated by large regions of clean Si. This leads to a spatially-modulated chemical reactivity which during subsequent growth by chemical vapor deposition (CVD) leads to formation of a rough surface. The implications of the atomic-level spatial distribution of dopants on the rates and mechanisms of CVD growth processes are discussed.

Drilling plastic formations using highly polished PDC cutters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R.H.; Lund, J.B.; Anderson, M.

1995-12-31

Highly plastic and over-pressured formations are troublesome for both roller cone and PDC bits. Thus far, attempts to increase penetration rates in these formations have centered around re-designing the bit or modifying the cutting structure. These efforts have produced only moderate improvements. This paper presents both laboratory and field data to illustrate the benefits of applying a mirror polished surface to the face of PDC cutters in drilling stressed formations. These cutters are similar to traditional PDC cutters, with the exception of the reflective mirror finish, applied to the diamond table surfaces prior to their installation in the bit. Resultsmore » of tests conducted in a single point cutter apparatus and a full-scale drilling simulator will be presented and discussed. Field results will be presented that demonstrate the effectiveness of polished cutters, in both water and oil-based muds. Increases in penetration rates of 300-400% have been observed in the Wilcox formation and other highly pressured shales. Typically, the beneficial effects of polished cutters have been realized at depths greater than 7000 ft, and with mud weights exceeding 12 ppg.« less

Efficient star formation in the spiral arms of M51

NASA Technical Reports Server (NTRS)

Lord, Steven D.; Young, Judith S.

1990-01-01

The molecular, neutral, and ionized hydrogen distributions in the Sbc galaxy M51 (NGC 5194) are compared. To estimate H2 surface densities observations of the CO (J = 1 - 0) transition were made in 60 positions out to a radius of 155 arcsec. Extinction-corrected H-alpha intensities were used to compute the detailed massive star formation rates (MSFRs) in the disk. Estimates of the gas surface density, the MSFR, and the ratio of these quantities, MSFR/sigma(p), were then examined. The spiral arms were found to exhibit an excess gas density, measuring between 1.4 and 1.6 times the interarm values at 45 arcsec resolution. The total (arm and interarm) gas content and massive star formation rates in concentric annuli in the disk of M51 were computed. The two quantities fall off together with radius, yielding a relatively constant MSFR/sigma(p) with radius. This behavior is not explained by current models of star formation in galactic disks.

Air-sea fluxes and satellite-based estimation of water masses formation

NASA Astrophysics Data System (ADS)

Sabia, Roberto; Klockmann, Marlene; Fernandez-Prieto, Diego; Donlon, Craig

2015-04-01

Recent work linking satellite-based measurements of sea surface salinity (SSS) and sea surface temperature (SST) with traditional physical oceanography has demonstrated the capability of generating routinely satellite-derived surface T-S diagrams [1] and analyze the distribution/dynamics of SSS and its relative surface density with respect to in-situ measurements. Even more recently [2,3], this framework has been extended by exploiting these T-S diagrams as a diagnostic tool to derive water masses formation rates and areas. A water mass describes a water body with physical properties distinct from the surrounding water, formed at the ocean surface under specific conditions which determine its temperature and salinity. The SST and SSS (and thus also density) at the ocean surface are largely determined by fluxes of heat and freshwater. The surface density flux is a function of the latter two and describes the change of the density of seawater at the surface. To obtain observations of water mass formation is of great interest, since they serve as indirect observations of the thermo-haline circulation. The SSS data which has become available through the SMOS [4] and Aquarius [5] satellite missions will provide the possibility of studying also the effect of temporally-varying SSS fields on water mass formation. In the present study, the formation of water masses as a function of SST and SSS is derived from the surface density flux by integrating the latter over a specific area and time period in bins of SST and SSS and then taking the derivative of the total density flux with respect to density. This study presents a test case using SMOS SSS, OSTIA SST, as well as Argo ISAS SST and SSS for comparison, heat fluxes from the NOCS Surface Flux Data Set v2.0, OAFlux evaporation and CMORPH precipitation. The study area, initially referred to the North Atlantic, is extended over two additional ocean basins and the study period covers the 2011-2012 timeframe. Yearly, seasonal and monthly water mass formation rates for different SST and SSS ranges are presented. The formation peaks are remapped geographically, to analyze the extent of the formation area. Water mass formation derived from SMOS and OSTIA compares well with the results obtained from in-situ data, although slight differences in magnitude and peak location occur. Known water masses can then be identified. Ongoing/future work aims at extending this study along different avenues by: 1) expand systematically the spatial and temporal domain of the study to additional ocean basins and to the entire time period of available SSS observations from SMOS/Aquarius; 2) perform a thorough error propagation to assess how errors in satellite SSS and SST translate into errors in water masses formation rates and geographical areas extent; and 3) explore the different options to connect the surface information to the vertical buoyancy structure to assess potential density instability (e.g., Turner angle). References [1] Sabia, R., M. Klockmann, D. Fernández-Prieto, and C. Donlon (2014), A first estimation of SMOS-based ocean surface T-S diagrams, J. Geophys. Res. Oceans, 119, 7357-7371, doi:10.1002/2014JC010120. [2] Klockmann, M., R. Sabia, D. Fernández-Prieto, C. Donlon, J. Font; Towards an estimation of water masses formation areas from SMOS-based T-S diagrams; EGU general assembly 2014, April 27-May 2, 2014. [3] Klockmann, M., R. Sabia, D. Fernández-Prieto, C. Donlon, Linking satellite SSS and SST to water mass formation; Ocean salinity science and salinity remote sensing workshop, Exeter, UK, November 26-28, 2014. [4] Font, J., A. Camps, A. Borges, M. Martín-Neira, J. Boutin, N. Reul, Y. H. Kerr, A. Hahne, and S. Mecklenburg, "SMOS: The challenging sea surface salinity measurement from space," Proceedings of the IEEE, vol. 98, pp. 649-665, 2010. [5] Le Vine, D.M.; Lagerloef, G.S.E.; Torrusio, S.E.; "Aquarius and Remote Sensing of Sea Surface Salinity from Space," Proceedings of the IEEE , vol.98, no.5, pp.688-703, May 2010, doi: 10.1109/JPROC.2010.2040550.

Resolving molecular gas to ~500 pc in a unique star forming disk galaxy at z~2

NASA Astrophysics Data System (ADS)

Brisbin, Drew; Aravena, Manuel; Hodge, Jacqueline; Carilli, Chris Luke; Daddi, Emanuele; Dannerbauer, Helmut; Riechers, Dominik; Wagg, Jeff

2018-06-01

We have resolved molecular gas in a 'typical' star forming disk galaxy at z>2 down to the scale of ~500 pc. Previous observations of CO and [CI] lines on larger spatial scales have revealed bulk molecular and atomic gas properties indicating that the target is a massive disk galaxy with large gas reserves. Unlike many galaxies studied at high redshift, it is undergoing modest quiescent star formation rather than bursty centrally concentrated star formation. Therefore this galaxy represents an under-studied, but cosmologically important population in the early universe. Our new observations of CO (4-3) highlight the clumpy molecular gas fuelling star formation throughout the disk. Underlying continuum from cold dust provides a key constraint on star formation rate surface densities, allowing us to examine the star formation rate surface density scaling law in a never-before-tested regime of early universe galaxies.These observations enable an unprecedented view of the obscured star formation that is hidden to optical/UV imaging and trace molecular gas on a fine enough scale to resolve morphological traits and provide a view akin to single dish surveys in the local universe.

Chemistry and Formation of the Beilby Layer During Polishing of Fused Silica Glass

DOE PAGES

Suratwala, Tayyab; Steele, William; Wong, Lana; ...

2015-05-19

The chemical characteristics and the proposed formation mechanisms of the modified surface layer (called the Beilby layer) on polished fused silica glasses are described. Fused silica glass samples were polished using different slurries, polyurethane pads, and at different rotation rates. The concentration profiles of several key contaminants, such as Ce, K, and H, were measured in the near surface layer of the polished samples using Secondary Ion Mass Spectroscopy (SIMS). The penetration of K, originating from KOH used for pH control during polishing, decreased with increase in polishing material removal rate. In contrast, penetration of the Ce and H increasedmore » with increase in polishing removal rate. In addition, Ce penetration was largely independent of the other polishing parameters (e.g., particle size distribution and the properties of the polishing pad). The resulting K concentration depth profiles are described using a two-step diffusion process: (1) steady-state moving boundary diffusion (due to material removal during polishing) followed by (2) simple diffusion during ambient postpolishing storage. Using known alkali metal diffusion coefficients in fused silica glass, this diffusion model predicts concentration profiles that are consistent with the measured data at various polishing material removal rates. On the other hand, the observed Ce profiles are inconsistent with diffusion based transport. Rather we propose that Ce penetration is governed by the ratio of Ce–O–Si and Si–O–Si hydrolysis rates; where this ratio increases with interface temperature (which increases with polishing material removal rate) resulting in greater Ce penetration into the Beilby layer. Calculated Ce surface concentrations using this mechanism are in good agreement to the observed change in measured Ce surface concentrations with polishing material removal rate. In conclusion, these new insights into the chemistry of the Beilby layer, combined together with details of the single particle removal function during polishing, are used to develop a more detailed and quantitative picture of the polishing process and the formation of the Beilby layer.« less

An Archival COS Study of Multi-phase Galactic Outflows and Their Dependence on Host Galaxy Properties

NASA Astrophysics Data System (ADS)

Chisholm, John

2013-10-01

Galactic outflows have become vital for understanding galaxy evolution. Outflows have been used to explain the mass-metallicity relation, the star formation history of the universe, and the shape of the baryonic mass function. However, few studies have focused on the basic question of how outflow velocities depend upon the physical properties of their host galaxies. Here we propose an archival project utilizing 52 COS spectra of local star-forming galaxies spanning four decades of star formation rate, and stellar mass. We will preform a self-consistent analysis of trends between galactic properties {star formation rate, stellar mass, specific star formation rate and star formation rate surface density} and outflow velocities measured from interstellar metal absorption lines {e.g., CII 1335}. We will extend this analysis to different gas phases - cold, warm, and hot - to gain a more comprehensive understanding of the physics of multi-phase outflows. The trends we observe will provide insights into the feedback process and will be crucial new benchmarks for simulations.

Plasma variables and tribological properties of coatings in low pressure (0.1 - 10.0 torr) plasma systems

NASA Technical Reports Server (NTRS)

Avni, R.; Spalvins, T.

1984-01-01

A detailed treatment is presented of the dialog known as plasma surface interactions (PSI) with respect to the coating process and its tribological behavior. Adsorption, morphological changes, defect formation, sputtering, chemical etching, and secondary electron emission are all discussed as promoting and enhancing the surface chemistry, thus influencing the tribological properties of the deposited flux. Phenomenological correlations of rate of deposition, flux composition, microhardness, and wear with the plasma layer variables give an insight to the formation of chemical bonding between the deposited flux and the substrate surface.

Experimental determination of the kinetics of formation of the benzene-ethane co-crystal and implications for Titan

NASA Astrophysics Data System (ADS)

Cable, Morgan L.; Vu, Tuan H.; Hodyss, Robert; Choukroun, Mathieu; Malaska, Michael J.; Beauchamp, Patricia

2014-08-01

Benzene is found on Titan and is a likely constituent of the putative evaporite deposits formed around the hydrocarbon lakes. We have recently demonstrated the formation of a benzene-ethane co-crystal under Titan-like surface conditions. Here we investigate the kinetics of formation of this new structure as a function of temperature. We show that the formation process would reach completion under Titan surface conditions in ~18 h and that benzene precipitates from liquid ethane as the co-crystal. This suggests that benzene-rich evaporite basins around ethane/methane lakes and seas may not contain pure crystalline benzene, but instead benzene-ethane co-crystals. This co-crystalline form of benzene with ethane represents a new class of materials for Titan's surface, analogous to hydrated minerals on Earth. This new structure may also influence evaporite characteristics such as particle size, dissolution rate, and infrared spectral properties.

Molecular dynamics simulations of bubble formation and cavitation in liquid metals.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Insepov, Z.; Hassanein, A.; Bazhirov, T. T.

2007-11-01

Thermodynamics and kinetics of nano-scale bubble formation in liquid metals such as Li and Pb were studied by molecular dynamics (MD) simulations at pressures typical for magnetic and inertial fusion. Two different approaches to bubble formation were developed. In one method, radial densities, pressures, surface tensions, and work functions of the cavities in supercooled liquid lithium were calculated and compared with the surface tension experimental data. The critical radius of a stable cavity in liquid lithium was found for the first time. In the second method, the cavities were created in the highly stretched region of the liquid phase diagram;more » and then the stability boundary and the cavitation rates were calculated in liquid lead. The pressure dependences of cavitation frequencies were obtained over the temperature range 700-2700 K in liquid Pb. The results of MD calculations for cavitation rate were compared with estimates of classical nucleation theory (CNT).« less

Morphological and proteomic analysis of biofilms from the Antarctic archaeon, Halorubrum lacusprofundi.

PubMed

Liao, Y; Williams, T J; Ye, J; Charlesworth, J; Burns, B P; Poljak, A; Raftery, M J; Cavicchioli, R

2016-11-22

Biofilms enhance rates of gene exchange, access to specific nutrients, and cell survivability. Haloarchaea in Deep Lake, Antarctica, are characterized by high rates of intergenera gene exchange, metabolic specialization that promotes niche adaptation, and are exposed to high levels of UV-irradiation in summer. Halorubrum lacusprofundi from Deep Lake has previously been reported to form biofilms. Here we defined growth conditions that promoted the formation of biofilms and used microscopy and enzymatic digestion of extracellular material to characterize biofilm structures. Extracellular DNA was found to be critical to biofilms, with cell surface proteins and quorum sensing also implicated in biofilm formation. Quantitative proteomics was used to define pathways and cellular processes involved in forming biofilms; these included enhanced purine synthesis and specific cell surface proteins involved in DNA metabolism; post-translational modification of cell surface proteins; specific pathways of carbon metabolism involving acetyl-CoA; and specific responses to oxidative stress. The study provides a new level of understanding about the molecular mechanisms involved in biofilm formation of this important member of the Deep Lake community.

Morphological and proteomic analysis of biofilms from the Antarctic archaeon, Halorubrum lacusprofundi

PubMed Central

Liao, Y.; Williams, T. J.; Ye, J.; Charlesworth, J.; Burns, B. P.; Poljak, A.; Raftery, M. J.; Cavicchioli, R.

2016-01-01

Biofilms enhance rates of gene exchange, access to specific nutrients, and cell survivability. Haloarchaea in Deep Lake, Antarctica, are characterized by high rates of intergenera gene exchange, metabolic specialization that promotes niche adaptation, and are exposed to high levels of UV-irradiation in summer. Halorubrum lacusprofundi from Deep Lake has previously been reported to form biofilms. Here we defined growth conditions that promoted the formation of biofilms and used microscopy and enzymatic digestion of extracellular material to characterize biofilm structures. Extracellular DNA was found to be critical to biofilms, with cell surface proteins and quorum sensing also implicated in biofilm formation. Quantitative proteomics was used to define pathways and cellular processes involved in forming biofilms; these included enhanced purine synthesis and specific cell surface proteins involved in DNA metabolism; post-translational modification of cell surface proteins; specific pathways of carbon metabolism involving acetyl-CoA; and specific responses to oxidative stress. The study provides a new level of understanding about the molecular mechanisms involved in biofilm formation of this important member of the Deep Lake community. PMID:27874045

Formation of coffee-stain patterns at the nanoscale: The role of nanoparticle solubility and solvent evaporation rate.

PubMed

Zhang, Jianguo; Milzetti, Jasmin; Leroy, Frédéric; Müller-Plathe, Florian

2017-03-21

When droplets of nanoparticle suspension evaporate from surfaces, they leave behind a deposit of nanoparticles. The mechanism of evaporation-induced pattern formation in the deposit is studied by molecular dynamics simulations for sessile nanodroplets. The influence of the interaction between nanoparticles and liquid molecules and the influence of the evaporation rate on the final deposition pattern are addressed. When the nanoparticle-liquid interaction is weaker than the liquid-liquid interaction, an interaction-driven or evaporation-induced layer of nanoparticles appears at the liquid-vapor interface and eventually collapses onto the solid surface to form a uniform deposit independently of the evaporation rate. When the nanoparticle-liquid and liquid-liquid interactions are comparable, the nanoparticles are dispersed inside the droplet and evaporation takes place with the contact line pinned at a surface defect. In such a case, a pattern with an approximate ring-like shape is found with fast evaporation, while a more uniform distribution is observed with slower evaporation. When the liquid-nanoparticle interaction is stronger than the liquid-liquid interaction, evaporation always occurs with receding contact line. The final deposition pattern changes from volcano-like to pancake-like with decreasing evaporation rate. These findings might help to design nanoscale structures like nanopatterns or nanowires on surface through controlled solvent evaporation.

Formation of coffee-stain patterns at the nanoscale: The role of nanoparticle solubility and solvent evaporation rate

NASA Astrophysics Data System (ADS)

Zhang, Jianguo; Milzetti, Jasmin; Leroy, Frédéric; Müller-Plathe, Florian

2017-03-01

When droplets of nanoparticle suspension evaporate from surfaces, they leave behind a deposit of nanoparticles. The mechanism of evaporation-induced pattern formation in the deposit is studied by molecular dynamics simulations for sessile nanodroplets. The influence of the interaction between nanoparticles and liquid molecules and the influence of the evaporation rate on the final deposition pattern are addressed. When the nanoparticle-liquid interaction is weaker than the liquid-liquid interaction, an interaction-driven or evaporation-induced layer of nanoparticles appears at the liquid-vapor interface and eventually collapses onto the solid surface to form a uniform deposit independently of the evaporation rate. When the nanoparticle-liquid and liquid-liquid interactions are comparable, the nanoparticles are dispersed inside the droplet and evaporation takes place with the contact line pinned at a surface defect. In such a case, a pattern with an approximate ring-like shape is found with fast evaporation, while a more uniform distribution is observed with slower evaporation. When the liquid-nanoparticle interaction is stronger than the liquid-liquid interaction, evaporation always occurs with receding contact line. The final deposition pattern changes from volcano-like to pancake-like with decreasing evaporation rate. These findings might help to design nanoscale structures like nanopatterns or nanowires on surface through controlled solvent evaporation.

Influence of surfaces on sulphidogenic bacteria.

PubMed

Bass, C J; Webb, J S; Sanders, P F; Lappin-Scott, H M

1996-01-01

Sulphidogenic bacteria in oil reservoirs are of great economic importance in terms of souring, fouling and corrosion. Mixed cultures containing these bacteria were isolated from chalk formations in North Sea oil reservoirs. These were thermophilic cultures, growing optimally at 60°C. Oil formations are porous matrices, providing a very large surface area and ideal conditions for bacterial attachment, survival and growth. This study included assessments of sulphide production rates of thermophilic (t-)sulphidogen consortia with and without additional surfaces. The availability of a surface contributed significantly to the rate and extent of sulphide generation. Surfaces were offered in varying amounts to growing planktonic cultures: significantly more sulphide was produced from cultures in contact with a surface than from identical cultures in the absence of a surface. In another series of experiments, t-sulphidogens were added to chalk rock chips in the presence of nutrients and incubated for several months. This resulted in rapid sulphide generation, the final concentration being related to the initial nutrient concentration. Subsequent nutrient addition resulted in renewed sulphide generation. It is suggested that bacteria in reservoirs can withstand long periods of nutrient deprivation while attached within the porous rock matrix and opportunistically utilise nutrients when they become available.

Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beste, Ariana; Steven Overbury

2015-01-08

We have performed computations to better understand how surface structure affects selectivity in dehydrogenation and dehydration reactions of alcohols. Ethanol reactions on the (111) and (100) ceria surfaces were studied starting from the dominant surface species, ethoxy. We used DFT (PBE+U) to explore reaction pathways leading to ethylene and acetaldehyde and calculated estimates of rate constants employing transition state theory. To assess pathway contributions, we carried out kinetic analysis. Our results show that intermediate and transition state structures are stabilized on the (100) surface compared to the (111) surface. Formation of acetaldehyde over ethylene is kinetically and thermodynamically preferred onmore » both surfaces. Our results are consistent with temperature programmed surface reaction and steady-state experiments, where acetaldehyde was found as the main product and evidence was presented that ethylene formation at higher temperature originates from changes in adsorbate and surface structure.« less

Dissolution of minerals with rough surfaces

NASA Astrophysics Data System (ADS)

de Assis, Thiago A.; Aarão Reis, Fábio D. A.

2018-05-01

We study dissolution of minerals with initial rough surfaces using kinetic Monte Carlo simulations and a scaling approach. We consider a simple cubic lattice structure, a thermally activated rate of detachment of a molecule (site), and rough surface configurations produced by fractional Brownian motion algorithm. First we revisit the problem of dissolution of initial flat surfaces, in which the dissolution rate rF reaches an approximately constant value at short times and is controlled by detachment of step edge sites. For initial rough surfaces, the dissolution rate r at short times is much larger than rF ; after dissolution of some hundreds of molecular layers, r decreases by some orders of magnitude across several time decades. Meanwhile, the surface evolves through configurations of decreasing energy, beginning with dissolution of isolated sites, then formation of terraces with disordered boundaries, their growth, and final smoothing. A crossover time to a smooth configuration is defined when r = 1.5rF ; the surface retreat at the crossover is approximately 3 times the initial roughness and is temperature-independent, while the crossover time is proportional to the initial roughness and is controlled by step-edge site detachment. The initial dissolution process is described by the so-called rough rates, which are measured for fixed ratios between the surface retreat and the initial roughness. The temperature dependence of the rough rates indicates control by kink site detachment; in general, it suggests that rough rates are controlled by the weakest microscopic bonds during the nucleation and formation of the lowest energy configurations of the crystalline surface. Our results are related to recent laboratory studies which show enhanced dissolution in polished calcite surfaces. In the application to calcite dissolution in alkaline environment, the minimal values of recently measured dissolution rate spectra give rF ∼10-9 mol/(m2 s), and the calculated rate laws of our model give rough rates in the range 10-6 -10-5 mol/(m2 s). This estimate is consistent with the range of calcite dissolution rates obtained in a recent work after treatment of literature data, which suggests the universal control of kink site dissolution in short term laboratory works. The weak effects of lattice size on our results also suggest that smoothing of mineral grain surfaces across geological times may be a microscopic explanation for the difference of chemical weathering rate of silicate minerals in laboratory and in the environment.

A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

USGS Publications Warehouse

Davis, J.A.; Fuller, C.C.; Cook, A.D.

1987-01-01

The rate of Cd2+ sorption by calcite was determined as a function of pH and Mg2+ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO3. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca2+ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd2+ sorption decrease with increasing pH or with increasing Mg2+. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer. A model is presented which is consistent with the rates of Cd2+ sorption and Ca2+ isotopic exchange. In the model, the first step in Cd2+ sorption involves a fast adsorption reaction that is followed by diffusion of Cd2+ into a surface layer of hydrated CaCO3 that overlies crystalline calcite. Desorption of Cd2+ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO3, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution. ?? 1987.

A High-Latitude Winter Continental Low Cloud Feedback Suppresses Arctic Air Formation in Warmer Climates

NASA Astrophysics Data System (ADS)

Cronin, T.; Tziperman, E.; Li, H.

2015-12-01

High latitude continents have warmed much more rapidly in recent decades than the rest of the globe, especially in winter, and the maintenance of warm, frost-free conditions in continental interiors in winter has been a long-standing problem of past equable climates. It has also been found that the high-latitude lapse rate feedback plays an important role in Arctic amplification of climate change in climate model simulations, but we have little understanding of why lapse rates at high latitudes change so strongly with warming. To better understand these problems, we study Arctic air formation - the process by which a high-latitude maritime air mass is advected over a continent during polar night, cooled at the surface by radiation, and transformed into a much colder continental polar air mass - and its sensitivity to climate warming. We use a single-column version of the WRF model to conduct two-week simulations of the cooling process across a wide range of initial temperature profiles and microphysics schemes, and find that a low cloud feedback suppresses Arctic air formation in warmer climates. This cloud feedback consists of an increase in low cloud amount with warming, which shields the surface from radiative cooling, and increases the continental surface air temperature by roughly two degrees for each degree increase of the initial maritime surface air temperature. The time it takes for the surface air temperature to drop below freezing increases nonlinearly to ~10 days for initial maritime surface air temperatures of 20 oC. Given that this is about the time it takes an air mass starting over the Pacific to traverse the north American continent, this suggests that optically thick stratus cloud decks could help to maintain frost-free winter continental interiors in equable climates. We find that CMIP5 climate model runs show large increases in cloud water path and surface cloud longwave forcing in warmer climates, consistent with the proposed low-cloud feedback. The suppression of Arctic air formation with warming may act as a significant amplifier of climate change at high latitudes, and offers a mechanistic perspective on the high-latitude "lapse rate feedback" diagnosed in climate models.

Spin decoherence of InAs surface electrons by transition metal ions

NASA Astrophysics Data System (ADS)

Zhang, Yao; Soghomonian, V.; Heremans, J. J.

2018-04-01

Spin interactions between a two-dimensional electron system at the InAs surface and transition metal ions, Fe3 +, Co2 +, and Ni2 +, deposited on the InAs surface, are probed by antilocalization measurements. The spin-dependent quantum interference phenomena underlying the quantum transport phenomenon of antilocalization render the technique sensitive to the spin states of the transition metal ions on the surface. The experiments yield data on the magnitude and temperature dependence of the electrons' inelastic scattering rates, spin-orbit scattering rates, and magnetic spin-flip rates as influenced by Fe3 +, Co2 +, and Ni2 +. A high magnetic spin-flip rate is shown to mask the effects of spin-orbit interaction, while the spin-flip rate is shown to scale with the effective magnetic moment of the surface species. The spin-flip rates and their dependence on temperature yield information about the spin states of the transition metal ions at the surface, and in the case of Co2 + suggest either a spin transition or formation of a spin-glass system.

Soot Surface Growth in Laminar Hydrocarbon/Air Diffusion Flames. Appendix J

NASA Technical Reports Server (NTRS)

El-Leathy, A. M.; Xu, F.; Kim, C. H.; Faeth, G. M.; Yuan, Z.-G. (Technical Monitor); Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

2003-01-01

The structure and soot surface growth properties of round laminar jet diffusion flames were studied experimentally. Measurements were made along the axes of ethylene-, propylene-propane- and acetylene-benzene-fueled flames burning in coflowing air at atmospheric pressure with the reactants at normal temperature. The measurements included soot structure, soot concentrations, soot temperatures, major gas species concentrations, some radial species (H, OH and 0) concentrations, and gas velocities. These measurements yielded the local flame properties that are thought to affect soot surface growth as well as local soot surface growth rates. When present results were combined with similar earlier observations of acetylene-fueled laminar jet diffusion flames, the results suggested that soot surface growth involved decomposition of the original fuel to form acetylene and H, which were the main reactants for soot surface growth, and that the main effect of the parent fuel on soot surface growth involved its yield of acetylene and H for present test conditions. Thus, as the distance increased along the axes of the flames, soot formation (which was dominated by soot surface growth) began near the cool core of the flow once acetylene and H appeared together and ended near the flame sheet when acetylene disappeared. Species mainly responsible for soot oxidation - OH and 02 were present throughout the soot formation region so that soot surface growth and oxidation proceeded at the same time. Present measurements of soot surface growth rates (corrected for soot surface oxidation) in laminar jet diffusion flames were consistent with earlier measurements of soot surface growth rates in laminar premixed flames and exhibited good agreement with existing Hydrogen-Abstraction/Carbon-Addition (HACA) soot surface growth mechanisms in the literature with steric factors in these mechanisms having values on the order of unity, as anticipated.

Soot Surface Growth in Laminar Hydrocarbon/Air Diffusion Flames. Appendix B

NASA Technical Reports Server (NTRS)

El-Leathy, A. M.; Xu, F.; Kim, C. H.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

2001-01-01

The structure and soot surface growth properties of round laminar jet diffusion flames were studied experimentally. Measurements were made along the axes of ethylene-, propylene-propane- and acetylene-benzene-fueled flames burning in coflowing air at atmospheric pressure with the reactants at normal temperature. The measurements included soot structure, soot concentrations, soot temperatures, major gas species concentrations, some radial species (H, OH and O) concentrations, and gas velocities. These measurements yielded the local flame properties that are thought to affect soot surface growth as well as local soot surface growth rates. When present results were combined with similar earlier observations of acetylene-fueled laminar jet diffusion flames, the results suggested that soot surface growth involved decomposition of the original fuel to form acetylene and H, which were the main reactants for soot surface growth, and that the main effect of the parent fuel on soot surface growth involved its yield of acetylene and H for present test conditions. Thus, as the distance increased along the axes of the flames, soot formation (which was dominated by soot surface growth) began near the cool core of the flow once acetylene and H appeared together and ended near the flame sheet when acetylene disappeared. Species mainly responsible for soot oxidation - OH and O2 were present throughout the soot formation region so that soot surface growth and oxidation proceeded at the same time. Present measurements of soot surface growth rates (corrected for soot surface oxidation) in laminar jet diffusion flames were consistent with earlier measurements of soot surface growth rates in laminar premixed flames and exhibited good agreement with existing Hydrogen-Abstraction/Carbon-Addition (HACA) soot surface growth mechanisms in the literature with steric factors in these mechanisms having values on the order of unity, as anticipated.

Kinetic Monte Carlo simulations of ion-induced ripple formation: Dependence on flux, temperature, and defect concentration in the linear regime

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chason, E.; Chan, W. L.; Bharathi, M. S.

Low-energy ion bombardment produces spontaneous periodic structures (sputter ripples) on many surfaces. Continuum theories describe the pattern formation in terms of ion-surface interactions and surface relaxation kinetics, but many features of these models (such as defect concentration) are unknown or difficult to determine. In this work, we present results of kinetic Monte Carlo simulations that model surface evolution using discrete atomistic versions of the physical processes included in the continuum theories. From simulations over a range of parameters, we obtain the dependence of the ripple growth rate, wavelength, and velocity on the ion flux and temperature. The results are discussedmore » in terms of the thermally dependent concentration and diffusivity of ion-induced surface defects. We find that in the early stages of ripple formation the simulation results are surprisingly well described by the predictions of the continuum theory, in spite of simplifying approximations used in the continuum model.« less

Influence of flow variability on floodplain formation and destruction, Little Missouri River, North Dakota

USGS Publications Warehouse

Miller, J.R.; Friedman, J.M.

2009-01-01

Resolving observations of channel change into separate planimetric measurements of floodplain formation and destruction reveals distinct relations between these processes and the flow regime. We analyzed a time sequence of eight bottomland images from 1939 to 2003 along the Little Missouri River, North Dakota, to relate geomorphic floodplain change to flow along this largely unregulated river. At the decadal scale, floodplain formation and destruction varied independently. Destruction was strongly positively correlated with the magnitude of infrequent high flows that recur every 5-10 yr, whereas floodplain formation was negatively correlated with the magnitude of frequent low flows exceeded 80% of the time. At the century scale, however, a climatically induced decrease in peak flows has reduced the destruction rate, limiting the area made available for floodplain formation. The rate of destruction was not uniform across the floodplain. Younger surfaces were consistently destroyed at a higher rate than older surfaces, suggesting that throughput of contaminants would have occurred more rapidly than predicted by models that assume uniform residence time of sediment across the floodplain. Maps of floodplain ages produced by analysis of sequential floodplain images are similar to maps of forest ages produced through dendrochronology, confirming the assumption of dendrogeomorphic studies that riparian tree establishment in this system is limited to recent channel locations. ?? 2009 Geological Society of America.

Droplet Kinetic Energy from Center-Pivot Sprinklers

USDA-ARS?s Scientific Manuscript database

The kinetic energy of discrete water drops impacting a bare soil surface is generally observed to lead to a drastic reduction in water infiltration rate due to soil surface seal formation. Under center-pivot sprinkler irrigation, kinetic energy transferred to the soil prior to crop canopy developmen...

Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

PubMed

Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

2016-02-01

This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

Soot Formation in Laminar Premixed Ethylene/Air Flames at Atmospheric Pressure. Appendix G

NASA Technical Reports Server (NTRS)

Xu, F.; Sunderland, P. B.; Faeth, G. M.; Urban, D. L. (Technical Monitor)

2001-01-01

Soot formation was studied within laminar premixed ethylene/air flames (C/O ratios of 0.78-0.98) stabilized on a flat-flame burner operating at atmospheric pressure. Measurements included soot volume fractions by both laser extinction and gravimetric methods, temperatures by multiline emission, soot structure by thermophoretic sampling and transmission electron microscopy, major gas species concentrations by sampling and gas chromatography, concentrations of condensable hydrocarbons by gravimetric sampling. and velocities by laser velocimetry. These data were used to find soot surface growth rates and primary soot particle nucleation rates along the axes of the flames. Present measurements of soot surface growth rates were correlated successfully by predictions based on typical hydrogen-abstraction/carbon-addition (HACA) mechanisms of Frenklach and co-workers and Colket and Hall. These results suavest that reduced soot surface growth rates with increasing residence time seen in the present and other similar flames were mainly caused by reduced rates of surface activation due to reduced H atom concentrations as temperatures decrease as a result of radiative heat losses. Primary soot particle nucleation rates exhibited variations with temperature and acetylene concentrations that were similar to recent observations for diffusion flames; however, nucleation rates in the premixed flames were significantly lower than in, the diffusion flames for reasons that still must be explained. Finally, predictions of yields of major gas species based on mechanisms from both Frenklach and co-workers and Leung and Lindstedt were in good agreement with present measurements and suggest that H atom concentrations (relevant to HACA mechanisms) approximate estimates based on local thermodynamic equilibrium in the present flames.

Accelerated and enhanced bone formation on novel simvastatin-loaded porous titanium oxide surfaces.

PubMed

Nyan, Myat; Hao, Jia; Miyahara, Takayuki; Noritake, Kanako; Rodriguez, Reena; Kasugai, Shohei

2014-10-01

With increasing application of dental implants in poor-quality bones, the need for implant surfaces ensuring accelerated osseointegration and enhanced peri-implant bone regeneration is increased. A study was performed to evaluate the osseointegration and bone formation on novel simvastatin-loaded porous titanium oxide surface. Titanium screws were treated by micro-arc oxidation to form porous oxide surface and 25 or 50 μg of simvastatin was loaded. The nontreated control, micro-arc oxidized, and simvastatin-loaded titanium screws were surgically implanted into the proximal tibia of 16-week-old male Wistar rats (n = 36). Peri-implant bone volume, bone-implant contact, and mineral apposition rates were measured at 2 and 4 weeks. Data were analyzed by one-way analysis of variance followed by Tukey's post hoc test. New bone was formed directly on the implant surface in the bone marrow cavity in simvastatin-loaded groups since 2 weeks. Bone-implant contact values were significantly higher in simvastatin-loaded groups than control and micro-arc oxidized groups at both time points (p < .05). Peri-implant bone volume and mineral apposition rate of simvastatin-loaded groups were significantly higher than control and micro-arc oxidized groups at 2 weeks (p < .05). These data suggested that simvastatin-loaded porous titanium oxide surface provides faster osseointegration and peri-implant bone formation and it would be potentially applicable in poor-quality bones. © 2013 Wiley Periodicals, Inc.

A Comparison of Young Star Properties with Local Galactic Environment for LEGUS/LITTLE THINGS Dwarf Irregular Galaxies

NASA Astrophysics Data System (ADS)

Hunter, Deidre A.; Adamo, Angela; Elmegreen, Bruce G.; Gallardo, Samavarti; Lee, Janice C.; Cook, David O.; Thilker, David; Kayitesi, Bridget; Kim, Hwihyun; Kahre, Lauren; Ubeda, Leonardo; Bright, Stacey N.; Ryon, Jenna E.; Calzetti, Daniela; Tosi, Monica; Grasha, Kathryn; Messa, Matteo; Fumagalli, Michele; Dale, Daniel A.; Sabbi, Elena; Cignoni, Michele; Smith, Linda J.; Gouliermis, Dimitrios M.; Grebel, Eva K.; Aloisi, Alessandra; Whitmore, Bradley C.; Chandar, Rupali; Johnson, Kelsey E.

2018-07-01

We have explored the role environmental factors play in determining characteristics of young stellar objects in nearby dwarf irregular and blue compact dwarf galaxies. Star clusters are characterized by concentrations, masses, and formation rates; OB associations by mass and mass surface density; O stars by their numbers and near-ultraviolet absolute magnitudes; and H II regions by Hα surface brightnesses. These characteristics are compared to surrounding galactic pressure, stellar mass density, H I surface density, and star formation rate (SFR) surface density. We find no trend of cluster characteristics with environmental properties, implying that larger-scale effects are more important in determining cluster characteristics or that rapid dynamical evolution erases any memory of the initial conditions. On the other hand, the most massive OB associations are found at higher pressure and H I surface density, and there is a trend of higher H II region Hα surface brightness with higher pressure, suggesting that a higher concentration of massive stars and gas is found preferentially in regions of higher pressure. At low pressures we find massive stars but not bound clusters and OB associations. We do not find evidence for an increase of cluster formation efficiency as a function of SFR density. However, there is an increase in the ratio of the number of clusters to the number of O stars with increasing pressure, perhaps reflecting an increase in clustering properties with SFR.

Impaired osteoblast function in osteoporosis: comparison between calcium balance and dynamic histomorphometry.

PubMed

Arlot, M; Edouard, C; Meunier, P J; Neer, R M; Reeve, J

1984-09-01

Osteoblast function was investigated in 27 patients with idiopathic osteoporosis. Transiliac bone biopsy specimens were taken after double labelling with tetracycline, and metabolic calcium balance was studied almost simultaneously. Many of the patients showed poor double labelling of their otherwise unremarkable trabecular osteoid, suggesting impaired formation of bone at many of these surfaces. This phenomenon was not accompanied by increased width of osteoid seams (as seen in osteomalacia), indicating that formation of the matrix and its mineralisation were in equilibrium. For the first time, highly significant positive correlations (p less than 0.01) were found between indices of bone formation, determined by labelling with tetracycline, and calcium balance. Thus some patients with osteoporosis who are rapidly losing bone have low rates of formation of trabecular bone both by individual osteoblasts and in relation to available bone surfaces. As histological indices of bone resorption also independently correlated strongly and inversely (p less than 0.01) with calcium balance the rate of initiation of new basic multicellular units by osteoclastic resorption of trabecular surfaces (or the depth of resorption at these surfaces) also appears to be an important determinant of mineral balance. The mechanisms that regulate the effective life span of mature osteoblasts require further investigation, particularly as some promising treatments that can increase trabecular bone volume in osteoporosis, such as parathyroid peptide hPTH (1-34) and sodium fluoride, must work through a reversal of osteoblastic depression.

Molecular Hydrogen Formation : Effect of Dust Grain Temperature Fluctuations

NASA Astrophysics Data System (ADS)

Bron, Emeric; Le Bourlot, Jacques; Le Petit, Franck

2013-06-01

H_{2} formation is a hot topic in astrochemistry. Thanks to Copernicus and FUSE satellites, its formation rate on dust grains in diffuse interstellar gas has been inferred (Jura 1974, Gry et al. 2002). Nevertheless, detection of H_2 emission in PDRs by ISO and Spitzer (Habart et al., 2004, 2005, 2011 ) showed that its formation mechanism can be efficient on warm grains (warmer than 30K), whereas experimental studies showed that Langmuir-Hinshelwood mechanism is only efficient in a narrow window of grain temperatures (typically between 10-20 K). The Eley-Rideal mechanism, in which H atoms are chemically bound to grains surfaces could explain such a formation rate in PDRs (Le Bourlot et al. 2012 ). Usual dust size distributions (e.g. Mathis et al. 1977 ) favor smaller grains in a way that makes most of the available grain surface belong to small grains. As small grains are subject to large temperature fluctuations due to UV-photons absorption, calculations at a fixed temperature give incorrect results under strong UV-fields. Here, we present a comprehensive study of the influence of this stochastic effect on H_2 formation by Langmuir-Hinshelwood and Eley-Rideal mechanisms. We use a master equation approach to calculate the statistics of coupled fluctuations of the temperature and adsorbed H population of a grain. Doing so, we are able to calculate the formation rate on a grain under a given radiation field and given gas conditions. We find that the Eley-Rideal mechanism remains an efficient mechanism in PDRs, and that the Langmuir-Hinshelwood mechanism is more efficient than expected on warm grains. This procedure is then coupled to full cloud simulations with the Meudon PDR code. We compare the new results with more classical evaluations of the formation rate, and present the differences in terms of chemical structure of the cloud and observable line intensities. We will also highlight the influence of some microphysical parameters on the results.

Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2004-01-01

Dissolution and precipitation rates of brucite (Mg(OH) 2) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10 -4 to 3 M), saturation index (-12 < log Ω < 0.4) and aqueous magnesium concentrations (10 -6 to 5·10 -4 M). Brucite surface charge and isoelectric point (pH IEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pH IEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m 2) and lack of dependence on ionic strength predicts the dominance of >MgOH 2+ species at pH < 8 and their progressive replacement by >MgOH° and >MgO - as pH increases to 10-12. Rates are proportional to the square of >MgOH 2+ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH 2+ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity: R=k Mg+ · {>MgOH 2+} 2 · (1-Ω 2) where kMg+ is the dissolution rate constant, {> i} is surface species concentration (mol/m 2), and Ω is the solution saturation index with respect to brucite. Measurements of nonsteady state brucite dissolution rates, in response to cycling the pH from 12 to 2 (pH-jump experiments), indicate the important role of surface hydroxylation — that leads to the formation of Mg oxo or -hydroxo complexes — in the formation of dissolution-active sites. Replacement of water molecules by these oxygen donor complexes in the Mg coordination sphere has a labilizing effect on the dynamics of the remaining water molecules and thus increases reaction rates.

Evaluating the influence of process parameters on soluble microbial products formation using response surface methodology coupled with grey relational analysis.

PubMed

Xu, Juan; Sheng, Guo-Ping; Luo, Hong-Wei; Fang, Fang; Li, Wen-Wei; Zeng, Raymond J; Tong, Zhong-Hua; Yu, Han-Qing

2011-01-01

Soluble microbial products (SMPs) present a major part of residual chemical oxygen demand (COD) in the effluents from biological wastewater treatment systems, and the SMP formation is greatly influenced by a variety of process parameters. In this study, response surface methodology (RSM) coupled with grey relational analysis (GRA) method was used to evaluate the effects of substrate concentration, temperature, NH(4)(+)-N concentration and aeration rate on the SMP production in batch activated sludge reactors. Carbohydrates were found to be the major component of SMP, and the influential priorities of these factors were: temperature>substrate concentration > aeration rate > NH(4)(+)-N concentration. On the basis of the RSM results, the interactive effects of these factors on the SMP formation were evaluated, and the optimal operating conditions for a minimum SMP production in such a batch activated sludge system also were identified. These results provide useful information about how to control the SMP formation of activated sludge and ensure the bioreactor high-quality effluent. Copyright © 2010 Elsevier Ltd. All rights reserved.

SDSS-IV MaNGA: Spatially Resolved Star Formation Main Sequence and LI(N)ER Sequence

NASA Astrophysics Data System (ADS)

Hsieh, B. C.; Lin, Lihwai; Lin, J. H.; Pan, H. A.; Hsu, C. H.; Sánchez, S. F.; Cano-Díaz, M.; Zhang, K.; Yan, R.; Barrera-Ballesteros, J. K.; Boquien, M.; Riffel, R.; Brownstein, J.; Cruz-González, I.; Hagen, A.; Ibarra, H.; Pan, K.; Bizyaev, D.; Oravetz, D.; Simmons, A.

2017-12-01

We present our study on the spatially resolved Hα and M * relation for 536 star-forming and 424 quiescent galaxies taken from the MaNGA survey. We show that the star formation rate surface density ({{{Σ }}}{SFR}), derived based on the Hα emissions, is strongly correlated with the M * surface density ({{{Σ }}}* ) on kiloparsec scales for star-forming galaxies and can be directly connected to the global star-forming sequence. This suggests that the global main sequence may be a consequence of a more fundamental relation on small scales. On the other hand, our result suggests that ∼20% of quiescent galaxies in our sample still have star formation activities in the outer region with lower specific star formation rate (SSFR) than typical star-forming galaxies. Meanwhile, we also find a tight correlation between {{{Σ }}}{{H}α } and {{{Σ }}}* for LI(N)ER regions, named the resolved “LI(N)ER” sequence, in quiescent galaxies, which is consistent with the scenario that LI(N)ER emissions are primarily powered by the hot, evolved stars as suggested in the literature.

Effect of hydrodynamics and surface roughness on the electrochemical behaviour of carbon steel in CSG produced water

NASA Astrophysics Data System (ADS)

Eyu, Gaius Debi; Will, Geoffrey; Dekkers, Willem; MacLeod, Jennifer

2015-12-01

The influence of fluid flow, surface roughness and immersion time on the electrochemical behaviour of carbon steel in coal seam gas produced water under static and hydrodynamic conditions has been studied. The disc electrode surface morphology before and after the corrosion test was characterized using scanning electron microscopy (SEM). The corrosion product was examined using X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD).The results show that the anodic current density increased with increasing surface roughness and consequently a decrease in corrosion surface resistance. Under dynamic flow conditions, the corrosion rate increased with increasing rotating speed due to the high mass transfer coefficient and formation of non-protective akaganeite β-FeO(OH) and goethite α-FeO(OH) corrosion scale at the electrode surface. The corrosion rate was lowest at 0 rpm. The corrosion rate decreased in both static and dynamic conditions with increasing immersion time. The decrease in corrosion rate is attributed to the deposition of corrosion products on the electrode surface. SEM results revealed that the rougher surface exhibited a great tendency toward pitting corrosion.

40 CFR 60.641 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... formations beneath the earth's surface. The principal hydrocarbon constituent is methane. Onshore means all... sulfur compounds means H2S, carbonyl sulfide (COS), and carbon disulfide (CS2). Sulfur production rate... efficiency achieved in percent, carried to one decimal place. SThe sulfur production rate, kilograms per hour...

40 CFR 60.641 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... formations beneath the earth's surface. The principal hydrocarbon constituent is methane. Onshore means all... sulfur compounds means H2S, carbonyl sulfide (COS), and carbon disulfide (CS2). Sulfur production rate... efficiency achieved in percent, carried to one decimal place. SThe sulfur production rate, kilograms per hour...

Carbon-containing compounds on fusion-related surfaces: Thermal and ion-induced formation and erosion

NASA Astrophysics Data System (ADS)

Linsmeier, Christian

2004-12-01

The deposition of carbon on metals is the unavoidable consequence of the application of different wall materials in present and future fusion experiments like ITER. Presently used and prospected materials besides carbon (CFC materials in high heat load areas) are tungsten and beryllium. The simultaneous application of different materials leads to the formation of surface compounds due to the erosion, transport and re-deposition of material during plasma operations. The formation and erosion processes are governed by widely varying surface temperatures and kinetic energies as well as the spectrum of impinging particles from the plasma. The knowledge of the dependence on these parameters is crucial for the understanding and prediction of the compound formation on wall materials. The formation of surface layers is of great importance, since they not only determine erosion rates, but also influence the ability of the first wall for hydrogen isotope inventory accumulation and release. Surface compound formation, diffusion and erosion phenomena are studied under well-controlled ultra-high vacuum conditions using in-situ X-ray photoelectron spectroscopy (XPS) and ion beam analysis techniques available at a 3 MV tandem accelerator. XPS provides chemical information and allows distinguishing elemental and carbidic phases with high surface sensitivity. Accelerator-based spectroscopies provide quantitative compositional analysis and sensitivity for deuterium in the surface layers. Using these techniques, the formation of carbidic layers on metals is studied from room temperature up to 1700 K. The formation of an interfacial carbide of several monolayers thickness is not only observed for metals with exothermic carbide formation enthalpies, but also in the cases of Ni and Fe which form endothermic carbides. Additional carbon deposited at 300 K remains elemental. Depending on the substrate, carbon diffusion into the bulk starts at elevated temperatures together with additional carbide formation. Depending on the bond nature in the carbide (metallic in the transition metal carbides, ionic e.g. in Be2C), the surface carbide layer is dissolved upon further increased temperatures or remains stable. Carbide formation can also be initiated by ion bombardment, both of chemically inert noble gas ions or C+ or CO+ ions. In the latter case, a deposition-erosion equilibrium develops which leads to a ternary surface layer of constant thickness. A chemical erosion channel is also discussed for the enhanced erosion of thin carbon films on metals by deuterium ions.

Droplet kinetic energy of moving spray-plate center-pivot irrigation sprinklers

USDA-ARS?s Scientific Manuscript database

The kinetic energy of discrete water drops impacting a bare soil surface generally leads to a drastic reduction in water infiltration rate due to formation of a seal on the soil surface. Under center-pivot sprinkler irrigation, kinetic energy transferred to the soil prior to crop canopy development ...

Polyacrylamide Molecular Weight and Phosphogypsum Effects on Infiltration and Erosion in Semi-Arid Soils

USDA-ARS?s Scientific Manuscript database

Seal formation at the surface of semi-arid soils during rainstorms reduces soil infiltration rate (IR) and causes runoff and erosion. Surface application of dry anionic polyacrylamide (PAM) with high molecular weight (MW) has been found to be effective in stabilizing soil aggregates, and decreasing ...

Polyacrylamide molecular weight and phosphogypsum effects on infiltration and erosion in semi-arid soils

USDA-ARS?s Scientific Manuscript database

Seal formation at the surface of semi-arid soils during rainstorms reduces soil infiltration rate (IR) and causes runoff and erosion. Surface application of dry anionic polyacrylamide (PAM) with high molecular weight (MW) has been found to be effective in stabilizing soil aggregates, and decreasing ...

Determination of kinetic energy applied by center pivot sprinklers

USDA-ARS?s Scientific Manuscript database

The kinetic energy of discrete drops impacting a bare soil surface is generally observed to lead to a drastic reduction in water infiltration rate due to soil surface seal formation. Under center pivot sprinkler irrigation, kinetic energy transferred to the soil prior to crop canopy development can...

[Indoor simulation on dew formation on plant leaves].

PubMed

Gao, Zhi-Yong; Wang, You-Ke; Wei, Xin-Guang; Liu, Shou-Yang; He, Zi-Li; Zhou, Yu-Hong

2014-03-01

Dew forming on plant leaves through water condensation plays a significant ecological role in arid and semi-arid areas as an ignorable fraction of water resources. In this study, an artificial intelligent climate chamber and an automatic temperature-control system for leaves were implemented to regulate the ambient temperature, the leaf surface temperature and the leaf inclination for dew formation. The impact of leaf inclination, ambient temperature and dew point-leaf temperature depression on the rate and quantity of dew accumulation on leaf surface were analyzed. The results indicated that the accumulation rate and the maximum volume of dew on leaves decreased with increasing the leaf inclination while increased with the increment of dew point-leaf temperature depression, ambient temperature and relative humidity. Under the horizontal configuration, dew accumulated linearly on leaf surface over time until the maximum volume (0.80 mm) was reached. However, dew would fall down after reaching the maximum volume when the leaf inclination existed (45 degrees or 90 degrees), significantly slowing down the accumulative rate, and the zigzag pattern for the dynamic of dew accumulation appeared.

Tunneling Rate Constants for H2CO+H on Amorphous Solid Water Surfaces

NASA Astrophysics Data System (ADS)

Song, Lei; Kästner, Johannes

2017-12-01

Formaldehyde (H2CO) is one of the most abundant molecules observed in the icy mantle covering interstellar grains. Studying its evolution can contribute to our understanding of the formation of complex organic molecules in various interstellar environments. In this work, we investigated the hydrogenation reactions of H2CO yielding CH3O, CH2OH, and the hydrogen abstraction resulting in H2+HCO on an amorphous solid water (ASW) surface using a quantum mechanics/molecular mechanics (QM/MM) model. The binding energies of H2CO on the ASW surface vary broadly, from 1000 to 9370 K. No correlation was found between binding energies and activation energies of hydrogenation reactions. Combining instanton theory with QM/MM modeling, we calculated rate constants for the Langmuir-Hinshelwood and the Eley-Rideal mechanisms for the three product channels of H+H2CO surface reactions down to 59 K. We found that the channel producing CH2OH can be ignored, owing to its high activation barrier leading to significantly lower rates than the other two channels. The ASW surface influences the reactivity in favor of formation of CH3O (branching ratio ˜80%) and hinders the H2CO dissociation into H2+HCO. In addition, kinetic isotope effects are strong in all reaction channels and vary strongly between the channels. Finally, we provide fits of the rate constants to be used in astrochemical models.

Potential Impacts from Using Photoactive Roads as AN Air Quality Mitigation Strategy

NASA Astrophysics Data System (ADS)

Toro, C.; Jobson, B. T.; Shen, S.; Chung, S. H.; Haselbach, L.

2013-12-01

Mobile sources are major contributors to photochemical air pollution in urban areas. It has been proposed that the use of TiO2 coated roadways ('photoactive roads') could be an effective approach to reduce mobile source emissions by oxidizing NOx and VOC emissions at the roadway surface. However, studies have shown that formation of HONO and aldehydes can occur from some TiO2 treated surfaces during the photocatalytic oxidation of NOx and VOC, respectively. By changing the NOx-to-VOC ratio and generating photolabile HOx radical precursors, photoactive roads may enhance ozone formation rates in urban areas. In this work we present results that quantify NOx and VOC loss rates onto TiO2 treated asphalt and concrete samples, as well as HONO and aldehydes yields that result from the photocatalytic process. The treatment used a commercially available product. These objectives are relevant considering that the quantification of pollutant loss rates and yields of byproducts have not been determined for asphalt and that in the US more than 90% of the roadway surface is made of this material. Surface reaction probabilities (γ) and byproduct yields were determined using a CSTR photochemical chamber under varying conditions of water vapor and UV-A light intensity. Our results indicate that asphalt surfaces have a significantly higher molar yield of HONO compared to concrete surfaces with similar TiO2 loading. Concrete surfaces have reaction probabilities with NO one order of magnitude higher than asphalt samples. Fresh asphalt samples showed negligible photocatalytic activity, presumably due to absorption of TiO2 into the bitumen substrate. Laboratory-prepared asphalt samples with a higher degree of exposed aggregates showed increased HONO molar yields when compared to real-road asphalt samples, whose HONO molar yield was ~1%. Preliminary results for aldehydes formation showed similar molar yields between aged asphalt and concrete, even though aged asphalt samples had twice the TiO2 loading than concrete samples.

Rates of surface lowering and landscape development in southern South Africa: a cosmogenic view

NASA Astrophysics Data System (ADS)

Richardson, Janet; Vanacker, Veerle; Lang, Andreas; Hodgson, David

2016-04-01

The landscape of southern South Africa is characterised by large-scale erosion surfaces, including extensive pediments and multiple strath terraces, which document discordant river evolution through resistant quarzitic lithologies of the Cape Fold Belt (CFB). The timing and rate of erosion is poorly constrained. New cosmogenic ages from surfaces in South Africa are presented using in situ produced 10Be. Strath terraces in deeply incised rivers at two sites within the CFB indicate slow rates of erosion (1.54 - 11.79 m/Ma), which are some of the lowest rates recorded globally. Four pediment surfaces and a depth profile of the thickest pediment were also dated, and the results indicate that there are low rates of surface lowering on the pediments (0.44 - 1.24 m/Ma). The pediments are long-lived features (minimum exposure ages of 0.47 - 1.09 Ma), and are now deeply dissected. Given the minimum exposure ages, calculated river incision rates (42- 203 m/Ma) suggest that after a long period of geomorphic stability during pediment formation there was a discrete phase of increased geomorphic activity. The calculated minimum exposure ages are considered dubious because: 1) known rates of surrounding river incision (published and ours); 2) the climate conditions and time necessary for ferricrete formation on the pediment surfaces and; 3) the deeply incised catchments in the CFB on which the pediments sit, which all point to the pediments being much older. The pediments are fossilised remnants of a much larger geomorphic surface that formed after the main phase of exhumation in southern Africa. They form a store of sediment that currently sit above the surrounding rivers that have some of the lowest erosion rates in the world. These results indicate that steep topography can prevail even in areas of low erosion and tectonic quiescence, and that whilst cosmogenic dating of landscapes is an exciting development in earth sciences, care is needed especially in ancient settings. We strongly suggest benchmarking chronometric information with geomorphic and stratigraphic information.

Candida krusei form mycelia along agar surfaces towards each other and other Candida species.

PubMed

Fleischmann, Jacob; Broeckling, Corey D; Lyons, Sarah

2017-03-11

Candida krusei has been known to exhibit communal interactions such as pellicle formation and crawling out of nutritional broth. We noticed another possible interaction on agar surfaces, where C. krusei yeast cells formed mycelia along agar surfaces toward each other. We report here the results of experiments to study this interaction. When C.krusei yeast cells are plated in parallel streaks, they form mycelia along agar surfaces toward other yeasts. They also detect the presence of Candida albicans and Candida glabrata across agar surfaces, while the latter two react neither to their own kind, nor to C. krusei. Secreted molecule(s) are likely involved as C.krusei does not react to heat killed C. krusei. Timing and rate of mycelia formation across distances suggests that mycelia start forming when a secreted molecule(s) on agar surface reaches a certain concentration. We detected farnesol, tyrosol and tryptophol molecules that may be involved with mycelial formation, on the agar surfaces between yeast streaks. Unexpectedly the amounts detected between streaks were significantly higher than would have expected from additive amounts of two streaks. All three Candida species secreted these molecules. When tested on agar surface however, none of these molecules individually or combined induced mycelia formation by C. krusei. Our data confirms another communal interaction by C. krusei, manifested by formation of mycelia by yeast cells toward their own kind and other yeasts on agar surfaces. We detected secretion of farnesol, tyrosol and tryptophol by C. krusei but none of these molecules induced this activity on agar surface making it unlikely that they are the ones utilized by this yeast for this activity.

Dense Gas, Dynamical Equilibrium Pressure, and Star Formation in Nearby Star-forming Galaxies

NASA Astrophysics Data System (ADS)

Gallagher, Molly J.; Leroy, Adam K.; Bigiel, Frank; Cormier, Diane; Jiménez-Donaire, María J.; Ostriker, Eve; Usero, Antonio; Bolatto, Alberto D.; García-Burillo, Santiago; Hughes, Annie; Kepley, Amanda A.; Krumholz, Mark; Meidt, Sharon E.; Meier, David S.; Murphy, Eric J.; Pety, Jérôme; Rosolowsky, Erik; Schinnerer, Eva; Schruba, Andreas; Walter, Fabian

2018-05-01

We use new ALMA observations to investigate the connection between dense gas fraction, star formation rate (SFR), and local environment across the inner region of four local galaxies showing a wide range of molecular gas depletion times. We map HCN (1–0), HCO+ (1–0), CS (2–1), 13CO (1–0), and C18O (1–0) across the inner few kiloparsecs of each target. We combine these data with short-spacing information from the IRAM large program EMPIRE, archival CO maps, tracers of stellar structure and recent star formation, and recent HCN surveys by Bigiel et al. and Usero et al. We test the degree to which changes in the dense gas fraction drive changes in the SFR. {I}HCN}/{I}CO} (tracing the dense gas fraction) correlates strongly with I CO (tracing molecular gas surface density), stellar surface density, and dynamical equilibrium pressure, P DE. Therefore, {I}HCN}/{I}CO} becomes very low and HCN becomes very faint at large galactocentric radii, where ratios as low as {I}HCN}/{I}CO}∼ 0.01 become common. The apparent ability of dense gas to form stars, {{{Σ }}}SFR}/{{{Σ }}}dense} (where Σdense is traced by the HCN intensity and the star formation rate is traced by a combination of Hα and 24 μm emission), also depends on environment. {{{Σ }}}SFR}/{{{Σ }}}dense} decreases in regions of high gas surface density, high stellar surface density, and high P DE. Statistically, these correlations between environment and both {{{Σ }}}SFR}/{{{Σ }}}dense} and {I}HCN}/{I}CO} are stronger than that between apparent dense gas fraction ({I}HCN}/{I}CO}) and the apparent molecular gas star formation efficiency {{{Σ }}}SFR}/{{{Σ }}}mol}. We show that these results are not specific to HCN.

Catalytic carbide formation at aluminium-carbon interfaces

NASA Technical Reports Server (NTRS)

Maruyama, B.; Rabenberg, L.; Ohuchi, F. S.

1990-01-01

X-ray photoelectron spectroscopy investigations of the reaction of several monolayer-thick films of aluminum with glassy carbon substrates are presented. The influence of molecular oxygen and water vapor on the rate of reaction is examined. It is concluded that water vapor catalyzed the formation of aluminum carbide from aluminum and carbon by forming active sites which weakened carbon-carbon bonds at the glassy carbon surface, thus assisting their cleavage. The rate of carbide formation for undosed and molecular oxygen-dosed examples was less as neither metallic aluminum nor oxygen-formed alumina could bond to the carbon atom with sufficient strength to dissociate it quickly.

Extracellular enzymes facilitate electron uptake in biocorrosion and bioelectrosynthesis.

PubMed

Deutzmann, Jörg S; Sahin, Merve; Spormann, Alfred M

2015-04-21

Direct, mediator-free transfer of electrons between a microbial cell and a solid phase in its surrounding environment has been suggested to be a widespread and ecologically significant process. The high rates of microbial electron uptake observed during microbially influenced corrosion of iron [Fe(0)] and during microbial electrosynthesis have been considered support for a direct electron uptake in these microbial processes. However, the underlying molecular mechanisms of direct electron uptake are unknown. We investigated the electron uptake characteristics of the Fe(0)-corroding and electromethanogenic archaeon Methanococcus maripaludis and discovered that free, surface-associated redox enzymes, such as hydrogenases and presumably formate dehydrogenases, are sufficient to mediate an apparent direct electron uptake. In genetic and biochemical experiments, we showed that these enzymes, which are released from cells during routine culturing, catalyze the formation of H2 or formate when sorbed to an appropriate redox-active surface. These low-molecular-weight products are rapidly consumed by M. maripaludis cells when present, thereby preventing their accumulation to any appreciable or even detectable level. Rates of H2 and formate formation by cell-free spent culture medium were sufficient to explain the observed rates of methane formation from Fe(0) and cathode-derived electrons by wild-type M. maripaludis as well as by a mutant strain carrying deletions in all catabolic hydrogenases. Our data collectively show that cell-derived free enzymes can mimic direct extracellular electron transfer during Fe(0) corrosion and microbial electrosynthesis and may represent an ecologically important but so far overlooked mechanism in biological electron transfer. The intriguing trait of some microbial organisms to engage in direct electron transfer is thought to be widespread in nature. Consequently, direct uptake of electrons into microbial cells from solid surfaces is assumed to have a significant impact not only on fundamental microbial and biogeochemical processes but also on applied bioelectrochemical systems, such as microbial electrosynthesis and biocorrosion. This study provides a simple mechanistic explanation for frequently observed fast electron uptake kinetics in microbiological systems without a direct transfer: free, cell-derived enzymes can interact with cathodic surfaces and catalyze the formation of intermediates that are rapidly consumed by microbial cells. This electron transfer mechanism likely plays a significant role in various microbial electron transfer reactions in the environment. Copyright © 2015 Deutzmann et al.

Chemical desorption and diffusive dust chemistry

NASA Astrophysics Data System (ADS)

Dulieu, Francois; Pirronello, Valerio; Minissale, Marco; Congiu, Emanuele; Baouche, Saoud; Chaabouni, Henda; Moudens, Audrey; Accolla, Mario; Cazaux, Stephanie; Manicò, Giulio

In molecular clouds, gaseous species can accrete efficiently on the cold surfaces of dust grains. As for radical-radical reactions, the surface of the grains acts as a third body, and changes dramatically the efficiency of the reactions (i.e., H2 formation), or lowers considerably the barrier to formation (i.e., H2O synthesis) in comparison with gas phase reaction processes. These properties make dust grains efficient catalytic templates. However, the chemical role of dust grains depends on the diffusive properties of the reactive partners. Over the last years, we have developed experimental tools and methods to explore the chemistry occurring on cold (6-50K) surfaces. We have obtained some hints about the diffusivity of H on amorphous ice, and studied in detail the diffusion of O atoms. The latter species appears to have a hopping rate in the range 0.01-100 hops/sec. The diffusion rate of O atoms is dependent on the surface morphology and on the surface temperature. The diffusion law is compatible with a diffusion dominated by quantum tunnelling rather than classical thermal hopping. Using H, O, N atoms and, indirectly, OH and HCO radicals, we have begun to explore many chemical reactive networks. In this presentation, I will focus on the formation of H2O and CO2, and will propose many possible formation routes to obtain these chemical traps. The molecules formed on surfaces have a certain probability of desorbing upon their formation. This non-thermal desorption mechanism, or chemical desorption, has been proposed to explain why some molecules can be detected in the gas phase of those region where they were believed to be part of the icy mantles covering dust grains. We have shown that this process can be very efficient, but is very sensitive to the substrate and the surroundings of the reaction site, is dependent on the kind of molecule formed and its chemical pathway. In my presentation I will present how the surface coverage and the type of reaction can play a major role in the chemical desorption process. I will discuss of possible key parameters that rule this process.

Prediction of terrestrial gamma dose rate based on geological formations and soil types in the Johor State, Malaysia.

PubMed

Saleh, Muneer Aziz; Ramli, Ahmad Termizi; bin Hamzah, Khaidzir; Alajerami, Yasser; Moharib, Mohammed; Saeed, Ismael

2015-10-01

This study aims to predict and estimate unmeasured terrestrial gamma dose rate (TGDR) using statistical analysis methods to derive a model from the actual measurement based on geological formation and soil type. The measurements of TGDR were conducted in the state of Johor with a total of 3873 measured points which covered all geological formations, soil types and districts. The measurements were taken 1 m above the soil surface using NaI [Ti] detector. The measured gamma dose rates ranged from 9 nGy h(-1) to 1237 nGy h(-1) with a mean value of 151 nGy h(-1). The data have been normalized to fit a normal distribution. Tests of significance were conducted among all geological formations and soil types, using the unbalanced one way ANOVA. The results indicated strong significant differences due to the different geological formations and soil types present in Johor State. Pearson Correlation was used to measure the relations between gamma dose rate based on geological formation and soil type (D(G,S)) with the gamma dose rate based on geological formation (D(G)) or soil type (D(s)). A very good correlation was found between D(G,S) and D(G) or D(G,S) and D(s). A total of 118 pairs of geological formations and soil types were used to derive the statistical contribution of geological formations and soil types to gamma dose rates. The contribution of the gamma dose rate from geological formation and soil type were found to be 0.594 and 0.399, respectively. The null hypotheses were accepted for 83% of examined data, therefore, the model could be used to predict gamma dose rates based on geological formation and soil type information. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dynamic features of bubble induced by a nanosecond pulse laser in still and flowing water

NASA Astrophysics Data System (ADS)

Charee, Wisan; Tangwarodomnukun, Viboon

2018-03-01

Underwater laser ablation techniques have been developed and employed to synthesis nanoparticles, to texture workpiece surface and to assist the material removal in laser machining process. However, the understanding of laser-material-water interactions, bubble formation and effects of water flow on ablation performance has still been very limited. This paper thus aims at exploring the formation and collapse of bubbles during the laser ablation of silicon in water. The effects of water flow rate on bubble formation and its consequences to the laser disturbance and cut features obtained in silicon were observed by using a high speed camera. A nanosecond pulse laser emitting the laser pulse energy of 0.2-0.5 mJ was employed in the experiment. The results showed that the bubble size was found to increase with the laser pulse energy. The use of high water flow rate can importantly facilitate the ejection of ablated particles from the workpiece surface, hence resulting in less deposition to the work surface and minimizing any disturbance to the laser beam during the ablation in water. Furthermore, a clean micro-groove in silicon wafer can successfully be produced when the process was performed in the high water flow rate condition. The findings of this study could provide an essential guideline for process selection, control and improvement in the laser micro-/submicro-fabrication using the underwater technique.

Formation and Growth of New Organic Aerosol Particles over the Deepwater Horizon Oil Spill

NASA Astrophysics Data System (ADS)

Brock, C. A.; Murphy, D. M.; Bahreini, R.; Middlebrook, A. M.; De Gouw, J. A.

2011-12-01

Aerosol size distributions were measured in June 2010 downwind of the surface oil slick produced by the Deepwater Horizon oil spill in the Gulf of Mexico. Rapid condensation of partially oxidized hydrocarbons was responsible for formation of a plume of secondary organic aerosol downwind of the spill region. New particles were nucleated upwind of the freshest surface oil but downwind of oil that surfaced less than 100 hours previously. These new particles grew by condensation at rates of ~20 nm hr-1; preexisting accumulation mode particles grew by ~10 nm hr-1. The gas-phase concentration of a condensing species necessary to support the observed growth rate assuming irreversible adsorption with unit accommodation coefficient is estimated to be ~0.04-0.09 μg m-3 (~3-8 pptv). The ratio of growth rates for newly formed particles to accumulation mode particles was consistent within error limits with irreversible condensation. Because new particle formation did not occur in areas away from the <100 hr-old oil slick, these results indicate that the oxidation products of VOC species, probably C14-C16 compounds, were directly involved in the growth of the new particles. While a unique and extreme environment, the oil spill plume provides insight into similar processes that may occur in urban and industrial areas where petrochemical products are produced and consumed.

Dynamic Pattern Formation in Electron-Beam-Induced Etching [Emergent formation of dynamic topographic patterns in electron beam induced etching

DOE PAGES

Martin, Aiden A.; Bahm, Alan; Bishop, James; ...

2015-12-15

Here, we report highly ordered topographic patterns that form on the surface of diamond, span multiple length scales, and have a symmetry controlled by the precursor gas species used in electron-beam-induced etching (EBIE). The pattern formation dynamics reveals an etch rate anisotropy and an electron energy transfer pathway that is overlooked by existing EBIE models. Therefore, we, modify established theory such that it explains our results and remains universally applicable to EBIE. Furthermore, the patterns can be exploited in controlled wetting, optical structuring, and other emerging applications that require nano- and microscale surface texturing of a wide band-gap material.

TRMM Gridded Text Products

NASA Technical Reports Server (NTRS)

Stocker, Erich Franz

2007-01-01

NASA's Tropical Rainfall Measuring Mission (TRMM) has many products that contain instantaneous or gridded rain rates often among many other parameters. However, these products because of their completeness can often seem intimidating to users just desiring surface rain rates. For example one of the gridded monthly products contains well over 200 parameters. It is clear that if only rain rates are desired, this many parameters might prove intimidating. In addition, for many good reasons these products are archived and currently distributed in HDF format. This also can be an inhibiting factor in using TRMM rain rates. To provide a simple format and isolate just the rain rates from the many other parameters, the TRMM product created a series of gridded products in ASCII text format. This paper describes the various text rain rate products produced. It provides detailed information about parameters and how they are calculated. It also gives detailed format information. These products are used in a number of applications with the TRMM processing system. The products are produced from the swath instantaneous rain rates and contain information from the three major TRMM instruments: radar, radiometer, and combined. They are simple to use, human readable, and small for downloading.

Tectonics, climate and mountain building in the forearc of southern Peru recorded in the 10Be chronology of low-relief surface abandonment

NASA Astrophysics Data System (ADS)

Hall, S. R.; Farber, D.; Audin, L.; Finkel, R. C.

2009-12-01

Regional low-relief surfaces have long been recognized as key features to understanding the response of landscapes to surface uplift. The canonical models of low-relief surface formation involve an extended period of tectonic quiescence during which, the fluvial systems bevel the landscape to a uniform elevation. This quiescent period is punctuated by a period(s) of surface uplift, which causes fluvial incision thereby abandoning the low-relief landscape. Over time, as rivers continue to incise in response to changes in sediment supply, river discharge, and base level fall, pieces of the relict low-relief landscape are left as abandoned remnants stranded above active channels. By determining the age of abandoned surfaces, previous workers have identified the onset of a change in the tectonic or climatic setting. One key assumption of this model is that the low-relief surfaces are truly abandoned with no current processes further acting on the surface. To improve our understanding of the underlying assumptions and problems of low-relief surface formation, we have used detailed mapping and absolute dating with cosmogenic 10Be to investigate surfaces in the hyperarid forearc region of southern Peru between ~14° and 18°S. Within this region, marine terraces and strath terraces reflect Plio-Pleistocene surface uplift, and together with the hyperarid climate, ongoing surface uplift provides a perfect natural laboratory to examine the processes affecting low-relief surface abandonment and preservation. With our new chronology we address: 1) the space and time correlations of surfaces, 2) incision rates of streams in response to base-level fall, and 3) surface erosion rates. Multiple surfaces have yielded 10Be surface abandonment ages that span >2 Ma - ~35 ka. While most of the surfaces we have dated are considerably less than 1 Ma, we have located two surfaces which are likely older than 2 Ma and constrain regional erosion rates to be <0.5mm/yr. Where the surface age and elevation relative to current base level are known, we can estimate incision (uplift) rates of ~0.1-0.3mm/yr. These ages, erosion rates, and uplift rates suggest that the hyperarid forearc landscape has been recently modified (surface uplift, climate events), while paradoxically, very little erosion is occurring on these surfaces. The four surface abandonment age clusters we observe correlate with cold wet periods preceding deglaciation on the Altiplano. Thus, we suggest that the recorded chronology of Pleistocene surface abandonment results from the interaction and linkage of surface uplift in the forearc, to specific climatic periods in the high Andes that produce high discharge through the fluvial system.

Enhancement of peptide bond formation by polyribonucleotides on clay surfaces in fluctuating environments

NASA Technical Reports Server (NTRS)

White, D. H.; Erickson, J. C.

1981-01-01

The selective effects of polyribonucleotides on the formation of glycine peptide bonds in glycine on clay surfaces are investigated as a model for a template mechanism for the effects of polynucleotides on peptide bond formation. Free oligoglycine yields were determined for the cycling reaction of glycine in the presence and absence of clay and polyribonucleotides or polydeoxyribonucleotides. The polyribonucleotides are observed to lead to increases of up to fourfold increases in oligoglycine formed, with greater enhancements for poly-G nucleotides than for poly-A, poly-U and poly-C, indicating a codonic bias. Polydeoxyribonucleotides are found to provide no enhancement in peptide formation rates, and yields were also greatly reduced in the absence of clay. A mechanism for peptide synthesis is proposed which involves the activation of glycine on the clay surface, followed by the formation of esters between glycine and the 2-prime OH groups of the polyribonucleotide and peptide bonds between adjacent amino acyl esters. It is pointed out that if this mechanism is correct, it may provide a basis for a direct template translation process, which would produce a singlet genetic code.

Formation and interpretation of eskers beneath retreating ice sheets

NASA Astrophysics Data System (ADS)

Creyts, T. T.; Hewitt, I.

2017-12-01

The retreat of the ice sheets during the Pleistocene left large and spectacular subglacial features exposed. Understanding these features gives us insight into how the ice sheets retreated, how meltwater influenced retreat, and can help inform our understanding of potential future rates of ice sheet retreat. Among these features, eskers, long sinuous ridges primarily composed of clastic sediments, lack a detailed explanation of how surface melt rates and ice sheet retreat rates influence their growth and spatial distribution. Here, we develop a theory for esker formation based on the initial work of Rothlisberger modified for sediment transport and inclusion of surface meltwater forcing. The primary subglacial ingredients include water flow through subglacial tunnels with the addition of mass balances for sediment transport. We show how eskers when water flow slows below a critical stress for sediment motion. This implies that eskers are deposited in a localized region near the snout of the ice sheet. Our findings suggest that very long eskers form sequentially as the ice front retreats. The position of the esker follows the path of the channel mouth through time, which does not necessarily coincide with the instantaneous route of the feeding channel. However, in most cases, we expect those locations to be similar. The role of surface meltwater and the climatology associated with the forcing is crucial to the lateral spacing of the eskers. We predict that high surface melt rates lead to narrower catchments but that the greater extent of the ablation area means that channels are likely larger. At the same time, for a given channel size (and hence sediment flux), the size of a deposited esker depends on a margin retreat rate. Hence, the size of the eskers is related delicately to the balance between surface melt rates and margin retreat rates. We discuss how our theory can be combined with observed esker distributions to infer the relationship between these two rates and help understand the melt history of ice sheets.

Extracellular Enzymes Facilitate Electron Uptake in Biocorrosion and Bioelectrosynthesis

PubMed Central

Deutzmann, Jörg S.; Sahin, Merve

2015-01-01

ABSTRACT Direct, mediator-free transfer of electrons between a microbial cell and a solid phase in its surrounding environment has been suggested to be a widespread and ecologically significant process. The high rates of microbial electron uptake observed during microbially influenced corrosion of iron [Fe(0)] and during microbial electrosynthesis have been considered support for a direct electron uptake in these microbial processes. However, the underlying molecular mechanisms of direct electron uptake are unknown. We investigated the electron uptake characteristics of the Fe(0)-corroding and electromethanogenic archaeon Methanococcus maripaludis and discovered that free, surface-associated redox enzymes, such as hydrogenases and presumably formate dehydrogenases, are sufficient to mediate an apparent direct electron uptake. In genetic and biochemical experiments, we showed that these enzymes, which are released from cells during routine culturing, catalyze the formation of H2 or formate when sorbed to an appropriate redox-active surface. These low-molecular-weight products are rapidly consumed by M. maripaludis cells when present, thereby preventing their accumulation to any appreciable or even detectable level. Rates of H2 and formate formation by cell-free spent culture medium were sufficient to explain the observed rates of methane formation from Fe(0) and cathode-derived electrons by wild-type M. maripaludis as well as by a mutant strain carrying deletions in all catabolic hydrogenases. Our data collectively show that cell-derived free enzymes can mimic direct extracellular electron transfer during Fe(0) corrosion and microbial electrosynthesis and may represent an ecologically important but so far overlooked mechanism in biological electron transfer. PMID:25900658

Acoustic Effects in Classical Nucleation Theory

NASA Technical Reports Server (NTRS)

Baird, J. K.; Su, C.-H.

2017-01-01

The effect of sound wave oscillations on the rate of nucleation in a parent phase can be calculated by expanding the free energy of formation of a nucleus of the second phase in powers of the acoustic pressure. Since the period of sound wave oscillation is much shorter than the time scale for nucleation, the acoustic effect can be calculated as a time average of the free energy of formation of the nucleus. The leading non-zero term in the time average of the free energy is proportional to the square of the acoustic pressure. The Young-Laplace equation for the surface tension of the nucleus can be used to link the time average of the square of the pressure in the parent phase to its time average in the nucleus of the second phase. Due to the surface tension, the pressure in the nuclear phase is higher than the pressure in the parent phase. The effect is to lower the free energy of formation of the nucleus and increase the rate of nucleation.

Modeling the Formation of CO2 Frost Halos on the South Polar Residual Cap of Mars

NASA Astrophysics Data System (ADS)

Becerra, P.; Byrne, S.; HiRISE Team

2011-03-01

We introduce a model for the formation of bright halos seen by HiRISE on the edges of scarps and "swiss cheese" features in the south polar residual cap of Mars. We propose that they are formed from differences between the sublimation rates of sloped and flat surfaces.

A Technique for the Microstructural Examination of Polycrystalline Graphites

DTIC Science & Technology

1959-02-01

dichromate in concentrated phosphoric acid . This etchsnt reacted quite readily with the graphite surface, yet at a rate that was...formation of lamellar compounds, and carbide formation at high temperatues . Of the three classes of reaction, oxidation seems to...reagents and conditions were directed toward preliminary studies of such chemical oxidants as potassium dichromate-phosphoric acid mixtures

Geohydrology and susceptibility of major aquifers to surface contamination in Alabama, area 7

USGS Publications Warehouse

Mooty, W.S.

1987-01-01

The geohydrology and susceptibility of the seven major aquifers to surface contamination in Area 7 - Bibb, Dallas, Hale, Perry, and Wilcox Counties, are described. Aquifers in the northern part of the study area are in Paleozoic limestones and dolomite formations. Deposits in the central part of the study area are predominately of Cretaceous age and contain the Coker, Gordo, and Eutaw aquifers. Although the southern part of the study area has many deposits of Tertiary age, the Ripley Formation of Cretaceous age is the major aquifer. Contamination of any of the major aquifers is improbable because the majority of the recharge area for the primary aquifers is woodland, pasture, or farmland. Downdip from their outcrops, the major aquifers in the study area are protected from land surface contamination by relatively impermeable layers of clay and chalk. The aquifers that are highly susceptible to contamination are the ones in the limestone and dolomite formations in northern Bibb County. Sinkholes exist in the recharge area of these formations and could provide a direct link for contaminates from the land surface to the water table. An area northeast of the Selma well field is also highly susceptible to contamination. The Eutaw Formation in this area is overlain by alluvial deposits that could increase recharge to the aquifer by slowing the runoff rate of surface water. (USGS)

Definition of hydraulic stability of KVGM-100 hot-water boiler and minimum water flow rate

NASA Astrophysics Data System (ADS)

Belov, A. A.; Ozerov, A. N.; Usikov, N. V.; Shkondin, I. A.

2016-08-01

In domestic power engineering, the methods of quantitative and qualitative-quantitative adjusting the load of the heat supply systems are widely distributed; furthermore, during the greater part of the heating period, the actual discharge of network water is less than estimated values when changing to quantitative adjustment. Hence, the hydraulic circuits of hot-water boilers should ensure the water velocities, minimizing the scale formation and excluding the formation of stagnant zones. The results of the calculations of hot-water KVGM-100 boiler and minimum water flow rate for the basic and peak modes at the fulfillment of condition of the lack of surface boil are presented in the article. The minimal flow rates of water at its underheating to the saturation state and the thermal flows in the furnace chamber were defined. The boiler hydraulic calculation was performed using the "Hydraulic" program, and the analysis of permissible and actual velocities of the water movement in the pipes of the heating surfaces was carried out. Based on the thermal calculations of furnace chamber and thermal- hydraulic calculations of heating surfaces, the following conclusions were drawn: the minimum velocity of water movement (by condition of boiling surface) at lifting movement of environment increases from 0.64 to 0.79 m/s; it increases from 1.14 to 1.38 m/s at down movement of environmental; the minimum water flow rate by the boiler in the basic mode (by condition of the surface boiling) increased from 887 t/h at the load of 20% up to 1074 t/h at the load of 100%. The minimum flow rate is 1074 t/h at nominal load and is achieved at the pressure at the boiler outlet equal to 1.1 MPa; the minimum water flow rate by the boiler in the peak mode by condition of surface boiling increases from 1669 t/h at the load of 20% up to 2021 t/h at the load of 100%.

Characterizing droplet kinetic energy applied by moving spray-plate center pivot irrigation sprinklers

USDA-ARS?s Scientific Manuscript database

The kinetic energy of discrete drops impacting a bare soil surface is generally observed to lead to a drastic reduction in water infiltration rate due to soil surface seal formation. Under center pivot sprinkler irrigation, kinetic energy transferred to the soil prior to crop canopy development can...

HIGH STAR FORMATION RATES IN TURBULENT ATOMIC-DOMINATED GAS IN THE INTERACTING GALAXIES IC 2163 AND NGC 2207

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elmegreen, Bruce G.; Kaufman, Michele; Bournaud, Frédéric

CO observations of the interacting galaxies IC 2163 and NGC 2207 are combined with HI, H α , and 24 μ m observations to study the star formation rate (SFR) surface density as a function of the gas surface density. More than half of the high-SFR regions are HI dominated. When compared to other galaxies, these HI-dominated regions have excess SFRs relative to their molecular gas surface densities but normal SFRs relative to their total gas surface densities. The HI-dominated regions are mostly located in the outer part of NGC 2207 where the HI velocity dispersion is high, 40–50 kmmore » s{sup −1}. We suggest that the star-forming clouds in these regions have envelopes at lower densities than normal, making them predominantly atomic, and cores at higher densities than normal because of the high turbulent Mach numbers. This is consistent with theoretical predictions of a flattening in the density probability distribution function for compressive, high Mach number turbulence.« less

Dynamic oxidation behavior of TD-NiCr alloy with different surface pretreatments

NASA Technical Reports Server (NTRS)

Young, C. T.; Tenney, D. R.; Herring, H. W.

1975-01-01

Oxidation tests of TD-NiCr alloy with different surface pretreatments were conducted in a Mach-5 arc-jet at 1200 C and 0.002 lb/sec flowing air environment. The mechanisms responsible for the observed oxidation behavior are examined. The presence of atomic oxygen in the air stream plays a significant role in determining the oxidation characteristic of the alloy. The rate of Cr2O3 vaporization by formation of volatile CrO3 is greatly enhanced by the flowing conditions. The typical microstructure of oxides formed in the dynamic tests consists of an external layer of NiO with a porous mushroom-type morphology, an intermediate layer of NiO and Cr2O3 oxide mixture, and a continuous inner layer of Cr2O3 in contact with the Cr-depleted alloy substrate. Three basic processes underlying the formation of mushroom-type NiO are identified and discussed. The oxidation rate is determined by the rate of vaporization of NiO. Surface pretreatment has a significant effect on the oxidation behavior of the alloy in the early stage of oxidation, but becomes less important as exposure time increases. Mechanical polishing induces surface recrystallization, but promotes the concurrence of external growth of NiO and internal oxidation of the alloy in the dynamic atmosphere.

Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

NASA Astrophysics Data System (ADS)

Reddy, Michael M.

2012-08-01

Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10-4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10-4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

USGS Publications Warehouse

Reddy, Michael M.

2012-01-01

Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10−4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10−4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

Kinetics of the sorption of triterpene saponin by hypercrosslinked polystyrene

NASA Astrophysics Data System (ADS)

Mironenko, N. V.; Brezhneva, T. A.; Selemenev, V. F.

2013-03-01

The kinetics of sorption of triterpene saponin by the polymer sorbent NM-200 is considered. The influence of the surface activity of glycoside on the rate of formation and structure of the adsorption layer on the sorbent's surface is established. The rate-determining step of sorption is found to be diffusion into the sorbent grain. The value of the activation energy demonstrates the determining role of dispersion forces in the interaction between triterpene saponin and the polymer sorbent MN-200.

The distribution of star formation and metals in the low surface brightness galaxy UGC 628

NASA Astrophysics Data System (ADS)

Young, J. E.; Kuzio de Naray, Rachel; Wang, Sharon X.

2015-09-01

We introduce the MUSCEL Programme (MUltiwavelength observations of the Structure, Chemistry and Evolution of LSB galaxies), a project aimed at determining the star-formation histories of low surface brightness galaxies. MUSCEL utilizes ground-based optical spectra and space-based UV and IR photometry to fully constrain the star-formation histories of our targets with the aim of shedding light on the processes that led low surface brightness galaxies down a different evolutionary path from that followed by high surface brightness galaxies, such as our Milky Way. Here we present the spatially resolved optical spectra of UGC 628, observed with the VIRUS-P IFU at the 2.7-m Harlen J. Smith Telescope at the McDonald Observatory, and utilize emission-line diagnostics to determine the rate and distribution of star formation as well as the gas-phase metallicity and metallicity gradient. We find highly clustered star formation throughout UGC 628, excluding the core regions, and a log(O/H) metallicity around -4.2, with more metal-rich regions near the edges of the galactic disc. Based on the emission-line diagnostics alone, the current mode of star formation, slow and concentrated in the outer disc, appears to have dominated for quite some time, although there are clear signs of a much older stellar population formed in a more standard inside-out fashion.

Cell/surface interactions on laser micro-textured titanium-coated silicon surfaces.

PubMed

Mwenifumbo, Steven; Li, Mingwei; Chen, Jianbo; Beye, Aboubaker; Soboyejo, Wolé

2007-01-01

This paper examines the effects of nano-scale titanium coatings, and micro-groove/micro-grid patterns on cell/surface interactions on silicon surfaces. The nature of the cellular attachment and adhesion to the coated/uncoated micro-textured surfaces was elucidated by the visualization of the cells and relevant cytoskeletal & focal adhesion proteins through scanning electron microscopy and immunofluorescence staining. Increased cell spreading and proliferation rates are observed on surfaces with 50 nm thick Ti coatings. The micro-groove geometries have been shown to promote contact guidance, which leads to reduced scar tissue formation. In contrast, smooth surfaces result in random cell orientations and the increased possibility of scar tissue formation. Immunofluorescence cell staining experiments also reveal that the actin stress fibers are aligned along the groove dimensions, with discrete focal adhesions occurring along the ridges, within the grooves and at the ends of the cell extensions. The implications of the observed cell/surface interactions are discussed for possible applications of silicon in implantable biomedical systems.

Surface-Bound Intermediates in Low-Temperature Methanol Synthesis on Copper. Participants and Spectators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Yong; Mei, Donghai; Peden, Charles H.F.

The reactivity of surface adsorbed species present on copper catalysts during methanol synthesis at low temperatures was studied by simultaneous infrared spectroscopy (IR) and mass spectroscopy (MS) measurements during “titration” (transient surface reaction) experiments with isotopic tracing. The results show that adsorbed formate is a major bystander species present on the surface under steady-state methanol synthesis reaction conditions, but it cannot be converted to methanol by reaction with pure H 2, nor with H 2 plus added water. Formate-containing surface adlayers for these experiments were produced during steady state catalysis in (a) H 2:CO 2 (with substantial formate coverage) andmore » (b) moist H 2:CO (with no IR visible formate species). Both these reaction conditions produce methanol at steady state with relatively high rates. Adlayers containing formate were also produced by (c) formic acid adsorption. Various "titration" gases were used to probe these adlayers at modest temperatures (T = 410-450K) and 6 bar total pressure. Methanol gas (up to ~1% monolayer equivalent) was produced in "titration" from the H 2:CO 2 catalytic adlayers by H 2 plus water, but not by dry hydrogen. The decay in the formate IR features accelerated in the presence of added water vapor. The H 2:CO:H 2O catalytic adlayer produced similar methanol titration yields in H 2 plus water but showed no surface formate features in IR (less than 0.2% monolayer coverage). Finally, formate from formic acid chemisorption produced no methanol under any titration conditions. Even under (H 2:CO 2) catalytic reaction conditions, isotope tracing showed that pre-adsorbed formate from formic acid did not contribute to the methanol produced. Although non-formate intermediates exist during low temperature methanol synthesis on copper which can be converted to methanol gas by titration with pure H 2 plus water in sufficient quantities for that intermediate to be observable by IR, formate itself is only a "spectator" in this reaction and gives no observable methanol upon any titration we performed with H 2 or H 2 plus water.« less

Surface functional group dependent apatite formation on bacterial cellulose microfibrils network in a simulated body fluid.

PubMed

Nge, Thi Thi; Sugiyama, Junji

2007-04-01

The apatite forming ability of biopolymer bacterial cellulose (BC) has been investigated by soaking different BC specimens in a simulated body fluid (1.5 SBF) under physiological conditions, at 37 degrees C and pH 7.4, mimicking the natural process of apatite formation. From ATR-FTIR spectra and ICP-AES analysis, the crystalline phase nucleated on the BC microfibrils surface was calcium deficient carbonated apatite through initial formation of octacalcium phosphate (OCP) or OCP like calcium phosphate phase regardless of the substrates. Morphology of the deposits from SEM, FE-SEM, and TEM observations revealed the fine structure of thin film plates uniting together to form apatite globules of various size (from <1 mum to 3 mum) with respect to the substrates. Surface modification by TEMPO (2,2,6,6-tetramethylpyperidine-1-oxyl)-mediated oxidation, which can readily form active carboxyl functional groups upon selective oxidation of primary hydroxyl groups on the surface of BC microfibrils, enhanced the rate of apatite nucleation. Ion exchanged treatment with calcium chloride solution after TEMPO-mediated oxidation was found to be remarkably different from other BC substrates with the highest deposit weight and the smallest apatite globules size. The role of BC substrates to induce mineralization rate differs according to the nature of the BC substrates, which strongly influences the growth behavior of the apatite crystals. (c) 2006 Wiley Periodicals, Inc.

Study of TLIPSS formation on different metals and alloys and their selective etching

NASA Astrophysics Data System (ADS)

Dostovalov, Alexandr V.; Korolkov, Victor P.; Terentiev, Vadim S.; Okotrub, Konstantin A.; Dultsev, Fedor N.; Nemykin, Anton; Babin, Sergey A.

2017-02-01

Experimental investigation of thermochemical laser-induced periodic surface structures (TLIPSS) formation on metal films (Ti, Cr, Ni, NiCr) at different processing conditions is presented. The hypothesis that the TLIPSS formation depends significantly on parabolic rate constant for oxide thin film growth is discussed. Evidently, low value of this parameter for Ni is the reason of TLIPSS absence on Ni and NiCr film with low Cr content. The effect of simultaneous ablative (with period ≍λ) and thermochemical (with period ≍λ) LIPSS formation was observed. The formation of structures after TLIPSS selective etching was demonstrated.

A microphysical parameterization of aqSOA and sulfate formation in clouds

NASA Astrophysics Data System (ADS)

McVay, Renee; Ervens, Barbara

2017-07-01

Sulfate and secondary organic aerosol (cloud aqSOA) can be chemically formed in cloud water. Model implementation of these processes represents a computational burden due to the large number of microphysical and chemical parameters. Chemical mechanisms have been condensed by reducing the number of chemical parameters. Here an alternative is presented to reduce the number of microphysical parameters (number of cloud droplet size classes). In-cloud mass formation is surface and volume dependent due to surface-limited oxidant uptake and/or size-dependent pH. Box and parcel model simulations show that using the effective cloud droplet diameter (proportional to total volume-to-surface ratio) reproduces sulfate and aqSOA formation rates within ≤30% as compared to full droplet distributions; other single diameters lead to much greater deviations. This single-class approach reduces computing time significantly and can be included in models when total liquid water content and effective diameter are available.

Experimental study of fs-laser induced sub-100-nm periodic surface structures on titanium.

PubMed

Nathala, Chandra S R; Ajami, Ali; Ionin, Andrey A; Kudryashov, Sergey I; Makarov, Sergey V; Ganz, Thomas; Assion, Andreas; Husinsky, Wolfgang

2015-03-09

In this work the formation of laser-induced periodic surface structures (LIPSS) on a titanium surface upon irradiation by linearly polarized femtosecond (fs) laser pulses with a repetition rate of 1 kHz in air environment was studied experimentally. In particular, the dependence of high-spatial-frequency-LIPSS (HSFL) characteristics on various laser parameters: fluence, pulse number, wavelength (800 nm and 400 nm), pulse duration (10 fs - 550 fs), and polarization was studied in detail. In comparison with low-spatial-frequency-LIPSS (LSFL), the HSFL emerge at a much lower fluence with orientation perpendicular to the ridges of the LSFL. It was observed that these two types of LIPSS demonstrate different fluence, shot number and wavelength dependencies, which suggest their origin is different. Therefore, the HSFL formation mechanism cannot be described by the widely accepted interference model developed for describing LSFL formation.

The critical density for star formation in HII galaxies

NASA Technical Reports Server (NTRS)

Taylor, Christopher L.; Brinks, Elias; Skillman, Evan D.

1993-01-01

The star formation rate (SFR) in galaxies is believed to obey a power law relation with local gas density, first proposed by Schmidt (1959). Kennicutt (1989) has shown that there is a threshold density above which star formation occurs, and for densities at or near the threshold density, the DFR is highly non-linear, leading to bursts of star formation. Skillman (1987) empirically determined this threshold for dwarf galaxies to be approximately 1 x 10(exp 21) cm(exp -2), at a linear resolution of 500pc. During the course of our survey for HI companion clouds to HII galaxies, we obtained high resolution HI observations of five nearby HII galaxies. HII galaxies are low surface brightness, rich in HI, and contain one or a few high surface brightness knots whose optical spectra resemble those of HII regions. These knots are currently experiencing a burst of star formation. After Kennicutt (1989) we determine the critical density for star formation in the galaxies, and compare the predictions with radio and optical data.

Mechanism and kinetics of the electrocatalytic reaction responsible for the high cost of hydrogen fuel cells.

PubMed

Cheng, Tao; Goddard, William A; An, Qi; Xiao, Hai; Merinov, Boris; Morozov, Sergey

2017-01-25

The sluggish oxygen reduction reaction (ORR) is a major impediment to the economic use of hydrogen fuel cells in transportation. In this work, we report the full ORR reaction mechanism for Pt(111) based on Quantum Mechanics (QM) based Reactive metadynamics (RμD) simulations including explicit water to obtain free energy reaction barriers at 298 K. The lowest energy pathway for 4 e - water formation is: first, *OOH formation; second, *OOH reduction to H 2 O and O*; third, O* hydrolysis using surface water to produce two *OH and finally *OH hydration to water. Water formation is the rate-determining step (RDS) for potentials above 0.87 Volt, the normal operating range. Considering the Eley-Rideal (ER) mechanism involving protons from the solvent, we predict the free energy reaction barrier at 298 K for water formation to be 0.25 eV for an external potential below U = 0.87 V and 0.41 eV at U = 1.23 V, in good agreement with experimental values of 0.22 eV and 0.44 eV, respectively. With the mechanism now fully understood, we can use this now validated methodology to examine the changes upon alloying and surface modifications to increase the rate by reducing the barrier for water formation.

Highly concentrated phenolic wastewater treatment by heterogeneous and homogeneous photocatalysis: mechanism study by FTIR-ATR.

PubMed

Araña, J; Tello-Rendón, E; Doña-Rodríguez, J M; Campo, C V; Herrera-Melidán, J A; González-Díaz; Pérez-Peña, J

2001-01-01

The degradation of high phenol concentrations (1 g/L) in water solutions by TiO2 photocatalysis and the photo-Fenton reaction has been studied. From the obtained data it may be suggested that degradation of phenol by TiO2-UV takes place onto the catalyst surface by means of peroxo-compounds formation. At low phenol concentrations other mechanism, the insertion of OH. radicals, may be favored. On the other hand, highly concentrated phenol aqueous solutions treatment by the photo-Fenton reaction gives rise to the formation of polyphenolic polymers. These seem to reduce the process rate. Degradation intermediates have been identified by HPLC and FTIR. The FTIR study of the catalyst surface has shown infrared bands attributable to different chemisorbed peroxo-compounds, formates, ortho-formates and carboxylates that can inactivate the catalyst.

Surface Formation and Preservation of Very-Low-Porosity Thin Crusts ( "Glazes") at the WAIS Divide Site, West Antarctica

NASA Astrophysics Data System (ADS)

Fegyveresi, J. M.; Alley, R. B.; Muto, A.; Spencer, M. K.; Orsi, A. J.

2014-12-01

Observations at the WAIS Divide site show that near-surface snow is strongly altered by weather-related processes, producing features that are recognizable in the ice core. Prominent reflective "glazed" surface crusts develop frequently during the summer. Observations during austral summers 2008-09 through 2012-13, supplemented by Automated Weather Station data with insolation sensors, documented formation of such crusts during relatively low-wind, low-humidity, clear-sky periods with intense daytime sunshine. After formation, such glazed surfaces typically developed cracks in a polygonal pattern with few-meter spacing, likely from thermal contraction at night. Cracking was commonest when several clear days occurred in succession, and was generally followed by surface hoar growth. Temperature and radiation observations showed that solar heating often warmed the near-surface snow above the air temperature, contributing to mass transfer favoring crust formation. Subsequent investigation of the WDC06A deep ice core revealed that preserved surface crusts were seen in the core at an average rate of ~4.3 ± 2 yr-1 over the past 5500 years. They are about 40% more common in layers deposited during summers than during winters. The total summertime crust frequency also covaried with site temperature, with more present during warmer periods. We hypothesize that the mechanism for glaze formation producing single-grain-thick very-low-porosity thin crusts (i.e. "glazes") involves additional in-filling of open pores. The thermal conductivity of ice greatly exceeds that of air, so heat transport in firn is primarily conductive. Because heat flow is primarily through the grain structure, for a temperature inversion (colder upper surface) beneath a growing thin crust at the upper surface, pores will be colder than interconnected grains, favoring mass transport into those pores. Transport may occur by vapor, surface, or volume diffusion, although vapor diffusion and surface transport in pre-melted films are likely to dominate. On-site wintertime observations have not been made, but crust formation during winter may be favored by greater wind-packing, large meteorologically-forced temperature changes reaching as high as -15oC in midwinter, and perhaps longer intervals of surface stability.

Control of surface defects on plasma-MIG hybrid welds in cryogenic aluminum alloys

NASA Astrophysics Data System (ADS)

Lee, Hee-Keun; Chun, Kwang-San; Park, Sang-Hyeon; Kang, Chung-Yun

2015-07-01

Lately, high production rate welding processes for Al alloys, which are used as LNG FPSO cargo containment system material, have been developed to overcome the limit of installation and high rework rates. In particular, plasma-metal inert gas (MIG) hybrid (PMH) welding can be used to obtain a higher deposition rate and lower porosity, while facilitating a cleaning effect by preheating and post heating the wire and the base metal. However, an asymmetric undercut and a black-colored deposit are created on the surface of PMH weld in Al alloys. For controlling the surface defect formation, the wire feeding speed and nozzle diameter in the PMH weld was investigated through arc phenomena with high-speed imaging and metallurgical analysis.

A local leaky-box model for the local stellar surface density-gas surface density-gas phase metallicity relation

NASA Astrophysics Data System (ADS)

Zhu, Guangtun Ben; Barrera-Ballesteros, Jorge K.; Heckman, Timothy M.; Zakamska, Nadia L.; Sánchez, Sebastian F.; Yan, Renbin; Brinkmann, Jonathan

2017-07-01

We revisit the relation between the stellar surface density, the gas surface density and the gas-phase metallicity of typical disc galaxies in the local Universe with the SDSS-IV/MaNGA survey, using the star formation rate surface density as an indicator for the gas surface density. We show that these three local parameters form a tight relationship, confirming previous works (e.g. by the PINGS and CALIFA surveys), but with a larger sample. We present a new local leaky-box model, assuming star-formation history and chemical evolution is localized except for outflowing materials. We derive closed-form solutions for the evolution of stellar surface density, gas surface density and gas-phase metallicity, and show that these parameters form a tight relation independent of initial gas density and time. We show that, with canonical values of model parameters, this predicted relation match the observed one well. In addition, we briefly describe a pathway to improving the current semi-analytic models of galaxy formation by incorporating the local leaky-box model in the cosmological context, which can potentially explain simultaneously multiple properties of Milky Way-type disc galaxies, such as the size growth and the global stellar mass-gas metallicity relation.

Predicting soil formation on the basis of transport-limited chemical weathering

NASA Astrophysics Data System (ADS)

Yu, Fang; Hunt, Allen Gerhard

2018-01-01

Soil production is closely related to chemical weathering. It has been shown that, under the assumption that chemical weathering is limited by solute transport, the process of soil production is predictable. However, solute transport in soil cannot be described by Gaussian transport. In this paper, we propose an approach based on percolation theory describing non-Gaussian transport of solute to predict soil formation (the net production of soil) by considering both soil production from chemical weathering and removal of soil from erosion. Our prediction shows agreement with observed soil depths in the field. Theoretical soil formation rates are also compared with published rates predicted using soil age-profile thickness (SAST) method. Our formulation can be incorporated directly into landscape evolution models on a point-to-point basis as long as such models account for surface water routing associated with overland flow. Further, our treatment can be scaled-up to address complications associated with continental-scale applications, including those from climate change, such as changes in vegetation, or surface flow organization. The ability to predict soil formation rates has implications for understanding Earth's climate system on account of the relationship to chemical weathering of silicate minerals with the associated drawdown of atmospheric carbon, but it is also important in geomorphology for understanding landscape evolution, including for example, the shapes of hillslopes, and the net transport of sediments to sedimentary basins.

Star Formation and Gas Dynamics in Galactic Disks: Physical Processes and Numerical Models

NASA Astrophysics Data System (ADS)

Ostriker, Eve C.

2011-04-01

Star formation depends on the available gaseous ``fuel'' as well as galactic environment, with higher specific star formation rates where gas is predominantly molecular and where stellar (and dark matter) densities are higher. The partition of gas into different thermal components must itself depend on the star formation rate, since a steady state distribution requires a balance between heating (largely from stellar UV for the atomic component) and cooling. In this presentation, I discuss a simple thermal and dynamical equilibrium model for the star formation rate in disk galaxies, where the basic inputs are the total surface density of gas and the volume density of stars and dark matter, averaged over ~kpc scales. Galactic environment is important because the vertical gravity of the stars and dark matter compress gas toward the midplane, helping to establish the pressure, and hence the cooling rate. In equilibrium, the star formation rate must evolve until the gas heating rate is high enough to balance this cooling rate and maintain the pressure imposed by the local gravitational field. In addition to discussing the formulation of this equilibrium model, I review the current status of numerical simulations of multiphase disks, focusing on measurements of quantities that characterize the mean properties of the diffuse ISM. Based on simulations, turbulence levels in the diffuse ISM appear relatively insensitive to local disk conditions and energetic driving rates, consistent with observations. It remains to be determined, both from observations and simulations, how mass exchange processes control the ratio of cold-to-warm gas in the atomic ISM.

The influence of the cluster environment on the star formation efficiency of 12 Virgo spiral galaxies

NASA Astrophysics Data System (ADS)

Vollmer, B.; Wong, O. I.; Braine, J.; Chung, A.; Kenney, J. D. P.

2012-07-01

The influence of the environment on gas surface density and star formation efficiency of cluster spiral galaxies is investigated. We extend previous work on radial profiles by a pixel-to pixel analysis looking for asymmetries due to environmental interactions. The star formation rate is derived from GALEX UV and Spitzer total infrared data based on the 8, 24, 70, and 160 μm data. As in field galaxies, the star formation rate for most Virgo galaxies is approximately proportional to the molecular gas mass. Except for NGC 4438, the cluster environment does not affect the star formation efficiency with respect to the molecular gas. Gas truncation is not associated with major changes in the total gas surface density distribution of the inner disk of Virgo spiral galaxies. In three galaxies (NGC 4430, NGC 4501, and NGC 4522), possible increases in the molecular fraction and the star formation efficiency with respect to the total gas, of factors of 1.5 to 2, are observed on the windward side of the galactic disk. A significant increase of the star formation efficiency with respect to the molecular gas content on the windward side of ram pressure-stripped galaxies is not observed. The ram-pressure stripped extraplanar gas of 3 highly inclined spiral galaxies (NGC 4330, NGC 4438, and NGC 4522) shows a depressed star formation efficiency with respect to the total gas, and one of them (NGC 4438) shows a depressed rate even with respect to the molecular gas. The interpretation is that stripped gas loses the gravitational confinement and associated pressure of the galactic disk, and the gas flow is diverging, so the gas density decreases and the star formation rate drops. We found two such regions of low star formation efficiency in the more face-on galaxies NGC 4501 and NGC 4654 which are both undergoing ram pressure stripping. These regions show low radio continuum emission or unusually steep radio spectral index. However, the stripped extraplanar gas in one highly inclined galaxy (NGC 4569) shows a normal star formation efficiency with respect to the total gas. We propose this galaxy is different because it is observed long after peak pressure, and its extraplanar gas is now in a converging flow as it resettles back into the disk. Appendices are available in electronic form http://www.aanda.org

Sedimentation, bioturbation, and sedimentary fabric evolution on a modern mesotidal mudflat: A multi-tracer study of processes, rates, and scales

NASA Astrophysics Data System (ADS)

Bentley, Samuel J.; Swales, Andrew; Pyenson, Benjamin; Dawe, Justin

2014-03-01

A study of muddy tidal-flat sedimentation and bioturbation was undertaken in the Waitetuna Arm of Raglan Harbor, New Zealand, to evaluate the physical and biological processes that control cycling of sediment between the intertidal seabed and sediment-water interface, and also the formation of tidal flat sedimentary fabric and fine-scale stratigraphy. Cores were collected along an intertidal transect, and analyzed for sedimentary fabric, 210Pb and 7Be radiochemical distributions, and grain size. At the same locations, a new approach for time-series core-X-radiography study was undertaken (spanning 191 days), using magnetite-rich sand as a tracer for sedimentation and bioturbation processes in shallow tidal flat sediments. Sedimentary fabric consists of a shallow stratified layer overlying a deeper zone of intensely bioturbated shelly mud. Bioadvection mixes the deeper zone and contributes fine sediment to the surface stratified layer, via biodeposition. Physical resuspension and deposition of surface muds by wave and tidal flow are also likely contributors to formation of the surficial stratified layer, but physical stratification is not observed below this depth. The deliberate tracer study allowed calculation of bioadvection rates that control strata formation, and can be used to model diagenetic processes. Results suggest that the upper ˜15 cm of seabed can be fully mixed over timescales <1.75 y. Such mixing will erase pre-existing sedimentary fabric and transport buried sediment and chemical compounds back to the tidal-flat surface. Shallow biodiffusion also exists, but produces much slower and shallower mass transport. Best fits for 210Pb profiles using a diagenetic bioadvection/sedimentation model and independently measured tiered bioadvection rates suggest that sediment accumulation rates (SARs) on the tidal flat are ˜0.25 cm/y, near the low end of contemporary New Zealand muddy intertidal SARs. Frequent deposition and erosion of the surface layer demonstrates that long-term sediment accumulation captures only a small fraction of sediment deposited at any one time. Model results also suggest that our magnetite tracer method may slightly underestimate short-term shallow mixing rates (demonstrated by 7Be profiles), and slightly overestimate longer-term, deeper bioturbation rates (demonstrated by 210Pb profiles).

STAR FORMATION ON SUBKILOPARSEC SCALE TRIGGERED BY NON-LINEAR PROCESSES IN NEARBY SPIRAL GALAXIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Momose, Rieko; Koda, Jin; Donovan Meyer, Jennifer

We report a super-linear correlation for the star formation law based on new CO(J = 1-0) data from the CARMA and NOBEYAMA Nearby-galaxies (CANON) CO survey. The sample includes 10 nearby spiral galaxies, in which structures at sub-kpc scales are spatially resolved. Combined with the star formation rate surface density traced by H{alpha} and 24 {mu}m images, CO(J = 1-0) data provide a super-linear slope of N = 1.3. The slope becomes even steeper (N = 1.8) when the diffuse stellar and dust background emission is subtracted from the H{alpha} and 24 {mu}m images. In contrast to the recent resultsmore » with CO(J = 2-1) that found a constant star formation efficiency (SFE) in many spiral galaxies, these results suggest that the SFE is not independent of environment, but increases with molecular gas surface density. We suggest that the excitation of CO(J = 2-1) is likely enhanced in the regions with higher star formation and does not linearly trace the molecular gas mass. In addition, the diffuse emission contaminates the SFE measurement most in regions where the star formation rate is law. These two effects can flatten the power-law correlation and produce the apparent linear slope. The super-linear slope from the CO(J = 1-0) analysis indicates that star formation is enhanced by non-linear processes in regions of high gas density, e.g., gravitational collapse and cloud-cloud collisions.« less

The SAMI Galaxy Survey: spatially resolving the main sequence of star formation

NASA Astrophysics Data System (ADS)

Medling, Anne M.; Cortese, Luca; Croom, Scott M.; Green, Andrew W.; Groves, Brent; Hampton, Elise; Ho, I.-Ting; Davies, Luke J. M.; Kewley, Lisa J.; Moffett, Amanda J.; Schaefer, Adam L.; Taylor, Edward; Zafar, Tayyaba; Bekki, Kenji; Bland-Hawthorn, Joss; Bloom, Jessica V.; Brough, Sarah; Bryant, Julia J.; Catinella, Barbara; Cecil, Gerald; Colless, Matthew; Couch, Warrick J.; Drinkwater, Michael J.; Driver, Simon P.; Federrath, Christoph; Foster, Caroline; Goldstein, Gregory; Goodwin, Michael; Hopkins, Andrew; Lawrence, J. S.; Leslie, Sarah K.; Lewis, Geraint F.; Lorente, Nuria P. F.; Owers, Matt S.; McDermid, Richard; Richards, Samuel N.; Sharp, Robert; Scott, Nicholas; Sweet, Sarah M.; Taranu, Dan S.; Tescari, Edoardo; Tonini, Chiara; van de Sande, Jesse; Walcher, C. Jakob; Wright, Angus

2018-04-01

We present the ˜800 star formation rate maps for the Sydney-AAO Multi-object Integral field spectrograph (SAMI) Galaxy Survey based on H α emission maps, corrected for dust attenuation via the Balmer decrement, that are included in the SAMI Public Data Release 1. We mask out spaxels contaminated by non-stellar emission using the [O III]/H β, [N II]/H α, [S II]/H α, and [O I]/H α line ratios. Using these maps, we examine the global and resolved star-forming main sequences of SAMI galaxies as a function of morphology, environmental density, and stellar mass. Galaxies further below the star-forming main sequence are more likely to have flatter star formation profiles. Early-type galaxies split into two populations with similar stellar masses and central stellar mass surface densities. The main-sequence population has centrally concentrated star formation similar to late-type galaxies, while galaxies >3σ below the main sequence show significantly reduced star formation most strikingly in the nuclear regions. The split populations support a two-step quenching mechanism, wherein halo mass first cuts off the gas supply and remaining gas continues to form stars until the local stellar mass surface density can stabilize the reduced remaining fuel against further star formation. Across all morphologies, galaxies in denser environments show a decreased specific star formation rate from the outside in, supporting an environmental cause for quenching, such as ram-pressure stripping or galaxy interactions.

Surface morphology of molybdenum silicide films upon low-energy ion beam sputtering.

PubMed

Gago, R; Jaafar, M; Palomares, F J

2018-07-04

The surface morphology of molybdenum silicide (Mo x Si 1-x ) films has been studied after low-energy Ar + ion beam sputtering (IBS) to explore eventual pattern formation on compound targets and, simultaneously, gather information about the mechanisms behind silicide-assisted nanopatterning of silicon surfaces by IBS. For this purpose, Mo x Si 1-x films with compositions below, equal and above the MoSi 2 stoichiometry (x  =  0.33) have been produced by magnetron sputtering, as assessed by Rutherford backscattering spectrometry (RBS). The surface morphology of silicon and silicide films before and after IBS has been imaged by atomic force microscopy (AFM), comprising conditions where typical nanodot or ripple patterns emerge on the former. In the case of irradiated Mo x Si 1-x surfaces, AFM shows a marked surface smoothing at normal incidence with and without additional Mo incorporation (the former results in nanodot patterns on Si). The morphological analysis also provides no evidence of ion-induced phase separation in irradiated Mo x Si 1-x . Contrary to silicon, Mo x Si 1-x surfaces also do not display ripple formation for (impurity free) oblique irradiations, except at grazing incidence conditions where parallel ripples emerge in a more evident fashion than in the Si counterpart. By means of RBS, irradiated Mo x Si 1-x films with 1 keV Ar + at normal incidence have also been used to measure experimentally the (absolute) sputtering yield and rate of Si and Mo x Si 1-x materials. The analysis reveals that, under the present working conditions, the erosion rate of silicides is larger than for silicon, supporting simulations from the TRIDYN code. This finding questions the shielding effect from silicide regions as roughening mechanism in metal-assisted nanopatterning of silicon. On the contrary, the results highlight the relevance of in situ silicide formation. Ripple formation on Mo x Si 1-x under grazing incidence is also attributed to the dominance of sputtering effects under this geometry. In conclusion, our work provides some insights into the complex morphological evolution of compound surfaces and solid experimental evidences regarding the mechanisms behind silicide-assisted nanopatterning.

Formation of Oxides in the Interior of Friction Stir Welds

NASA Technical Reports Server (NTRS)

Schneider, Judy; Chen, Po; Nunes, Arthur C., Jr.

2016-01-01

In friction stir welding (FSWing) the actual solid state joining takes place between the faying surfaces which form the weld seam. Thus the seam trace is often investigated for clues when the strength of the weld is reduced. Aluminum and its alloys are known to form a native, protective oxide on the surface. If these native surface oxides are not sufficiently broken up during the FSW process, they are reported to remain in the FSW interior and weaken the bond strength. This type of weld defect has been referred to as a lazy "S", lazy "Z", joint line defect, kissing bond, or residual oxide defect. Usually these defects are mitigated by modification of the process parameters, such as increased tool rotation rate, which causes a finer breakup of the native oxide particles. This study proposes that there may be an alternative mechanism for formation of oxides found within the weld nugget. As the oxidation rate increases at elevated temperatures above 400ºC, it may be possible for enhanced oxidation to occur on the interior surfaces during the FSW process from entrained air entering the seam gap. Normally, FSWs of aluminum alloys are made without a purge gas and it is unknown how process parameters and initial fit up could affect a potential air path into the interior during the processing. In addition, variations in FSW parameters, such as the tool rotation, are known to have a strong influence on the FSW temperature which may affect the oxidation rate if internal surfaces are exposed to entrained air. A series of FSWs were made in 3 different thickness panels of AA2219 (0.95, 1.27 and 1.56 cm) at 2 different weld pitches. As the thickness of the panels increased, there was an increased tendency for a gap to form in advance of the weld tool. If sufficient air is able to enter the workpiece gap prior to consolidation, the weld temperature can increase the oxidation rate on the interior surfaces. These oxidation rates would also be accelerated in areas of localized liquation. Metallographs from the weld panels showed indications of liquation at the grain boundaries. In FSWs of thicker panels, these regions of liquation were found to be heavily oxidized. The quality of the FSWs was evaluated from tensile testing at room temperature. As the panel thickness increased, a slight decrease in tensile strength was observed which was attributed to the presence of oxides. No oxide formation was observed in the thinner workpieces, although there were indications of localized liquation at the grain boundaries. Results from this study will assist in a better understand of the mechanisms of oxide formation in FSW interiors and provide methodology for minimizing their occurrence.

Martian and Terrestrial Rock Abrasion from Wind Tunnel and Field Studies

NASA Technical Reports Server (NTRS)

Bridges, N. T.; Greeley, R.; Eddlemon, E.; Laity, J. E.; Meyer, C.; Phoreman, J.; White, B. R.

2003-01-01

Earth and Mars exhibit ventifacts, rocks that have been abraded by saltating sand. Previous theoretical and laboratory studies have determined abrasion susceptibilities of rocks as a function of sand type and impact angle and rock material strengths. For the last two years we have been engaged in wind tunnel and field studies to better understand the fundamental factors which control and influence rock abrasion and ventifact formation on Earth and Mars. In particular, we are examining: 1) What types of rocks (composition, texture, and shape) preferentially erode and what are the relative rates of one type vs. another? 2) What are the controlling factors of the aeolian sand cloud (flux, particle speed, surface roughness, etc) which favor rock abrasion?, 3) How do specific ventifact characteristics tie into their mode of formation and rock properties? We find several important factors: 1) Initial rock shape controls the rate of abrasion, with steeper faces abrading faster than shallower ones. The relationship is partly dependent on angle-dependent flux (proportional to sin[theta]) but exhibits additional non-linear effects from momentum transfer efficiency and rebound effects that vary with incidence angle. 2) Irregular targets with pits or grooves abrade at greater rates than targets with smooth surfaces, with indentations generally enlarging with time. Surfaces become rougher with time. 3) Targets also abrade via slope retreat, which is roughly dependent on the slope of the front face. The formation of basal sills is common, as observed on terrestrial and Martian ventifacts.

Unified interpretation of exciplex formation and marcus electron transfer on the basis of two-dimensional free energy surfaces.

PubMed

Murata, Shigeo; Tachiya, M

2007-09-27

The mechanism of exciplex formation proposed in a previous paper has been refined to show how exciplex formation and Marcus electron transfer (ET) in fluorescence quenching are related to each other. This was done by making simple calculations of the free energies of the initial (DA*) and final (D+A-) states of ET. First it was shown that the decrease in D-A distance can induce intermolecular ET even in nonpolar solvents where solvent orientational polarization is absent, and that it leads to exciplex formation. This is consistent with experimental results that exciplex is most often observed in nonpolar solvents. The calculation was then extended to ET in polar solvents where the free energies are functions of both D-A distance and solvent orientational polarization. This enabled us to discuss both exciplex formation and Marcus ET in the same D-A pair and solvent on the basis of 2-dimensional free energy surfaces. The surfaces contain more information about the rates of these reactions, the mechanism of fluorescence quenching by ET, etc., than simple reaction schemes. By changing the parameters such as the free energy change of reaction, solvent dielectric constants, etc., one can construct the free energy surfaces for various systems. The effects of free energy change of reaction and of solvent polarity on the mechanism and relative importance of exciplex formation and Marcus ET in fluorescence quenching can be well explained. The free energy surface will also be useful for discussion of other phenomena related to ET reactions.

Shewanella putrefaciens Adhesion and Biofilm Formation on Food Processing Surfaces

PubMed Central

Bagge, Dorthe; Hjelm, Mette; Johansen, Charlotte; Huber, Ingrid; Gram, Lone

2001-01-01

Laboratory model systems were developed for studying Shewanella putrefaciens adhesion and biofilm formation under batch and flow conditions. S. putrefaciens plays a major role in food spoilage and may cause microbially induced corrosion on steel surfaces. S. putrefaciens bacteria suspended in buffer adhered readily to stainless steel surfaces. Maximum numbers of adherent bacteria per square centimeter were reached in 8 h at 25°C and reflected the cell density in suspension. Numbers of adhering bacteria from a suspension containing 108 CFU/ml were much lower in a laminar flow system (modified Robbins device) (reaching 102 CFU/cm2) than in a batch system (reaching 107 CFU/cm2), and maximum numbers were reached after 24 h. When nutrients were supplied, S. putrefaciens grew in biofilms with layers of bacteria. The rate of biofilm formation and the thickness of the film were not dependent on the availability of carbohydrate (lactate or glucose) or on iron starvation. The number of S. putrefaciens bacteria on the surface was partly influenced by the presence of other bacteria (Pseudomonas fluorescens) which reduced the numbers of S. putrefaciens bacteria in the biofilm. Numbers of bacteria on the surface must be quantified to evaluate the influence of environmental factors on adhesion and biofilm formation. We used a combination of fluorescence microscopy (4′,6′-diamidino-2-phenylindole staining and in situ hybridization, for mixed-culture studies), ultrasonic removal of bacteria from surfaces, and indirect conductometry and found this combination sufficient to quantify bacteria on surfaces. PMID:11319118

Sensitivity of mineral dissolution rates to physical weathering : A modeling approach

NASA Astrophysics Data System (ADS)

Opolot, Emmanuel; Finke, Peter

2015-04-01

There is continued interest on accurate estimation of natural weathering rates owing to their importance in soil formation, nutrient cycling, estimation of acidification in soils, rivers and lakes, and in understanding the role of silicate weathering in carbon sequestration. At the same time a challenge does exist to reconcile discrepancies between laboratory-determined weathering rates and natural weathering rates. Studies have consistently reported laboratory rates to be in orders of magnitude faster than the natural weathering rates (White, 2009). These discrepancies have mainly been attributed to (i) changes in fluid composition (ii) changes in primary mineral surfaces (reactive sites) and (iii) the formation of secondary phases; that could slow natural weathering rates. It is indeed difficult to measure the interactive effect of the intrinsic factors (e.g. mineral composition, surface area) and extrinsic factors (e.g. solution composition, climate, bioturbation) occurring at the natural setting, in the laboratory experiments. A modeling approach could be useful in this case. A number of geochemical models (e.g. PHREEQC, EQ3/EQ6) already exist and are capable of estimating mineral dissolution / precipitation rates as a function of time and mineral mass. However most of these approaches assume a constant surface area in a given volume of water (White, 2009). This assumption may become invalid especially at long time scales. One of the widely used weathering models is the PROFILE model (Sverdrup and Warfvinge, 1993). The PROFILE model takes into account the mineral composition, solution composition and surface area in determining dissolution / precipitation rates. However there is less coupling with other processes (e.g. physical weathering, clay migration, bioturbation) which could directly or indirectly influence dissolution / precipitation rates. We propose in this study a coupling between chemical weathering mechanism (defined as a function of reactive area, solution composition, temperature, mineral composition) and the physical weathering module in the SoilGen model which calculates the evolution of particle size (used for surface area calculation) as influenced by temperature gradients. The solution composition in the SoilGen model is also influenced by other processes such as atmospheric inputs, organic matter decomposition, cation exchange, secondary mineral formation and leaching. We then apply this coupled mechanism on a case study involving 3 loess soil profiles to analyze the sensitivity of mineral weathering rates to physical weathering. Initial results show some sensitivity but not that dramatic. The less sensitivity was attributed to dominance of resistant primary minerals (> 70% quartz). Scenarios with different sets of mineralogy will be tested and sensitivity results in terms of silicate mineral dissolution rates and CO2-consumption will be presented in the conference. References Sverdrup H and Warfvinge P., 1993. Calculating field weathering rates using a mechanistic geochemical model PROFILE. Applied Geochemistry, 8:273-283. White, A.F., 2009. Natural weathering rates of silicate minerals. In: Drever, J.I. (Ed.), Surface and Ground Water, Weathering and Soils. In: Holland, H.D., Turekian, K.K. (Eds.), Treatise on Geochemistry. vol. 5. Elsevier-Pergamon, Oxford, pp. 133-168.

Kinetics of solvent supported tubule formation of Lotus (Nelumbo nucifera) wax on highly oriented pyrolytic graphite (HOPG) investigated by atomic force microscopy

PubMed Central

Koch, Kerstin; Barthlott, Wilhelm; Wandelt, Klaus

2018-01-01

The time dependence of the formation of lotus wax tubules after recrystallization from various chloroform-based solutions on an HOPG surface at room temperature was studied by atomic force microscopy (magnetic AC mode) taking series of consecutive images of the formation process. The growth of the tubules oriented in an upright fashion follows a sequential rodlet→ring→tubule behavior. The influence of a number of factors, e.g., different wax concentration in chloroform, the additional presence of water, or salts [(NH4)2SO4, NH4NO3] or a mixture of salt/water in the solution on the growth rate and orientation of the tubules is also investigated. Different wax concentrations were found to have no effect on the growth rate or the orientation of tubules in none of the solutions. The presence of water, however, considerably increased the growth rate of tubule formation, while the presence of salt was again found to have no effect on growth rate or orientation of tubules. PMID:29515959

On the role of extracellular polymeric substances during early stages of Xylella fastidiosa biofilm formation.

PubMed

Lorite, Gabriela S; de Souza, Alessandra A; Neubauer, Daniel; Mizaikoff, Boris; Kranz, Christine; Cotta, Mônica A

2013-02-01

The structural integrity and protection of bacterial biofilms are intrinsically associated with a matrix of extracellular polymeric substances (EPS) produced by the bacteria cells. However, the role of these substances during biofilm adhesion to a surface remains largely unclear. In this study, the influence of EPS on Xylella fastidiosa biofilm formation was investigated. This bacterium is associated with economically important plant diseases; it presents a slow growth rate and thus allows us to pinpoint more precisely the early stages of cell-surface adhesion. Scanning electron microscopy and atomic force microscopy show evidence of EPS production in such early stages and around individual bacteria cells attached to the substrate surface even a few hours after inoculation. In addition, EPS formation was investigated via attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FTIR). To this end, X. fastidiosa cells were inoculated within an ATR liquid cell assembly. IR-ATR spectra clearly reveal EPS formation already during the early stages of X. fastidiosa biofilm formation, thereby providing supporting evidence for the hypothesis of the relevance of the EPS contribution to the adhesion process. Copyright © 2012 Elsevier B.V. All rights reserved.

A unified model for galactic discs: star formation, turbulence driving, and mass transport

NASA Astrophysics Data System (ADS)

Krumholz, Mark R.; Burkhart, Blakesley; Forbes, John C.; Crocker, Roland M.

2018-06-01

We introduce a new model for the structure and evolution of the gas in galactic discs. In the model the gas is in vertical pressure and energy balance. Star formation feedback injects energy and momentum, and non-axisymmetric torques prevent the gas from becoming more than marginally gravitationally unstable. From these assumptions we derive the relationship between galaxies' bulk properties (gas surface density, stellar content, and rotation curve) and their star formation rates, gas velocity dispersions, and rates of radial inflow. We show that the turbulence in discs can be powered primarily by star formation feedback, radial transport, or a combination of the two. In contrast to models that omit either radial transport or star formation feedback, the predictions of this model yield excellent agreement with a wide range of observations, including the star formation law measured in both spatially resolved and unresolved data, the correlation between galaxies' star formation rates and velocity dispersions, and observed rates of radial inflow. The agreement holds across a wide range of galaxy mass and type, from local dwarfs to extreme starbursts to high-redshift discs. We apply the model to galaxies on the star-forming main sequence, and show that it predicts a transition from mostly gravity-driven turbulence at high redshift to star-formation-driven turbulence at low redshift. This transition and the changes in mass transport rates that it produces naturally explain why galaxy bulges tend to form at high redshift and discs at lower redshift, and why galaxies tend to quench inside-out.

Optimization of Processing Parameters in ECM of Die Tool Steel Using Nanofluid by Multiobjective Genetic Algorithm.

PubMed

Sathiyamoorthy, V; Sekar, T; Elango, N

2015-01-01

Formation of spikes prevents achievement of the better material removal rate (MRR) and surface finish while using plain NaNO3 aqueous electrolyte in electrochemical machining (ECM) of die tool steel. Hence this research work attempts to minimize the formation of spikes in the selected workpiece of high carbon high chromium die tool steel using copper nanoparticles suspended in NaNO3 aqueous electrolyte, that is, nanofluid. The selected influencing parameters are applied voltage and electrolyte discharge rate with three levels and tool feed rate with four levels. Thirty-six experiments were designed using Design Expert 7.0 software and optimization was done using multiobjective genetic algorithm (MOGA). This tool identified the best possible combination for achieving the better MRR and surface roughness. The results reveal that voltage of 18 V, tool feed rate of 0.54 mm/min, and nanofluid discharge rate of 12 lit/min would be the optimum values in ECM of HCHCr die tool steel. For checking the optimality obtained from the MOGA in MATLAB software, the maximum MRR of 375.78277 mm(3)/min and respective surface roughness Ra of 2.339779 μm were predicted at applied voltage of 17.688986 V, tool feed rate of 0.5399705 mm/min, and nanofluid discharge rate of 11.998816 lit/min. Confirmatory tests showed that the actual performance at the optimum conditions was 361.214 mm(3)/min and 2.41 μm; the deviation from the predicted performance is less than 4% which proves the composite desirability of the developed models.

Work Hardening Behavior of 1020 Steel During Cold-Beating Simulation

NASA Astrophysics Data System (ADS)

CUI, Fengkui; LING, Yuanfei; XUE, Jinxue; LIU, Jia; LIU, Yuhui; LI, Yan

2017-03-01

The present research of cold-beating formation mainly focused on roller design and manufacture, kinematics, constitutive relation, metal flow law, thermo-mechanical coupling, surface micro-topography and microstructure evolution. However, the research on surface quality and performance of workpieces in the process of cold-beating is rare. Cold-beating simulation experiment of 1020 steel is conducted at room temperature and strain rates ranging from 2000 to 4000 s-1 base on the law of plastic forming. According to the experimental data, the model of strain hardening of 1020 steel is established, Scanning Electron Microscopy(SEM) is conducted, the mechanism of the work hardening of 1020 steel is clarified by analyzing microstructure variation of 1020 steel. It is found that the strain rate hardening effect of 1020 steel is stronger than the softening effect induced by increasing temperatures, the process of simulation cold-beating cause the grain shape of 1020 steel significant change and microstructure elongate significantly to form a fibrous tissue parallel to the direction of deformation, the higher strain rate, the more obvious grain refinement and the more hardening effect. Additionally, the change law of the work hardening rate is investigated, the relationship between dislocation density and strain, the relationship between work hardening rate and dislocation density is obtained. Results show that the change trend of the work hardening rate of 1020 steel is divided into two stages, the work hardening rate decreases dramatically in the first stage and slowly decreases in the second stage, finally tending toward zero. Dislocation density increases with increasing strain and strain rate, work hardening rate decreases with increasing dislocation density. The research results provide the basis for solving the problem of improving the surface quality and performance of workpieces under cold-beating formation of 1020 steel.

From Aβ Filament to Fibril: Molecular Mechanism of Surface-Activated Secondary Nucleation from All-Atom MD Simulations.

PubMed

Schwierz, Nadine; Frost, Christina V; Geissler, Phillip L; Zacharias, Martin

2017-02-02

Secondary nucleation pathways in which existing amyloid fibrils catalyze the formation of new aggregates and neurotoxic oligomers are of immediate importance for the onset and progression of Alzheimer's disease. Here, we apply extensive all-atom molecular dynamics simulations in explicit water to study surface-activated secondary nucleation pathways at the extended lateral β-sheet surface of a preformed Aβ 9-40 filament. Calculation of free-energy profiles allows us to determine binding free energies and conformational intermediates for nucleation complexes consisting of 1-4 Aβ peptides. In addition, we combine the free-energy profiles with position-dependent diffusion profiles to extract complementary kinetic information and macroscopic growth rates. Single monomers bind to the β-sheet surface in a disordered, hydrophobically collapsed conformation, whereas dimers and larger oligomers can retain a cross-β conformation resembling a more ordered fibril structure. The association processes during secondary nucleation follow a dock/lock mechanism consisting of a fast initial encounter phase (docking) and a slow structural rearrangement phase (locking). The major driving forces for surface-activated secondary nucleation are the release of a large number of hydration water molecules and the formation of hydrophobic interface contacts, the latter being in contrast to the elongation process at filament tips, which is dominated by the formation of stable and highly specific interface hydrogen bonds. The calculated binding free energies and the association rates for the attachment of Aβ monomers and oligomers to the extended lateral β-sheet surface of the filament seed are higher compared to those for elongation at the filament tips, indicating that secondary nucleation pathways can become important once a critical concentration of filaments has formed.

Winds of change: reionization by starburst galaxies

NASA Astrophysics Data System (ADS)

Sharma, Mahavir; Theuns, Tom; Frenk, Carlos; Bower, Richard G.; Crain, Robert A.; Schaller, Matthieu; Schaye, Joop

2017-06-01

We investigate the properties of the galaxies that reionized the Universe and the history of cosmic reionization using the 'Evolution and Assembly of Galaxies and their Environments' (eagle) cosmological hydrodynamical simulations. We obtain the evolution of the escape fraction of ionizing photons in galaxies assuming that galactic winds create channels through which 20 per cent of photons escape when the local surface density of star formation is greater than 0.1 M⊙ yr-1 kpc-2. Such threshold behaviour for the generation of winds is observed, and the rare local objects that have such high star formation surface densities exhibit high escape fractions of ˜10 per cent. In our model, the luminosity-weighted mean escape fraction increases with redshift as \\bar{f}_esc=0.045 ((1+z)/4)^{1.1} at z > 3, and the galaxy number weighted mean as = 2.2 × 10-3 ((1 + z)/4)4, and becomes constant ≈0.2 at redshift z > 10. The escape fraction evolves as an increasingly large fraction of stars forms above the critical surface density of star formation at earlier times. This evolution of the escape fraction, combined with that of the star formation rate density from eagle, reproduces the inferred evolution of the filling factor of ionized regions during the reionization epoch (6 < z < 8), the evolution of the post-reionization (0 ≤ z < 6) hydrogen photoionization rate and the optical depth due to Thomson scattering of the cosmic microwave background photons measured by the Planck satellite.

Microwave-induced electrostatic etching: generation of highly reactive magnesium for application in Grignard reagent formation.

PubMed

van de Kruijs, Bastiaan H P; Dressen, Mark H C L; Meuldijk, Jan; Vekemans, Jef A J M; Hulshof, Lumbertus A

2010-04-07

A detailed study regarding the influence of microwave irradiation on the formation of a series of Grignard reagents in terms of rates and selectivities has revealed that these heterogeneous reactions may display a beneficial microwave effect. The interaction between microwaves and magnesium turnings generates violent electrostatic discharges. These discharges on magnesium lead to melting of the magnesium surface, thus generating highly active magnesium particles. As compared to conventional operation the microwave-induced discharges on the magnesium surface lead to considerably shorter initiation times for the insertion of magnesium in selected substrates (i.e. halothiophenes, halopyridines, octyl halides, and halobenzenes). Thermographic imaging and surface characterization by scanning electron microscopy showed that neither selective heating nor a "specific" microwave effect was causing the reduction in initiation times. This novel and straightforward initiation method eliminates the use of toxic and environmentally adverse initiators. Thus, this initiation method limits the formation of by-products. We clearly demonstrated that microwave irradiation enables fast Grignard reagent formation. Therefore, microwave technology is promising for process intensification of Grignard based coupling reactions.

Transthyretin Interferes with Aβ Amyloid Formation by Redirecting Oligomeric Nuclei into Non-Amyloid Aggregates.

PubMed

Nilsson, Lina; Pamrén, Annelie; Islam, Tohidul; Brännström, Kristoffer; Golchin, Solmaz A; Pettersson, Nina; Iakovleva, Irina; Sandblad, Linda; Gharibyan, Anna L; Olofsson, Anders

2018-06-08

The pathological Aβ aggregates associated with Alzheimer's disease follow a nucleation-dependent path of formation. A nucleus represents an oligomeric assembly of Aβ peptides that acts as a template for subsequent incorporation of monomers to form a fibrillar structure. Nuclei can form de novo or via surface-catalyzed secondary nucleation, and the combined rates of elongation and nucleation control the overall rate of fibril formation. Transthyretin (TTR) obstructs Aβ fibril formation in favor of alternative non-fibrillar assemblies, but the mechanism behind this activity is not fully understood. This study shows that TTR does not significantly disturb fibril elongation; rather, it effectively interferes with the formation of oligomeric nuclei. We demonstrate that this interference can be modulated by altering the relative contribution of elongation and nucleation, and we show how TTR's effects can range from being essentially ineffective to almost complete inhibition of fibril formation without changing the concentration of TTR or monomeric Aβ. Copyright © 2018. Published by Elsevier Ltd.

Simulations of chemical vapor deposition diamond film growth using a kinetic Monte Carlo model and two-dimensional models of microwave plasma and hot filament chemical vapor deposition reactors

NASA Astrophysics Data System (ADS)

May, P. W.; Harvey, J. N.; Allan, N. L.; Richley, J. C.; Mankelevich, Yu. A.

2010-12-01

A one-dimensional kinetic Monte Carlo (KMC) model has been developed to simulate the chemical vapor deposition of a diamond (100) surface under conditions used to grow single-crystal diamond (SCD), microcrystalline diamond (MCD), nanocrystalline diamond (NCD), and ultrananocrystalline diamond (UNCD) films. The model considers adsorption, etching/desorption, lattice incorporation and surface migration but not defect formation or renucleation processes. Two methods have been devised for estimation of the gas phase concentrations of species at the growing diamond surface, and are used to determine adsorption rates for C1Hx hydrocarbons for the different conditions. The rate of migration of adsorbed carbon species is governed by the availability of neighboring radical sites, which, in turn, depend upon the rates of H abstraction and of surface-radical migration. The KMC model predicts growth rates and surface roughness for each of diamond types consistent with experiment. In the absence of defect formation and renucleation the average surface diffusion length, ℓ, is a key parameter controlling surface morphology. When ℓ <2, surface migration is limited by the lack of availability of surface radical sites, and the migrating surface species simply hop back and forth between two adjacent sites but do not travel far beyond their initial adsorption site. Thus, Eley-Rideal processes dominate the growth, leading to the rough surfaces seen in NCD and UNCD. The maximum or "intrinsic" surface roughness occurs for nominally zero-migration conditions (ℓ =0) with an rms value of approximately five carbon atoms. Conversely, when migration occurs over greater distances (ℓ >2), Langmuir-Hinshelwood processes dominate the growth producing the smoother surfaces of MCD and SCD. By extrapolation, we predict that atomically smooth surfaces over large areas should occur once migrating species can travel approximately five sites (ℓ ˜5). β-scission processes are found to be unimportant for MCD and SCD growth conditions, but can remove up to 5% of the adsorbing carbon for NCD and UNCD growth. C1Hx insertion reactions also contribute <1% to the growth for nearly all conditions, while C2Hx (x <2) insertion reactions are negligible due their very low concentrations at the surface. Finally, the predictions for growth rate and morphology for UNCD deposition in a microwave system were found to be anomalous compared to those for all the other growth conditions, suggesting that carbonaceous particulates created in these plasmas may significantly affect the gas chemistry.

Environmental dependence of star formation induced by cloud collisions in a barred galaxy

NASA Astrophysics Data System (ADS)

Fujimoto, Yusuke; Tasker, Elizabeth J.; Habe, Asao

2014-11-01

Cloud collision has been proposed as a way to link the small-scale star formation process with the observed global relation between the surface star formation rate and gas surface density. We suggest that this model can be improved further by allowing the productivity of such collisions to depend on the relative velocity of the two clouds. Our adjustment implements a simple step function that results in the most successful collisions being at the observed velocities for triggered star formation. By applying this to a high-resolution simulation of a barred galaxy, we successfully reproduce the observational result that the star formation efficiency (SFE) in the bar is lower than that in the spiral arms. This is not possible when we use an efficiency dependent on the internal turbulence properties of the clouds. Our results suggest that high-velocity collisions driven by the gravitational pull of the clouds are responsible for the low bar SFE.

Formation of Ganymede's Grooved Terrain by Convection-Driven Resurfacing

NASA Astrophysics Data System (ADS)

Hammond, N. P.; Barr, A. C.

2013-12-01

Over half the surface of Ganymede, Jupiter's largest icy moon, is covered in grooved terrain, which is composed of 10-100 km wide swaths of sub-parallel ridges and troughs [1]. Convection in Ganymede's ice shell was originally suggested as a driving mechanism for grooved terrain formation [2] but subsequent work has argued that convective stresses were too weak to deform the surface [3] and that Ganymede's ice shell was thin and conductive during groove terrain formation [4]. However, the heat flow [5] and strain rate [6] inferred for grooved terrain formation resemble the conditions observed at the active Enceladus South Polar Terrain (SPT), where 'sluggish lid' convection may be occurring [7]. During 'sluggish lid' convection, thermal buoyancy stresses exceed the lithospheric yield stress, allowing convection to reach the surface and drive deformation [8]. Previous work shows that the heat flows and strain rates associated with sluggish lid convection are consistent with the observed heat flow and surface age of the Enceladus SPT [7, 9]. Here we use numerical models of convection in Ganymede's ice shell to show that convection can provide the heat flow and strain rate inferred for grooved terrain formation. We use the finite element model CITCOM [10] to model convection for a wide range of ice shell conditions. We use a newtonian temperature-dependent viscosity consistent with deformation by volume diffusion [11]. We impose a limited viscosity contrast between the surface and base of the ice shell to mimic the effect of an upper surface whose yield stress is less than the critical stress for sluggish lid convection [7, 12] due to impact fracturing [13], tidal flexing, and/or shallow tidal heating. We find that ice shells 10 to 80 km thick are consistent with the heat flow and strain rate inferred for grooved terrain formation. Regions above convective upwellings are consistent with conditions inferred at groove lanes. Regions above downwellings are consistent with heat flow estimates for dark terrain [14] and conditions which favor the formation of long-wavelength, low-amplitude compressional folds [15], similar to those observed on Europa [16]. Such folds may be detectable by the upcoming Jupiter-Icy-Moon-Explorer Mission. Acknowledgements: This work is supported by NASA PG&G #NNX12AI76G References: [1] Collins G. et al., (1998) GRL 25, 3, 233-236 [2] Lucchitta B. (1980) Icarus 44, 481-501 [3] Squyres S. & Croft S. (1986) Satellites 293-341 [4] Showman A. P. et al., (1997) Icarus 129, 367-383 [5] Nimmo F. et al. (2002) GRL 29, 62-65 [6] Bland M. & Showman A. (2007), Icarus 189, 439-456. [7] Barr A. C. (2008) JGR 113, E07009 14 [8] Solomatov V. (2004) JGR 109, B01412 [9] O'Neill C. & Nimmo F. (2010) Nat. Geo. 3 v2 88-91 [10] Moresi L. & Solomatov V. (1995) Phys. Fluids 7, 2154-2162 [11] Goldsby D. & Kohlstedt D. (2001) JGR 106, B6 11017-11030 [12] Solomatov V. (2004) JGR 109, B01412 [13] Nimmo F. & Schenk P. (2006) J. Struc. Geol. 28, 2194-2203 [14] Nimmo F. & Pappalardo R. (2004) GRL 31, L19701 [15] Bland M. & McKinnon W. (2012) Icarus 221, 2, 694-709 [16] Prockter L. & Pappalardo R. (2000) Science 289, 5481, 941-944

Mineral Surface Chemistry and Nanoparticle-aggregation Control Membrane Self-Assembly

NASA Astrophysics Data System (ADS)

Sahai, Nita; Kaddour, Hussein; Dalai, Punam; Wang, Ziqiu; Bass, Garrett; Gao, Min

2017-03-01

The self-assembly of lipid bilayer membranes to enclose functional biomolecules, thus defining a “protocell,” was a seminal moment in the emergence of life on Earth and likely occurred at the micro-environment of the mineral-water interface. Mineral-lipid interactions are also relevant in biomedical, industrial and technological processes. Yet, no structure-activity relationships (SARs) have been identified to predict lipid self-assembly at mineral surfaces. Here we examined the influence of minerals on the self-assembly and survival of vesicles composed of single chain amphiphiles as model protocell membranes. The apparent critical vesicle concentration (CVC) increased in the presence of positively-charged nanoparticulate minerals at high loadings (mg/mL) suggesting unfavorable membrane self-assembly in such situations. Above the CVC, initial vesicle formation rates were faster in the presence of minerals. Rates were correlated with the mineral’s isoelectric point (IEP) and reactive surface area. The IEP depends on the crystal structure, chemical composition and surface hydration. Thus, membrane self-assembly showed rational dependence on fundamental mineral properties. Once formed, membrane permeability (integrity) was unaffected by minerals. Suggesting that, protocells could have survived on rock surfaces. These SARs may help predict the formation and survival of protocell membranes on early Earth and other rocky planets, and amphiphile-mineral interactions in diverse other phenomena.

Mineral Surface Chemistry and Nanoparticle-aggregation Control Membrane Self-Assembly

PubMed Central

Sahai, Nita; Kaddour, Hussein; Dalai, Punam; Wang, Ziqiu; Bass, Garrett; Gao, Min

2017-01-01

The self-assembly of lipid bilayer membranes to enclose functional biomolecules, thus defining a “protocell,” was a seminal moment in the emergence of life on Earth and likely occurred at the micro-environment of the mineral-water interface. Mineral-lipid interactions are also relevant in biomedical, industrial and technological processes. Yet, no structure-activity relationships (SARs) have been identified to predict lipid self-assembly at mineral surfaces. Here we examined the influence of minerals on the self-assembly and survival of vesicles composed of single chain amphiphiles as model protocell membranes. The apparent critical vesicle concentration (CVC) increased in the presence of positively-charged nanoparticulate minerals at high loadings (mg/mL) suggesting unfavorable membrane self-assembly in such situations. Above the CVC, initial vesicle formation rates were faster in the presence of minerals. Rates were correlated with the mineral’s isoelectric point (IEP) and reactive surface area. The IEP depends on the crystal structure, chemical composition and surface hydration. Thus, membrane self-assembly showed rational dependence on fundamental mineral properties. Once formed, membrane permeability (integrity) was unaffected by minerals. Suggesting that, protocells could have survived on rock surfaces. These SARs may help predict the formation and survival of protocell membranes on early Earth and other rocky planets, and amphiphile-mineral interactions in diverse other phenomena. PMID:28266537

Fire characteristics charts for fire behavior and U.S. fire danger rating

Treesearch

Faith Ann Heinsch; Pat Andrews

2010-01-01

The fire characteristics chart is a graphical method of presenting U.S. National Fire Danger Rating indices or primary surface or crown fire behavior characteristics. A desktop computer application has been developed to produce fire characteristics charts in a format suitable for inclusion in reports and presentations. Many options include change of scales, colors,...

Drug release through liposome pores.

PubMed

Dan, Nily

2015-02-01

Electrical, ultrasound and other types of external fields are known to induce the formation of pores in cellular and model membranes. This paper examines drug release through field induced liposome pores using Monte Carlo simulations. We find that drug release rates vary as a function of pore size and spacing, as well as the overall fraction of surface area covered by pores: The rate of release from liposomes is found to increase rapidly with pore surface coverage, approaching that of the fully ruptured liposome at fractional pore areas. For a given pore surface coverage, the pore size affects the release rate in the limit of low coverage, but not when the pores cover a relatively high fraction of the liposome surface area. On the other hand, for a given pore size and surface coverage, the distribution of pores significantly affects the release in the limit of high surface coverage: The rate of release from a liposome covered with a regularly spaced array of pores is, in this limit, higher than the release rate from (most) systems where the pores are distributed randomly on the liposome surface. In contrast, there is little effect of the pore distribution on release when the pore surface coverage is low. The simulation results are in good agreement with the predictions of detailed diffusion models. Copyright © 2014 Elsevier B.V. All rights reserved.

Lack of enhanced photocatalytic formation of iodine on particulate semiconductor mixtures.

PubMed

Karunakaran, C; Anilkumar, P; Vinayagamoorthy, P

2012-12-01

Under UV-A light illumination, formation of iodine from iodide ion on the surfaces of anatase TiO(2), ZnO, Fe(2)O(3), CeO(2), MoO(3), Bi(2)O(3), and Nb(2)O(5) increases with the concentration of iodide ion, airflow rate and light intensity and conform to the Langmuir-Hinshelwood kinetic model. Measurement of the particle size of the semiconductor oxides by light scattering method and deduction of the same from the determined specific surface area show that the oxide particles agglomerate in suspension. However, mixtures of any two listed particulate semiconductors do not show enhanced photocatalytic formation of iodine indicating absence of interparticle charge transfer. The results are rationalized. Copyright © 2012 Elsevier B.V. All rights reserved.

A study on the probability of twin plane formation during the nucleation of AgBr and AgCl crystals in the aqueous gelatin solution

NASA Astrophysics Data System (ADS)

Ohzeki, Katsuhisa; Hosoya, Yoichi

2007-07-01

A study was made on the probability of twin plane formation during the nucleation of AgBr and AgCl crystals. The growth condition was controlled to keep the number of the nuclei, neither decreasing owing to their dissolution, nor increasing owing to the formation of a new nucleus during the growth process. Under the condition, the nuclei were grown to have {1 1 1} faces on their surfaces by controlling pAg in a reaction solution and by use of growth modifier in case of AgCl crystal formation. The number of twin planes in each crystal was judged according to a conventional way on the basis of its morphology. The dependence of the number of twin planes per crystal on the probability of twin plain formation was in accordance with Poisson distribution, indicating the random formation of a twin plane on the {1 1 1} faces of a nucleus. The result that the ratio of number of AgCl crystals with parallel twin planes to all the multiply twinned crystals was about 10% supports the random formation of a twin plane and suggests that the twin plane formation took place on {1 1 1} surfaces at the possible eight corner of a nucleus. On the other hand, the ratio of the number of AgBr crystals with parallel twin planes to all the multiply twinned crystals was more than 50%. The result was explained by the anisotropic growth of a singly twinned nucleus according to the higher growth rate of {1 0 0} surfaces than that of {1 1 1} surfaces.

PHIBSS: MOLECULAR GAS, EXTINCTION, STAR FORMATION, AND KINEMATICS IN THE z = 1.5 STAR-FORMING GALAXY EGS13011166

DOE Office of Scientific and Technical Information (OSTI.GOV)

Genzel, R.; Tacconi, L. J.; Kurk, J.

We report matched resolution imaging spectroscopy of the CO 3-2 line (with the IRAM Plateau de Bure millimeter interferometer) and of the H{alpha} line (with LUCI at the Large Binocular Telescope) in the massive z = 1.53 main-sequence galaxy EGS 13011166, as part of the ''Plateau de Bure high-z, blue-sequence survey'' (PHIBSS: Tacconi et al.). We combine these data with Hubble Space Telescope V-I-J-H-band maps to derive spatially resolved distributions of stellar surface density, star formation rate, molecular gas surface density, optical extinction, and gas kinematics. The spatial distribution and kinematics of the ionized and molecular gas are remarkably similarmore » and are well modeled by a turbulent, globally Toomre unstable, rotating disk. The stellar surface density distribution is smoother than the clumpy rest-frame UV/optical light distribution and peaks in an obscured, star-forming massive bulge near the dynamical center. The molecular gas surface density and the effective optical screen extinction track each other and are well modeled by a ''mixed'' extinction model. The inferred slope of the spatially resolved molecular gas to star formation rate relation, N = dlog{Sigma}{sub starform}/dlog{Sigma}{sub molgas}, depends strongly on the adopted extinction model, and can vary from 0.8 to 1.7. For the preferred mixed dust-gas model, we find N = 1.14 {+-} 0.1.« less

Photochemical influences on the air-water exchange of mercury

NASA Astrophysics Data System (ADS)

Vette, Alan Frederic

The formation of dissolved gaseous mercury (DGM) in natural waters is an important component in the biogeochemical cycle of mercury (Hg). The predominate form of DGM in natural waters, gaseous elemental Hg (Hg0), may be transferred from the water to the atmosphere. Gas exchange may reduce the amount of Hg available for methyl-Hg formation, the most toxic form of Hg that bioaccumulates in the food chain. Determining the mechanisms and rates of DGM formation is essential in understanding the fate and cycling of Hg in aquatic ecosystems. Field and laboratory experiments were conducted to evaluate the effect of light on DGM formation in surface waters containing different levels of dissolved organic carbon (DOC). Water samples collected from the Tahqwamenon River and Whitefish Bay on Lake Superior were amended with divalent Hg (Hg2+) and irradiated under a variety of reaction conditions to determine rates of DGM formation. The water samples were also analyzed for various Hg species (total, filtered, easily reducible and dissolved gaseous Hg), DOC and light attenuation. Additional field studies were conducted on Lake Michigan to measure gaseous Hg in air and water. These data were used to develop a mechanistic model to estimate air-water exchange of gaseous Hg. This research found that photochemical formation of DGM was affected by penetration of UV A radiation (320-400 nm). Formation of DGM was enhanced at higher DOC concentrations, indicating DOC photosensitized the reduction of Hg2+ to Hg0. Wavelength studies determined that formation of DGM was significantly reduced in the absence of UV A. Field studies showed DGM concentrations were highest near the water surface and peaked at mid-day, indicating a photo-induced source of DGM. The conversion of reducible Hg2+ to Hg0 was suppressed in high DOC waters where UV A penetration was limited. The mechanistic model predicted similar DGM concentrations to the observed values and demonstrated that deposition and emission fluxes of gaseous Hg were similar in Lake Michigan. In addition, deposition and emission fluxes of gaseous Hg were similar to Hg loadings by precipitation. The formation and emission of DGM from surface waters represents a significant contribution to the Hg cycle in aquatic ecosystems.

Cenosphere formation from heavy fuel oil: a numerical analysis accounting for the balance between porous shells and internal pressure

NASA Astrophysics Data System (ADS)

Reddy, Vanteru M.; Rahman, Mustafa M.; Gandi, Appala N.; Elbaz, Ayman M.; Schrecengost, Robert A.; Roberts, William L.

2016-01-01

Heavy fuel oil (HFO) as a fuel in industrial and power generation plants ensures the availability of energy at economy. Coke and cenosphere emissions from HFO combustion need to be controlled by particulate control equipment such as electrostatic precipitators, and collection effectiveness is impacted by the properties of these particulates. The cenosphere formation is a function of HFO composition, which varies depending on the source of the HFO. Numerical modelling of the cenosphere formation mechanism presented in this paper is an economical method of characterising cenosphere formation potential for HFO in comparison to experimental analysis of individual HFO samples, leading to better control and collection. In the present work, a novel numerical model is developed for understanding the global cenosphere formation mechanism. The critical diameter of the cenosphere is modelled based on the balance between two pressures developed in an HFO droplet. First is the pressure (Prpf) developed at the interface of the liquid surface and the inner surface of the accumulated coke due to the flow restriction of volatile components from the interior of the droplet. Second is the pressure due to the outer shell strength (PrC) gained from van der Walls energy of the coke layers and surface energy. In this present study it is considered that when PrC ≥ Prpf the outer shell starts to harden. The internal motion in the shell layer ceases and the outer diameter (DSOut) of the shell is then fixed. The entire process of cenosphere formation in this study is analysed in three phases: regression, shell formation and hardening, and post shell hardening. Variations in pressures during shell formation are analysed. Shell (cenosphere) dimensions are evaluated at the completion of droplet evaporation. The rate of fuel evaporation, rate of coke formation and coke accumulation are analysed. The model predicts shell outer diameters of 650, 860 and 1040 µm, and inner diameters are 360, 410 and 430 µm respectively, for 700, 900 and 1100 µm HFO droplets. The present numerical model is validated with experimental results available from the literature. Total variation between computational and experimental results is in the range of 3-7%.

The effect of charging rate on the graphite electrode of commercial lithium-ion cells: A post-mortem study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somerville, L.; Bareno, J.; Trask, S.

Increased charging rates negatively affect the lifetime of lithium-ion cells by increasing cell resistance and reducing capacity. This work is a post-mortem study of 18650 cells subjected to charge rates of 0.7-, 2-, 4-, and 6-C. For cells charged at 0.7-C to 4-C, this performance degradation is primarily related to surface film thickness with no observable change in surface film chemical composition. However, at charge rates of 6-C, the chemical composition of the surface film changes significantly, suggesting that this change is the reason for the sharper increase in cell resistance compared to the lower charge rates. In addition, wemore » found that surface film formation was not uniform across the electrode. Surface film was thicker and chemically different along the central band of the electrode “jelly roll”. This result is most likely attributable to an increase in temperature that results from non-uniform electrode wetting during manufacture. As a result, this non-uniform change further resulted in active material delamination from the current collector owing to chemical changes to the binder for the cell charged at 6-C.« less

The effect of charging rate on the graphite electrode of commercial lithium-ion cells: A post-mortem study

DOE PAGES

Somerville, L.; Bareno, J.; Trask, S.; ...

2016-10-22

Increased charging rates negatively affect the lifetime of lithium-ion cells by increasing cell resistance and reducing capacity. This work is a post-mortem study of 18650 cells subjected to charge rates of 0.7-, 2-, 4-, and 6-C. For cells charged at 0.7-C to 4-C, this performance degradation is primarily related to surface film thickness with no observable change in surface film chemical composition. However, at charge rates of 6-C, the chemical composition of the surface film changes significantly, suggesting that this change is the reason for the sharper increase in cell resistance compared to the lower charge rates. In addition, wemore » found that surface film formation was not uniform across the electrode. Surface film was thicker and chemically different along the central band of the electrode “jelly roll”. This result is most likely attributable to an increase in temperature that results from non-uniform electrode wetting during manufacture. As a result, this non-uniform change further resulted in active material delamination from the current collector owing to chemical changes to the binder for the cell charged at 6-C.« less

Estimation of the reactive mineral surface area during CO2-rich fluid-rock interaction: the influence of neogenic phases

NASA Astrophysics Data System (ADS)

Scislewski, A.; Zuddas, P.

2010-12-01

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water-rock interaction. It is however, difficult to estimate and well normalize bulk reaction rates if the mineral surface area exposed to the aqueous solution and effectively participating on the reactions is unknown. We evaluated the changing of the reactive mineral surface area during the interaction between CO2-rich fluids and Albitite/Granitoid rocks (similar mineralogy but different abundances), reacting under flow-through conditions. Our methodology, adopting an inverse modeling approach, is based on the estimation of dissolution rate and reactive surface area of the different minerals participating in the reactions by the reconstruction the chemical evolution of the interacting fluids. The irreversible mass-transfer processes is defined by a fractional degree of advancement, while calculations were carried out for Albite, Microcline, Biotite and Calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite. Irrespective of the mineral abundance in granite and albitite, we found that mineral dissolution rates did not change significantly in the investigated range of time where output solution’s pH remained in the range between 6 and 8, indicating that the observed variation in fluid composition depends not on pH but rather on the variation of the parent mineral’s reactive surface area. We found that the reactive surface area of Albite varied by more than 2 orders of magnitude, while Microcline, Calcite and Biotite surface areas changed by 1-2 orders of magnitude. We propose that parent mineral chemical heterogeneity and, particularly, the stability of secondary mineral phases may explain the observed variation of the reactive surface area of the minerals. Formation of coatings at the dissolving parent mineral surfaces significantly reduced the amount of surface available to react with CO2-rich fluids, decreasing the effective reactive surface area. Predictive models of CO2 sequestration under geological conditions should take into account the inhibiting role of surface coating formation. The CO2 rich fluid-rock interactions may also have significant consequences on metal mobilization. Our results indicated that the formation of stable carbonate complexes enhances the solubility of uranium minerals of both albitite and granite, facilitating the U(IV) oxidation, and limiting the extent of uranium adsorption onto particles in oxidized waters. This clearly produces an increase of the uranium mobility with significant consequences for the environment.

Formation of a deposit on workpiece surface in polishing nonmetallic materials

NASA Astrophysics Data System (ADS)

Filatov, Yu. D.; Monteil, G.; Sidorko, V. I.; Filatov, O. Y.

2013-05-01

During the last decades in the theory of machining nonmetallic materials some serious advances have been achieved in the field of applying fundamental scientific approaches to the grinding and polishing technologies for high-quality precision surfaces of electronic components, optical systems, and decorative articles made of natural and synthetic stone [1-9]. These achievements include a cluster model of material removal in polishing dielectric workpieces [1-3, 6-7] and a physical-statistical model of formation of debris (wear) particles and removal thereof from a workpiece surface [8-10]. The aforesaid models made it possible to calculate, without recourse to Preston's linear law, the removal rate in polishing nonmetallic materials and the wear intensity for bound-abrasive tools. Equally important for the investigation of the workpiece surface generation mechanism and formation of debris particles are the kinetic functions of surface roughness and reflectance of glass and quartz workpiece surfaces, which have been established directly in the course of polishing. During the in situ inspection of a workpiece surface by laser ellipsometry [11] and reflectometry [12] it was found out that the periodic change of the light reflection coefficient of a workpiece surface being polished is attributed to the formation of fragments of a deposit consisting of work material particles (debris particles) and tool wear particles [13, 14]. The subsequent studies of the mechanism of interaction between the debris particles and wear particles in the tool-workpiece contact zone, which were carried out based on classical concepts [15, 16], yielded some unexpected results. It was demonstrated that electrically charged debris and wear particles, which are located in the coolant-filled gap between a tool and a workpiece, move by closed circular trajectories enclosed in spheres measuring less than one fifth of the gap thickness. This implies that the probability of the debris and wear particles reaching the tool and workpiece surfaces and, especially, getting localized on the surfaces is extremely low, which contradicts the results of experimental examination of these surfaces. Based on the quantum-mechanical description of the process of scattering of the debris and wear particles that are as small as 3-4 nm in the tool-workpiece contact zone, the mechanism of formation of a workpiece microrelief and the mechanism of formation of a debris-particle deposit on the tool surface were clarified [17-21]. However, the mechanism of formation of the deposit fragments and their discrete arrangement on the workpiece surface in the process of polishing with a bound-abrasive tool has not been studied yet.

Charged particle space weathering rates at the Moon derived from ARTEMIS observations

NASA Astrophysics Data System (ADS)

Poppe, A. R.; Farrell, W. M.; Halekas, J. S.

2017-12-01

The weathering of airless bodies exposed to space is a fundamental process in the formation and evolution of planetary surfaces. At the Moon, space weathering induces a variety of physical, chemical, and optical changes including the formation of nanometer sized amorphous rims on individual lunar grains. These rims are formed by vapor redeposition from micrometeoroid impacts and ion irradiation-induced amorphization of the crystalline matrix. For ion irradiation-induced rims, however, laboratory experiments of the depth and formation timescales of these rims stand in stark disagreement with observations of lunar soil grains. We use observations by the ARTEMIS spacecraft in orbit around the Moon to compute the mean ion flux to the lunar surface and convolve this flux with ion irradiation-induced vacancy production rates calculated using the Stopping Range of Ions in Matter (SRIM) model. From this, we calculate the formation timescales for amorphous rim production as a function of depth and compare to laboratory experiments and observations of lunar soil. Our analysis resolves two outstanding issues: (1) the provenance of >100 nm amorphous rims on lunar grains and (2) the nature of the depth-age relationship for amorphous rims on lunar grains. We also present the hypothesis that ion beam-induced epitaxial crystallization is responsible for the discrepancy between observational and experimental results of the formation time of <100 nm amorphous rims.

Accelerated thermokarst formation in the McMurdo Dry Valleys, Antarctica.

PubMed

Levy, Joseph S; Fountain, Andrew G; Dickson, James L; Head, James W; Okal, Marianne; Marchant, David R; Watters, Jaclyn

2013-01-01

Thermokarst is a land surface lowered and disrupted by melting ground ice. Thermokarst is a major driver of landscape change in the Arctic, but has been considered to be a minor process in Antarctica. Here, we use ground-based and airborne LiDAR coupled with timelapse imaging and meteorological data to show that 1) thermokarst formation has accelerated in Garwood Valley, Antarctica; 2) the rate of thermokarst erosion is presently ~ 10 times the average Holocene rate; and 3) the increased rate of thermokarst formation is driven most strongly by increasing insolation and sediment/albedo feedbacks. This suggests that sediment enhancement of insolation-driven melting may act similarly to expected increases in Antarctic air temperature (presently occurring along the Antarctic Peninsula), and may serve as a leading indicator of imminent landscape change in Antarctica that will generate thermokarst landforms similar to those in Arctic periglacial terrains.

Accelerated thermokarst formation in the McMurdo Dry Valleys, Antarctica

PubMed Central

Levy, Joseph S.; Fountain, Andrew G.; Dickson, James L.; Head, James W.; Okal, Marianne; Marchant, David R.; Watters, Jaclyn

2013-01-01

Thermokarst is a land surface lowered and disrupted by melting ground ice. Thermokarst is a major driver of landscape change in the Arctic, but has been considered to be a minor process in Antarctica. Here, we use ground-based and airborne LiDAR coupled with timelapse imaging and meteorological data to show that 1) thermokarst formation has accelerated in Garwood Valley, Antarctica; 2) the rate of thermokarst erosion is presently ~ 10 times the average Holocene rate; and 3) the increased rate of thermokarst formation is driven most strongly by increasing insolation and sediment/albedo feedbacks. This suggests that sediment enhancement of insolation-driven melting may act similarly to expected increases in Antarctic air temperature (presently occurring along the Antarctic Peninsula), and may serve as a leading indicator of imminent landscape change in Antarctica that will generate thermokarst landforms similar to those in Arctic periglacial terrains. PMID:23881292

Dome growth at Mount Cleveland, Aleutian Arc, quantified by time-series TerraSAR-X imagery

USGS Publications Warehouse

Wang, Teng; Poland, Michael; Lu, Zhong

2016-01-01

Synthetic aperture radar imagery is widely used to study surface deformation induced by volcanic activity; however, it is rarely applied to quantify the evolution of lava domes, which is important for understanding hazards and magmatic system characteristics. We studied dome formation associated with eruptive activity at Mount Cleveland, Aleutian Volcanic Arc, in 2011–2012 using TerraSAR-X imagery. Interferometry and offset tracking show no consistent deformation and only motion of the crater rim, suggesting that ascending magma may pass through a preexisting conduit system without causing appreciable surface deformation. Amplitude imagery has proven useful for quantifying rates of vertical and areal growth of the lava dome within the crater from formation to removal by explosive activity to rebirth. We expect that this approach can be applied at other volcanoes that host growing lava domes and where hazards are highly dependent on dome geometry and growth rates.

Contact formation in gallium arsenide solar cells

NASA Technical Reports Server (NTRS)

Weizer, Victor G.; Fatemi, Navid S.

1988-01-01

Gold and gold-based alloys, commonly used as solar cell contact materials, are known to react readily with gallium arsenide. Experiments were performed to identify the mechanisms involved in these GaAs-metal interactions. It is shown that the reaction of GaAs with gold takes place via a dissociative diffusion process. It is shown further that the GaAs-metal reaction rate is controlled to a very great extent by the condition of the free surface of the contact metal, an interesting example of which is the previously unexplained increase in the reaction rate that has been observed for samples annealed in a vacuum environment as compared to those annealed in a gaseous ambient. A number of other hard-to-explain observations, such as the low-temperature formation of voids in the gold lattice and crystallite growth on the gold surface, are explained by invoking this mechanism.

[INVITED] Laser treatment of Inconel 718 alloy and surface characteristics

NASA Astrophysics Data System (ADS)

Yilbas, B. S.; Ali, H.; Al-Aqeeli, N.; Karatas, C.

2016-04-01

Laser surface texturing of Inconel 718 alloy is carried out under the high pressure nitrogen assisting gas. The combination of evaporation and melting at the irradiated surface is achieved by controlling the laser scanning speed and the laser output power. Morphological and metallurgical changes in the treated surface are analyzed using the analytical tools including optical, electron scanning, and atomic force microscopes, energy dispersive spectroscopy, and X-ray diffraction. Microhardnes and friction coefficient of the laser treated surface are measured. Residual stress formed in the surface region is determined from the X-ray diffraction data. Surface hydrophobicity of the laser treated layer is assessed incorporating the sessile drop method. It is found that laser treated surface is free from large size asperities including cracks and the voids. Surface microhardness increases significantly after the laser treatment process, which is attributed to the dense layer formation at the surface under the high cooling rates, dissolution of Laves phase in the surface region, and formation of nitride species at the surface. Residual stress formed is compressive in the laser treated surface and friction coefficient reduces at the surface after the laser treatment process. The combination of evaporation and melting at the irradiated surface results in surface texture composes of micro/nano-poles and pillars, which enhance the surface hydrophobicity.

Microstructure and mechanical behavior of pulsed laser surface melted AISI D2 cold work tool steel

NASA Astrophysics Data System (ADS)

Yasavol, N.; Abdollah-zadeh, A.; Ganjali, M.; Alidokht, S. A.

2013-01-01

D2 cold work tool steel (CWTS) was subjected to pulse laser surface melting (PLSM) at constant frequency of 20 Hz Nd: YAG laser with different energies, scanning rate and pulse durations radiated to the surface. Characterizing the PLSM, with optical and field emission scanning electron microscopy, electron backscattered diffraction and surface hardness mapping technique was used to evaluate the microhardness and mechanical behavior of different regions of melting pool. Increasing laser energy and reducing the laser scanning rate results in deeper melt pool formation. Moreover, PLSM has led to entirely dissolution of the carbides and re-solidification of cellular/dendritic structure of a fine scale surrounded by a continuous interdendritic network. This caused an increase in surface microhardness, 2-4 times over that of the base metal.

Principal curvatures and area ratio of propagating surfaces in isotropic turbulence

NASA Astrophysics Data System (ADS)

Zheng, Tianhang; You, Jiaping; Yang, Yue

2017-10-01

We study the statistics of principal curvatures and the surface area ratio of propagating surfaces with a constant or nonconstant propagating velocity in isotropic turbulence using direct numerical simulation. Propagating surface elements initially constitute a plane to model a planar premixed flame front. When the statistics of evolving propagating surfaces reach the stationary stage, the statistical profiles of principal curvatures scaled by the Kolmogorov length scale versus the constant displacement speed scaled by the Kolmogorov velocity scale collapse at different Reynolds numbers. The magnitude of averaged principal curvatures and the number of surviving surface elements without cusp formation decrease with increasing displacement speed. In addition, the effect of surface stretch on the nonconstant displacement speed inhibits the cusp formation on surface elements at negative Markstein numbers. In order to characterize the wrinkling process of the global propagating surface, we develop a model to demonstrate that the increase of the surface area ratio is primarily due to positive Lagrangian time integrations of the area-weighted averaged tangential strain-rate term and propagation-curvature term. The difference between the negative averaged mean curvature and the positive area-weighted averaged mean curvature characterizes the cellular geometry of the global propagating surface.

Shrink wrapping redox-active crystals of polyoxometalate open frameworks with organic polymers via crystal induced polymerisation.

PubMed

Takashima, Yohei; Miras, Haralampos N; Glatzel, Stefan; Cronin, Leroy

2016-06-14

We report examples of crystal surface modification of polyoxometalate open frameworks whereby the use of pyrrole or aniline as monomers leads to the formation of the corresponding polymers via an oxidative polymerization process initiated by the redox active POM scaffolds. Guest-exchange experiments demonstrate that the polymers can finely tune the guest exchange rate and their structural integrity is retained after the surface modifications. In addition, the formation of polyoxometalate-based self-fabricating tubes by the dissolution of Keggin-based network crystals were also modulated by the polymers, allowing a new type of hybrid inorganic polymer with an organic coating to be fabricated.

Dolomite dissolution rates and possible Holocene dedolomitization of water-bearing units in the Edwards aquifer, south-central Texas

USGS Publications Warehouse

Deike, R.G.

1990-01-01

Rates of dolomite dissolution can be used to test the concept, based on geomorphologic evidence, that a major part of the Edwards aquifer could have formed within the Holocene, a timeframe of approximately 10,000 years. During formation of the aquifer in the Edwards limestone (Cretaceous, Albian) of the Balcones fault zone, dolomite dissolution and porosity development were synchronous and the result of mixing-zone dedolomitization. Initiation of the mixing zone in the early Holocene (???11,000 years before present) is suggested by the maximum age of formation of major discharge sites that allowed the influx of meteoric water into brine-filled, dolomitic preaquifer units. Dedolomitization, the dissolution of dolomite and net precipitation of calcite, has left aquifer units that are calcitic, and 40 vol.% interconnected pore space. The mass of dolomite missing is obtained by comparison of stratigraphically equivalent altered and unaltered units. One dissolution rate (1.76 ?? 10-4 mmol dolomite kgH2O-1yr-1) is determined from this mass, 104yr reaction time, and a log-linear function describing the increase in mass discharge (three orders of magnitude) during aquifer formation. The second estimated dissolution rate is obtained from the mass transfer of dolomite to solution calculated from the increase in magnesium in pore fluids selected from the modern aquifer to represent a typical flowpath during aquifer formation. A reaction time of 104yr for this mass transfer yields a rate of 0.56 ?? 10-4 mmol dolomite kgH2O-1yr-1. Both of these rates are comparable to modern rates of dolomite dissolution (0.3 to 4.5 ?? 10-4 mmol dolomite kgH2O-1yr-1) calculated from measured reaction times in the Tertiary Floridan aquifer system in Florida and the Madison aquifer in the Mississippian Madison Limestone of the Northern Great Plains. Similarity of these rates to the estimated paleo-rates of dolomite dissolution supports a 104 yr reaction timeframe. The Holocene reaction time also can be compared to a series of reaction times calculated by assuming that the mass of dolomite missing from the Edwards was removed at rates observed in the Floridan and Madison aquifers. These reaction times (for complete removal of dolomite) range from 2700 to 58,500 yr and span the Pleistocene-Holocene boundary. Finally, an estimated dolomite reaction rate during dedolomitization of the Edwards aquifer based on surface area of exposed dolomite [mmol cm-2s-1 (millimoles per square centimeter per second)] may be approximated from reaction times. This rate is directly a function of the mass of dolomite removed and the surface area exposed per pore volume passing through the rock. The surface area is available from the observed dolomite rhomb size in unaltered rock. The rate of pore fluid movement is obtained from the averaged annual discharge. Rates during formation of the Edwards aquifer calculated from all reaction times range from 10-13 to 10-14 mmol dolomite cm-2s-1. These rates are faster than rates (10-18 mmol cm-2s-1), measured in the pure laboratory system, CaMg(CO3)2CO2H2O, but slower than rates determined in an alpine stream study (10-10 to 10-11 mmol cm-2s-1) where cold glacial melt water flows over dolostone. Dolomite dissolution rates from both the Edwards and other aquifers support the concept that a major part of the Edwards aquifer could have formed within the Holocene. ?? 1990.

Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

NASA Astrophysics Data System (ADS)

van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

2014-11-01

The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

The formation of hydrogen permeation barriers on steels by aluminising

NASA Astrophysics Data System (ADS)

Forcey, K. S.; Ross, D. K.; Wu, C. H.

1991-06-01

An extensive investigation has been carried out into the effectiveness of aluminised layers as permeation barriers on AISI 316L stainless and DIN 1.4914 martensitic steels. The study involved measurement of the hydrogen permeation rate through commercially aluminised steel discs of thicknesses in the range 1-1.6 mm, at temperatures between 250 and 600 °C and for an upstream hydrogen pressure of 10 5 Pa. The composition and structure of the aluminide layers were investigated by a number of techniques such as SEM, electron beam microprobe and X-ray diffraction. Accelerator based techniques such as RBS and NRA were employed to study the top micron or so of the surfaces of the samples. By these techniques it was found that the effectiveness of the permeation barrier depended on the formation of a thin surface oxide layer consisting of Al 2O 3. It was found that the permeation rate through the aluminised steels could be reduced by 3-4 orders of magnitude by forming a surface oxide layer up to a micron or so in thickness.

SDSS-IV MaNGA: the spatial distribution of star formation and its dependence on mass, structure, and environment

NASA Astrophysics Data System (ADS)

Spindler, Ashley; Wake, David; Belfiore, Francesco; Bershady, Matthew; Bundy, Kevin; Drory, Niv; Masters, Karen; Thomas, Daniel; Westfall, Kyle; Wild, Vivienne

2018-05-01

We study the spatially resolved star formation of 1494 galaxies in the SDSS-IV MaNGA Survey. Star formation rates (SFRs) are calculated using a two-step process, using H α in star-forming regions and Dn4000 in regions identified as active galactic nucleus/low-ionization (nuclear) emission region [AGN/LI(N)ER] or lineless. The roles of secular and environmental quenching processes are investigated by studying the dependence of the radial profiles of specific star formation rate on stellar mass, galaxy structure, and environment. We report on the existence of `centrally suppressed' galaxies, which have suppressed Specific Star Formation Rate (SSFR) in their cores compared to their discs. The profiles of centrally suppressed and unsuppressed galaxies are distributed in a bimodal way. Galaxies with high stellar mass and core velocity dispersion are found to be much more likely to be centrally suppressed than low-mass galaxies, and we show that this is related to morphology and the presence of AGN/LI(N)ER like emission. Centrally suppressed galaxies also display lower star formation at all radii compared to unsuppressed galaxies. The profiles of central and satellite galaxies are also compared, and we find that satellite galaxies experience lower specific star formation rates at all radii than central galaxies. This uniform suppression could be a signal of the stripping of hot halo gas in the process known as strangulation. We find that satellites are not more likely to be suppressed in their cores than centrals, indicating that the core suppression is an entirely internal process. We find no correlation between the local environment density and the profiles of star formation rate surface density.

Bone Formation is Affected by Matrix Advanced Glycation End Products (AGEs) In Vivo.

PubMed

Yang, Xiao; Mostafa, Ahmed Jenan; Appleford, Mark; Sun, Lian-Wen; Wang, Xiaodu

2016-10-01

Advanced glycation end products (AGEs) accumulate in bone extracellular matrix as people age. Although previous evidence shows that the accumulation of AGEs in bone matrix may impose significant effects on bone cells, the effect of matrix AGEs on bone formation in vivo is still poorly understood. To address this issue, this study used a unique rat model with autograft implant to investigate the in vivo response of bone formation to matrix AGEs. Fluorochrome biomarkers were sequentially injected into rats to label the dynamic bone formation in the presence of elevated levels of matrix AGEs. After sacrificing animals, dynamic histomorphometry was performed to determine mineral apposition rate (MAR), mineralized surface per bone surface (MS/BS), and bone formation rate (BFR). Finally, nanoindentation tests were performed to assess mechanical properties of newly formed bone tissues. The results showed that MAR, MS/BS, and BFR were significantly reduced in the vicinity of implant cores with high concentration of matrix AGEs, suggesting that bone formation activities by osteoblasts were suppressed in the presence of elevated matrix AGEs. In addition, MAR and BFR were found to be dependent on the surrounding environment of implant cores (i.e., cortical or trabecular tissues). Moreover, MS/BS and BFR were also dependent on how far the implant cores were away from the growth plate. These observations suggest that the effect of matrix AGEs on bone formation is dependent on the biological milieu around the implants. Finally, nanoindentation test results indicated that the indentation modulus and hardness of newly formed bone tissues were not affected by the presence of elevated matrix AGEs. In summary, high concentration of matrix AGEs may slow down the bone formation process in vivo, while imposing little effects on bone mineralization.

Topographic inversion of early interdune deposits, Navajo Sandstone (Lower Jurassic), Colorado Plateau, USA

NASA Astrophysics Data System (ADS)

Bromley, Michael

1992-09-01

Outliers of Navajo Sandstone (Lower Jurassic Glen Canyon Group) form low paleohills east of the main body of the Formation in the Salt Anticline region of southwestern Colorado. The paleohills consist of interdune deposits which developed topographic inversion during erosion of the Jurassic J-2 unconformity owing to a tough shell of early cemented sandstones and cherty limestones. The interdune deposits accumulated over playa mudstones of the Kayenta Formation which formed in a structural low between the Uncompahgre Uplift and the Paradox Valley salt anticline. Open-framework textures indicate the early formation of quartz or chert cement in sandstone beds immediately above the impermeable playa mudstones. The mudstones enhanced the subsequent formation of wet interdune deposits keeping groundwater near the surface. Microcrystalline quartz cements and fresh feldspars suggest that groundwater was alkaline. A source of alkalinity may have been eolian dust carried from emergent Pennsylvanian evaporite intrusions upwind of the playa deposits. The high specific surface of siliceous and evaporite dusts combined with shallow groundwater and high evaporation rates resulted in the rapid formation of quartzitic silcrete crusts above the playa mudstone aquacludes. As these early silcretes were buried, the impermeable mudstone foundations beneath them continued to serve as aquacludes. The inclined potentiometric surface of perched water tables above the isolated aquacludes intersected the land surface at progressively higher levels as the mudstone lenses were buried. Groundwater moving laterally from above the aquacludes carried dissolved material towards the inclined water tables at their margins. This mobilized material was redeposited as early cement where the capillary fringe intersected the land surface. As the land surface aggraded vertically, the zone of cement formation migrated laterally in response of a change of the relative positions of the land surface and an inclined perched water table. The final products of this process were topographic remnants of Navajo Sandstone with a resistant rind of cemented material enclosing a core of leached, compacted and friable sandstones. Erosion of the J-2 unconformity left the cemented rind in relief while removing all material around it. The resulting hills survived the onlap of the Middle Jurassic Entrada Formation, leaving considerable relief beneath the unconformity.

Advantages of low pH and limited oxygenation in arsenite removal from water by zero-valent iron.

PubMed

Klas, Sivan; Kirk, Donald W

2013-05-15

The removal of toxic arsenic species from contaminated waters by zero-valent iron (ZVI) has drawn considerable attention in recent years. In this approach, arsenic ions are mainly removed by adsorption to the iron corrosion products. Reduction to zero-valent arsenic on the ZVI surface is possible in the absence of competing oxidants and can reduce arsenic mobility and sludge formation. However, associated removal rates are relatively low. In the current study, simultaneous high reduction and removal rates of arsenite (H3AsO3), the more toxic and mobile environmentally occurring arsenic species, was demonstrated by reacting it with ZVI under limited aeration and relatively low pH. 90% of the removed arsenic was attached to the ZVI particles and 60% of which was in the elemental state. Under the same non-acidic conditions, only 40-60% of the removed arsenic was attached to the ZVI with no change in arsenic oxidation state. Under anaerobic conditions, reduction occurred but total arsenic removal rate was significantly lower and ZVI demand was higher. The effective arsenite removal under acidic oxygen-limited conditions was explained by formation of Fe(II)-solid intermediate on the ZVI surface that provided high surface area and reducing power. Copyright © 2013 Elsevier B.V. All rights reserved.

Star formation in massive Milky Way molecular clouds: Building a bridge to distant galaxies

NASA Astrophysics Data System (ADS)

Willis, Sarah Elizabeth

The Kennicutt-Schmidt relation is an empirical power-law linking the surface density of the star formation rate (SigmaSFR) to the surface density of gas (Sigmagas ) averaged over the observed face of a starforming galaxy Kennicutt (1998). The original presentation used observations of CO to measure gas density and H alpha emission to measure the population of hot, massive young stars (and infer the star formation rate). Observations of Sigma SFR from a census of young stellar objects in nearby molecular clouds in our Galaxy are up to 17 times higher than the extragalactic relation would predict given their Sigmagas. These clouds primarily form low-mass stars that are essentially invisible to star formation rate tracers. A sample of six giant molecular cloud (GMC) complexes with signposts of massive star formation was identified in our galaxy. The regions selected have a range of total luminosity and morphology. Deep ground-based observations in the near-infrared with NEWFIRM and IRAC observations with the Spitzer Space Telescope were used to conduct a census of the young stellar content associated with each of these clouds. The star formation rates from the stellar census in each of these regions was compared with the star formation rates measured by extragalactic star formation rate tracers based on monochromatic mid-infrared luminosities. Far-infrared Herschel observations from 160 through 500 mum were used to determine the column density and temperature in each region. The region NGC 6334 served as a test case to compare the Herschel column density measurements with the measurements for near-infrared extinction. The combination of the column density maps and the stellar census lets us examine SigmaSFR vs. Sigma gas for the massive GMCs. These regions are consistent with the results for the low-mass molecular clouds, indicating Sigma SFR levels that are higher than predicted based on Sigma gas. The overall Sigmagas levels are higher for the massive star forming regions, indicating that they have a higher fraction of dense gas than the clouds that are forming primarily low mass stars. There is still significant spread at a given average gas density, indicating that the star formation history and dense gas fraction play important roles in determining an individual molecular cloud's place in a Sigma SFR vs. Sigmagas diagram. Zooming in, SigmaSFR vs. Sigma gas was examined within the individual clouds, revealing a decrease relative to the spread that is observed for the average over whole clouds. The dependence of SigmaSFR on Sigma gas increases significantly above AV ˜ 5 - 10 which is consistent with previous measurements of a threshold for star formation around AV = 8 or Sigma gas = 0.04 g cm-2. NGC 6334 was found to be consistent with a threshold for massive star formation at Sigmagas = 1 g cm-2.

Composition-dependent metallic glass alloys correlate atomic mobility with collective glass surface dynamics.

PubMed

Nguyen, Duc; Zhu, Zhi-Guang; Pringle, Brian; Lyding, Joseph; Wang, Wei-Hua; Gruebele, Martin

2016-06-22

Glassy metallic alloys are richly tunable model systems for surface glassy dynamics. Here we study the correlation between atomic mobility, and the hopping rate of surface regions (clusters) that rearrange collectively on a minute to hour time scale. Increasing the proportion of low-mobility copper atoms in La-Ni-Al-Cu alloys reduces the cluster hopping rate, thus establishing a microscopic connection between atomic mobility and dynamics of collective rearrangements at a glass surface made from freshly exposed bulk glass. One composition, La60Ni15Al15Cu10, has a surface resistant to re-crystallization after three heating cycles. When thermally cycled, surface clusters grow in size from about 5 glass-forming units to about 8 glass-forming units, evidence of surface aging without crystal formation, although its bulk clearly forms larger crystalline domains. Such kinetically stable glass surfaces may be of use in applications where glassy coatings stable against heating are needed.

Correlation between rate of bony ingrowth to stainless steel, pure titanium, and titanium alloy implants in vivo and formation of hydroxyapatite on their surfaces in vitro.

PubMed

Oron, A; Agar, G; Oron, U; Stein, A

2009-12-15

The rate of bony ingrowth to identical metal implants made of either pure titanium (cpTi), titanium alloy (Ti-6Al-4V), or stainless steel 316L (SS) inserted to the medullar canal of the femur in rats was investigated. The kinetics of spontaneous deposition of hydroxyapatite (HA) globules on the aforementioned metals in vitro during incubation in simulated body fluid (SBF) was also studied. It was found that the rate of increased bonding strength between the cpTi implants and the host bone was the highest, whereas around the SS implants it was the slowest. At 10 days postimplant insertion, the shear strength of the cpTi implants was 2.2- and 4-fold significantly higher than for the Ti-6Al-4V and the SS implants, respectively. Spontaneous formation of the HA globules on the cpTi and Ti-6Al-4V implants that were incubated in the SBF was observed as early as 6 and 10 days after incubation in SBF, respectively, whereas on SS implants, deposition of HA was evident only after 2 weeks of in vitro incubation in SBF. It is concluded that the chemical surface characteristics and the biocompatibility of the implants probably play a key role in the process of bone growth next to them, during the formation of bone in vivo. The rate of bony ingrowth to various metal implants alloys inserted into the medullar canal of rats correlates well with the induction of apatite formation on them during incubation in vitro with SBF.

Formation of the InAs-, InSb-, GaAs-, and GaSb-polished surface

NASA Astrophysics Data System (ADS)

Levchenko, Iryna; Tomashyk, Vasyl; Stratiychuk, Iryna; Malanych, Galyna; Korchovyi, Andrii; Kryvyi, Serhii; Kolomys, Oleksandr

2018-04-01

The features of the InAs, InSb, GaAs, and GaSb ultra-smooth surface have been investigated using chemical-mechanical polishing with the (NH4)2Cr2O7-HBr-CH2(OH)CH2(OH)-etching solutions. The etching rate of the semiconductors has been measured as a function of the solution saturation by organic solvent (ethylene glycol). It was found that mechanical effect significantly increases the etching rate from 1.5 to 57 µm/min, and the increase of the organic solvent concentration promotes the decrease of the damaged layer-removing rate. According to AFM, RS, HRXRD results, the treatment with the (NH4)2Cr2O7-HBr-ethylene glycol solutions produces the clean surface of the nanosize level (R a < 0.5 nm).

Chemical reaction CO+OH • → CO 2+H • autocatalyzed by carbon dioxide: Quantum chemical study of the potential energy surfaces

DOE PAGES

Masunov, Artem E.; Wait, Elizabeth; Vasu, Subith S.

2016-06-28

The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO 2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO 2 to OH radical and CO molecule, hydrogen transfer frommore » oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO 2 medium. Furthermore, tt may open a new venue for controlling reaction rates for chemical manufacturing.« less

Time course of disassociation of bone formation signals with bone mass and bone strength in sclerostin antibody treated ovariectomized rats.

PubMed

Ma, Yanfei L; Hamang, Matthew; Lucchesi, Jonathan; Bivi, Nicoletta; Zeng, Qianqiang; Adrian, Mary D; Raines, Sarah E; Li, Jiliang; Kuhstoss, Stuart A; Obungu, Victor; Bryant, Henry U; Krishnan, Venkatesh

2017-04-01

Sclerostin antibodies increase bone mass by stimulating bone formation. However, human and animal studies show that bone formation increases transiently and returns to pre-treatment level despite ongoing antibody treatment. To understand its mechanism of action, we studied the time course of bone formation, correlating the rate and extent of accrual of bone mass and strength after sclerostin antibody treatment. Ovariectomized (OVX) rats were treated with a sclerostin-antibody (Scle-ab) at 20mg/kg sc once weekly and sacrificed at baseline and 2, 3, 4, 6, and 8weeks post-treatment. In Scle-ab treated rats, serum PINP and OCN rapidly increased at week 1, peaked around week 3, and returned to OVX control levels by week 6. Transcript analyses from the distal femur revealed an early increase in bone formation followed by a sustained decrease in bone resorption genes. Lumbar vertebral (LV) osteoblast surface increased 88% by week 2, and bone formation rate (BFR/BS) increased 138% by week 4. Both parameters were below OVX control by week 8. Bone formation was primarily a result of modeling based formation. Endocortical and periosteal BFR/BS peaked around week 4 at 313% and 585% of OVX control, respectively. BFR/BS then declined but remained higher than OVX control on both surfaces through week 8. Histomorphometric analyses showed LV-BV/TV did not further increase after week 4, while BMD continued to increase at LV, mid femur (MF), and femoral neck (FN) through week 8. Biomechanical tests showed a similar improvement in bone strength through 8weeks in MF and FN, but bone strength plateaued between weeks 6 and 8 for LV. Our data suggest that bone formation with Scle-ab treatment is rapid and modeling formation dominated in OVX rats. Although transient, the bone formation response persists longer in cortical than trabecular bone. Copyright © 2016 Elsevier Inc. All rights reserved.

Nanoscale oxidation and complex oxide growth on single crystal iron surfaces and external electric field effects.

PubMed

Jeon, Byoungseon; Van Overmeere, Quentin; van Duin, Adri C T; Ramanathan, Shriram

2013-02-14

Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.

Galaxy evolution. Evidence for mature bulges and an inside-out quenching phase 3 billion years after the Big Bang.

PubMed

Tacchella, S; Carollo, C M; Renzini, A; Förster Schreiber, N M; Lang, P; Wuyts, S; Cresci, G; Dekel, A; Genzel, R; Lilly, S J; Mancini, C; Newman, S; Onodera, M; Shapley, A; Tacconi, L; Woo, J; Zamorani, G

2015-04-17

Most present-day galaxies with stellar masses ≥10(11) solar masses show no ongoing star formation and are dense spheroids. Ten billion years ago, similarly massive galaxies were typically forming stars at rates of hundreds solar masses per year. It is debated how star formation ceased, on which time scales, and how this "quenching" relates to the emergence of dense spheroids. We measured stellar mass and star-formation rate surface density distributions in star-forming galaxies at redshift 2.2 with ~1-kiloparsec resolution. We find that, in the most massive galaxies, star formation is quenched from the inside out, on time scales less than 1 billion years in the inner regions, up to a few billion years in the outer disks. These galaxies sustain high star-formation activity at large radii, while hosting fully grown and already quenched bulges in their cores. Copyright © 2015, American Association for the Advancement of Science.

Massive star formation in 100,000 years from turbulent and pressurized molecular clouds.

PubMed

McKee, Christopher F; Tan, Jonathan C

2002-03-07

Massive stars (with mass m* > 8 solar masses Mmiddle dot in circle) are fundamental to the evolution of galaxies, because they produce heavy elements, inject energy into the interstellar medium, and possibly regulate the star formation rate. The individual star formation time, t*f, determines the accretion rate of the star; the value of the former quantity is currently uncertain by many orders of magnitude, leading to other astrophysical questions. For example, the variation of t*f with stellar mass dictates whether massive stars can form simultaneously with low-mass stars in clusters. Here we show that t*f is determined by the conditions in the star's natal cloud, and is typically about 105yr. The corresponding mass accretion rate depends on the pressure within the cloud--which we relate to the gas surface density--and on both the instantaneous and final stellar masses. Characteristic accretion rates are sufficient to overcome radiation pressure from about 100M middle dot in circle protostars, while simultaneously driving intense bipolar gas outflows. The weak dependence of t*f on the final mass of the star allows high- and low-mass star formation to occur nearly simultaneously in clusters.

Modeling and predicting the biofilm formation of Salmonella Virchow with respect to temperature and pH.

PubMed

Ariafar, M Nima; Buzrul, Sencer; Akçelik, Nefise

2016-03-01

Biofilm formation of Salmonella Virchow was monitored with respect to time at three different temperature (20, 25 and 27.5 °C) and pH (5.2, 5.9 and 6.6) values. As the temperature increased at a constant pH level, biofilm formation decreased while as the pH level increased at a constant temperature, biofilm formation increased. Modified Gompertz equation with high adjusted determination coefficient (Radj(2)) and low mean square error (MSE) values produced reasonable fits for the biofilm formation under all conditions. Parameters of the modified Gompertz equation could be described in terms of temperature and pH by use of a second order polynomial function. In general, as temperature increased maximum biofilm quantity, maximum biofilm formation rate and time of acceleration of biofilm formation decreased; whereas, as pH increased; maximum biofilm quantity, maximum biofilm formation rate and time of acceleration of biofilm formation increased. Two temperature (23 and 26 °C) and pH (5.3 and 6.3) values were used up to 24 h to predict the biofilm formation of S. Virchow. Although the predictions did not perfectly match with the data, reasonable estimates were obtained. In principle, modeling and predicting the biofilm formation of different microorganisms on different surfaces under various conditions could be possible.

Reaction Mechanisms for the Electrochemical Reduction of CO2 to CO and Formate on the Cu(100) Surface at 298K from Quantum Mechanics Free Energy Calculations with Explicit Water.

PubMed

Cheng, Tao; Xiao, Hai; Goddard, William A

2016-10-11

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions are not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). Here, we carry out Quantum Mechanics (QM) calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO2RR conditions) to examine the initial reaction pathways to form CO and formate (HCOO - ) from CO 2 through free energy calculations at 298K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ- ), with a free energy barrier of ΔG ‡ =0.43 eV, the rate determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 eV and 0.30 eV, respectively. HCOO - formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO - formation occurs in the first electron transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Thus, to alter the product distribution we need to control this first step of CO 2 binding, which might involve alloying or changing the structure at the nanoscale.

Combustion dynamics of low vapour pressure nanofuel droplets

NASA Astrophysics Data System (ADS)

Pandey, Khushboo; Chattopadhyay, Kamanio; Basu, Saptarshi

2017-07-01

Multiscale combustion dynamics, shape oscillations, secondary atomization, and precipitate formation have been elucidated for low vapour pressure nanofuel [n-dodecane seeded with alumina nanoparticles (NPs)] droplets. Dilute nanoparticle loading rates (0.1%-1%) have been considered. Contrary to our previous studies of ethanol-water blend (high vapour pressure fuel), pure dodecane droplets do not exhibit internal boiling after ignition. However, variation in surface tension due to temperature causes shape deformations for pure dodecane droplets. In the case of nanofuels, intense heat release from the enveloping flame leads to the formation of micron-size aggregates (of alumina NPS) which serve as nucleation sites promoting heterogeneous boiling. Three boiling regimes (A, B, and C) have been identified with varying bubble dynamics. We have deciphered key mechanisms responsible for the growth, transport, and rupture of the bubbles. Bubble rupture causes ejections of liquid droplets termed as secondary atomization. Ejection of small bubbles (mode 1) resembles the classical vapour bubble collapse mechanism near a flat free surface. However, large bubbles induce severe shape deformations as well as bulk oscillations. Rupture of large bubbles results in high speed liquid jet formation which undergoes Rayleigh-Plateau tip break-up. Both modes contribute towards direct fuel transfer from the droplet surface to flame envelope bypassing diffusion limitations. Combustion lifetime of nanofuel droplets consequently has two stages: stage I (where bubble dynamics are dominant) and stage II (formation of gelatinous mass due to continuous fuel depletion; NP agglomeration). In the present work, variation of flame dynamics and spatio-temporal heat release (HR) have been analysed using high speed OH* chemiluminescence imaging. Fluctuations in droplet shape and flame heat release are found to be well correlated. Droplet flame is bifurcated in two zones (I and II). Flame response is manifested in two frequency ranges: (i) buoyant flame flickering and (ii) auxiliary frequencies arising from high intensity secondary ejections due to bubble ruptures. Addition of alumina NPs enhances the heat absorption rate and ensures the rapid transfer of fuel parcels (detached daughter droplets) from droplet surface to flame front through secondary ejections. Therefore, average HR shows an increasing trend with particle loading rate (PLR). The perikinetic agglomeration model is used to explain the formation of gelatinous sheath during the last phase of droplet burning. Gelatinous mass formed results in bubble entrapment. SEM images of combustion precipitates show entrapped bubble cavities along with surface and sub-surface blowholes. Morphology of combustion precipitate shows a strong variation with PLRs. We have established the coupling mechanisms among heat release, shape oscillations, and secondary atomizations that underline the combustion behaviour of such low vapour pressure nanofuels.

[Effects of simulated body fluid flowing rate on bone-like apatite formation on porous calcium phosphate ceramics].

PubMed

Duan, You-rong; Liu, Ke-wei; Chen, Ji-yong; Zhang, Xing-dong

2002-06-01

Objective. Bone-like apatite formation on the surface of calcium phosphate ceramics was believed to be the necessary step that new bone grows on the ceramics and to be relative to the osteoinductivity of the material. This study aimed at investigating the influence of the flow rate of simulated body fluid (SBF) (2 ml/min) in skeletal muscle upon the formation of bone-like apatite on porous calcium phosphate ceramics. Method. The dynamic condition was realized by controlling the SBF flowing in/out of the sample chamber of 100 ml. The flow rate of 2 ml/min is close to that in human muscle environment. The pH and inorganic ionic composition of SBF are close to those of human body fluid. Result. Bone-like apatite formation was relatively easier to occur in static SBF than in dynamic SBF. Experiment with flowing SBF (dynamic SBF) is better in mimicking the living body fluid than static SBF. Conclusion. The results from dynamic SBF may more truly show the relation between apatite layer formation and osteoinduction in biomaterials than that from in vitro experiments before.

Sludge settling processes in SBR-related sewage treatment plants according to the Biocos method.

PubMed

Meusel, S; Englert, R

2004-01-01

This paper describes the investigations in a sedimentation and circulation reactor (SU-reactor) of a three-phase Biocos plant. The aim of these investigations was the determination of the temporal and depth-dependent distribution of suspended solid contents, as well as describing the sludge sedimentation curves. The calculated results reveal peculiarities of the Biocos method with regard to sedimentation processes. In the hydraulically uninterrupted (pre-)settling phase, a sludge level depth was observed, which remained constant over the reactor surface and increased linearly according to the sludge volume. The settling and the thickening processes of this phase corresponded to a large extent to the well-known settling test in a one-litre measuring cylinder. During the discharge phase, the investigated settling rate was overlaid by the surface loading rate and the sludge level changed depending on the difference between those two parameters. The solid distribution of the A-phase indicated a formation of functional zones, which were influenced by the surface loading. The formation was comparable to the formation of layers in secondary settling tanks with vertical flow. The concentration equalisation between the biological reactor and the SU-reactor proved to be problematic during the circulation phase, because a type of internal sludge circulation occurred in the SU-reactor. A permanent sludge recirculation seems to be highly recommendable.

Surface morphology of molybdenum silicide films upon low-energy ion beam sputtering

NASA Astrophysics Data System (ADS)

Gago, R.; Jaafar, M.; Palomares, F. J.

2018-07-01

The surface morphology of molybdenum silicide (Mo x Si1‑x ) films has been studied after low-energy Ar+ ion beam sputtering (IBS) to explore eventual pattern formation on compound targets and, simultaneously, gather information about the mechanisms behind silicide-assisted nanopatterning of silicon surfaces by IBS. For this purpose, Mo x Si1‑x films with compositions below, equal and above the MoSi2 stoichiometry (x  =  0.33) have been produced by magnetron sputtering, as assessed by Rutherford backscattering spectrometry (RBS). The surface morphology of silicon and silicide films before and after IBS has been imaged by atomic force microscopy (AFM), comprising conditions where typical nanodot or ripple patterns emerge on the former. In the case of irradiated Mo x Si1‑x surfaces, AFM shows a marked surface smoothing at normal incidence with and without additional Mo incorporation (the former results in nanodot patterns on Si). The morphological analysis also provides no evidence of ion-induced phase separation in irradiated Mo x Si1‑x . Contrary to silicon, Mo x Si1‑x surfaces also do not display ripple formation for (impurity free) oblique irradiations, except at grazing incidence conditions where parallel ripples emerge in a more evident fashion than in the Si counterpart. By means of RBS, irradiated Mo x Si1‑x films with 1 keV Ar+ at normal incidence have also been used to measure experimentally the (absolute) sputtering yield and rate of Si and Mo x Si1‑x materials. The analysis reveals that, under the present working conditions, the erosion rate of silicides is larger than for silicon, supporting simulations from the TRIDYN code. This finding questions the shielding effect from silicide regions as roughening mechanism in metal-assisted nanopatterning of silicon. On the contrary, the results highlight the relevance of in situ silicide formation. Ripple formation on Mo x Si1‑x under grazing incidence is also attributed to the dominance of sputtering effects under this geometry. In conclusion, our work provides some insights into the complex morphological evolution of compound surfaces and solid experimental evidences regarding the mechanisms behind silicide-assisted nanopatterning.

Microscale Confinement features in microfluidic devices can affect biofilm

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Aloke; Karig, David K; Neethirajan, Suresh

2013-01-01

Biofilms are aggregations of microbes that are encased by extra-cellular polymeric substances (EPS) and adhere to surfaces and interfaces. Biofilm development on abiotic surfaces is a dynamic process, which typically proceeds through an initial phase of adhesion of plankntonic microbes to the substrate, followed by events such as growth, maturation and EPS secretion. However, the coupling of hydrodynamics, microbial adhesion and biofilm growth remain poorly understood. Here, we investigate the effect of semiconfined features on biofilm formation. Using a microfluidic device and fluorescent time-lapse microscopy, we establish that confinement features can significantly affect biofilm formation. Biofilm dynamics change not onlymore » as a function of confinement features, but also of the total fluid flow rate, and our combination of experimental results and numerical simulations reveal insights into the link between hydrodynamics and biofilm formation.« less

Reactive Molecular Dynamics Investigations of Alkoxysilane Sol-Gel and Surface Coating Processes

NASA Astrophysics Data System (ADS)

Deetz, Joshua David

The ability to generate nanostructured materials with tailored morphology or chemistry is of great technological interest. One proven method of generating metal-oxide materials, and chemically modifying metal-oxide surfaces is through the reactions of molecular building blocks known as alkoxysilanes. Alkoxysilanes are a class of chemicals which contain one or more organic alkoxy groups bonded to silicon atoms. Alkoxysilane (Si-O-R) chemical groups can undergo reactions to form bridges (Si-O-M) with metal oxides. Due to their ability to "attach" to metal-oxides through condensation reactions, alkoxysilanes have a number of interesting applications, such as: the generation of synthetic siloxane materials through the sol-gel process, and the formation of functionalized surface coatings on metal-oxide surfaces. Despite widespread study of sol-gel and surface coatings processes, it is difficult to predict the morphology of the final products due to the large number of process variables involved, such as precursor molecule structure, solvent effects, solution composition, temperature, and pH. To determine the influence of these variables on the products of sol-gel and coatings processes reactive molecular dynamics simulations are used. A reactive force field was used (ReaxFF) to allow the chemical bonds in simulation to dynamically form and break. The force field parameters were optimized using a parallel optimization scheme with a combination of experimental information, and density functional theory calculations. Polycondensation of alkoxysilanes in mixtures of alcohol and water were studied. Steric effects were observed to influence the rates of hydrolysis and condensation in solutions containing different precursor monomers. By restricting the access of nucleophiles to the central silicon atom, the nucleation rate of siloxanes can be controlled. The influence of solution precursor, water, and methanol composition on reaction rates was explored. It was determined that the rate of alkoxysilane hydrolysis is strongly dependent on the concentration of water. The dynamics of siloxane cluster formation are revealed, which provides insight for experimentalists. The silanization of hydroxylated silica surfaces by alkoxysilanes was modeled in pseudo-infinite liquid solution. Butyl-, octyl-, or dodecylsilanes were exposed to hydroxylated silica surfaces in order to observe the influence of silyl headgroup size on the morphology and formation kinetics of silane films on silica substrates. The radius of gyration and order parameter of the hydrocarbon silyl groups were found to increase with grafting density. This was the first simulation study of the dynamic grafting of alkoxysilanes to a substrate.

Infrared Thermometers

ERIC Educational Resources Information Center

Schaefers, John

2006-01-01

An infrared (IR) thermometer lab offers the opportunity to give science students a chance to measure surface temperatures, utilizing off-the-shelf technology. Potential areas of study include astronomy (exoplanets), electromagnetic spectrum, chemistry, evaporation rates, anatomy, crystal formation, and water or liquids. This article presents one…

Stepped Single Crystals as Improved Model for Supported Catalysts: Ethylene, Methanol and Assorted Molecules on PLATINUM(511) and PLATINUM(331)

NASA Astrophysics Data System (ADS)

Spaendonk, Vincent Van

Past research has shown unusual activity of the (1 x 1)Pt(110) surface to break carbon-carbon and carbon -oxygen bonds. Methane formation from ethylene or ethane has been reported for supported platinum catalysts. A model for the methane formation on (1 x 1)Pt(110), was proposed by Yagasaki. In this study, the mechanism of methane formation has been further investigated, and Yagasaki's model tested, by studying the decomposition of ethylene and methanol on the stepped surfaces Pt(511) and Pt(331) with Temperature Programmed Desorption. The experiments have been carried out in a Ultra High Vacuum system, equipped with a mass spectrometer, LEED and AES. Hydrogen and carbon monoxide desorption show that on Pt(511) different adsorption sites are available than on Pt(331). Ethylene decomposition on Pt(511) leads to small amounts of methane formation compared to (1 x 1)Pt(110). The metastable (1 x 1) phase of Pt(511) is 2-3 times more active than the stable (hex) phase. When ^{13}C_2H _4 is used, ^{13 }CH_4 is not detected. Methane formation is not seen on the Pt(331) surface. Arguments are given why Pt(511) is a superior model for supported catalysts compared to (1 x 1)Pt(110). The carbon-oxygen bond of methanol is not broken on either Pt(511) or Pt(331), whether the surface is clean or covered with oxygen. Hydrogen saturating the surface, prevents the chemisorption of ethylene and the formation of methane. Postadsorption of hydrogen does not lead to an increase in methane formation. Coadsorption of ethylene with carbon monoxide shows a maximum methane formation at 0.3 L carbon monoxide exposure. Poison experiments with 'oxide' and carbon indicate that the active site for methane formation is located at the step. The amount of carbon deposited during ethylene decomposition, increases in the order (1 x 1)Pt(511) to (hex)Pt(511) to Pt(331). This is also the order for decreasing methane activity. In a new model, it is proposed that in order to be active for methane formation, a surface has to prevent the polymerization of single carbon species to inactive graphite. The model predicts that surfaces with large enough (111) terraces have higher diffusion rates and allow the single carbon species to convert to graphite before the species can be hydrogenated.

Star Cluster Formation in Cosmological Simulations. I. Properties of Young Clusters

NASA Astrophysics Data System (ADS)

Li, Hui; Gnedin, Oleg Y.; Gnedin, Nickolay Y.; Meng, Xi; Semenov, Vadim A.; Kravtsov, Andrey V.

2017-01-01

We present a new implementation of star formation in cosmological simulations by considering star clusters as a unit of star formation. Cluster particles grow in mass over several million years at the rate determined by local gas properties, with high time resolution. The particle growth is terminated by its own energy and momentum feedback on the interstellar medium. We test this implementation for Milky Way-sized galaxies at high redshift by comparing the properties of model clusters with observations of young star clusters. We find that the cluster initial mass function is best described by a Schechter function rather than a single power law. In agreement with observations, at low masses the logarithmic slope is α ≈ 1.8{--}2, while the cutoff at high mass scales with the star formation rate (SFR). A related trend is a positive correlation between the surface density of the SFR and fraction of stars contained in massive clusters. Both trends indicate that the formation of massive star clusters is preferred during bursts of star formation. These bursts are often associated with major-merger events. We also find that the median timescale for cluster formation ranges from 0.5 to 4 Myr and decreases systematically with increasing star formation efficiency. Local variations in the gas density and cluster accretion rate naturally lead to the scatter of the overall formation efficiency by an order of magnitude, even when the instantaneous efficiency is kept constant. Comparison of the formation timescale with the observed age spread of young star clusters provides an additional important constraint on the modeling of star formation and feedback schemes.

Amorphous layer formation in Al86.0Co7.6Ce6.4 glass-forming alloy by large-area electron beam irradiation

NASA Astrophysics Data System (ADS)

Li, C. L.; Murray, J. W.; Voisey, K. T.; Clare, A. T.; McCartney, D. G.

2013-09-01

Amorphous Al-Co-Ce alloys are of interest because of their resistance to corrosion, but high cooling rates are generally required to suppress the formation of crystalline phases. In this study, the surface of a bulk crystalline Al-Co-Ce alloy of a glass-forming composition was treated using large area electron beam (LAEB) irradiation. Scanning electron microscopy shows that, compared to the microstructure of the original crystalline material, the treated surface exhibits greatly improved microstructural and compositional uniformity. Glancing angle X-ray diffraction conducted on the surface of treated samples indicates the formation of the amorphous phase following 25 and 50 pulses at 35 kV cathode voltage. However, when the samples are treated with 100 and 150 pulses at 35 kV cathode voltage of electron beam irradiation, the treated layer comprises localised crystalline regions in an amorphous matrix. In addition, the formation of cracks in the treated layer is found to be localised around the Al8Co2Ce phase in the bulk material. Overall, crack length per unit area had no clear change with an increase in the number of pulses.

Impact of stratospheric aircraft on calculations of nitric acid trihydrate cloud surface area densities using NMC temperatures and 2D model constituent distributions

NASA Technical Reports Server (NTRS)

Considine, David B.; Douglass, Anne R.

1994-01-01

A parameterization of NAT (nitric acid trihydrate) clouds is developed for use in 2D models of the stratosphere. The parameterization uses model distributions of HNO3 and H2O to determine critical temperatures for NAT formation as a function of latitude and pressure. National Meteorological Center temperature fields are then used to determine monthly temperature frequency distributions, also as a function of latitude and pressure. The fractions of these distributions which fall below the critical temperatures for NAT formation are then used to determine the NAT cloud surface area density for each location in the model grid. By specifying heterogeneous reaction rates as functions of the surface area density, it is then possible to assess the effects of the NAT clouds on model constituent distributions. We also consider the increase in the NAT cloud formation in the presence of a fleet of stratospheric aircraft. The stratospheric aircraft NO(x) and H2O perturbations result in increased HNO3 as well as H2O. This increases the probability of NAT formation substantially, especially if it is assumed that the aircraft perturbations are confined to a corridor region.

Particle emission from artificial cometary materials

NASA Technical Reports Server (NTRS)

Koelzer, Gabriele; Kochan, Hermann; Thiel, Klaus

1992-01-01

During KOSI (comet simulation) experiments, mineral-ice mixtures are observed in simulated space conditions. Emission of ice-/dust particles from the sample surface is observed by means of different devices. The particle trajectories are recorded with a video system. In the following analysis we extracted the parameters: particle count rate, spatial distribution of starting points on the sample surface, and elevation angle and particle velocity at distances up to 5 cm from the sample surface. Different kinds of detectors are mounted on a frame in front of the sample to register the emitted particles and to collect their dust residues. By means of these instruments the particle count rates, the particle sizes and the composition of the particles can be correlated. The results are related to the gas flux density and the temperature on the sample surface during the insolation period. The particle emission is interpreted in terms of phenomena on the sample surface, e.g., formation of a dust mantle.

Local stability of galactic discs in modified dynamics

NASA Astrophysics Data System (ADS)

Shenavar, Hossein; Ghafourian, Neda

2018-04-01

The local stability of stellar and fluid discs, under a new modified dynamical model, is surveyed by using WKB approximation. The exact form of the modified Toomre criterion is derived for both types of systems and it is shown that the new model is, in all situations, more locally stable than Newtonian model. In addition, it has been proved that the central surface density of the galaxies plays an important role in the local stability in the sense that low surface brightness (LSB) galaxies are more stable than high surface brightness (HSBs). Furthermore, the growth rate in the new model is found to be lower than the Newtonian one. We found that, according to this model, the local instability is related to the ratio of surface density of the disc to a critical surface density Σcrit. We provide observational evidence to support this result based on star formation rate in HSBs and LSBs.

Surface Nanocrystallization and Amorphization of Dual-Phase TC11 Titanium Alloys under Laser Induced Ultrahigh Strain-Rate Plastic Deformation

PubMed Central

Luo, Sihai; Zhou, Liucheng; Wang, Xuede; Cao, Xin; Nie, Xiangfan

2018-01-01

As an innovative surface technology for ultrahigh strain-rate plastic deformation, laser shock peening (LSP) was applied to the dual-phase TC11 titanium alloy to fabricate an amorphous and nanocrystalline surface layer at room temperature. X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy (HRTEM) were used to investigate the microstructural evolution, and the deformation mechanism was discussed. The results showed that a surface nanostructured surface layer was synthesized after LSP treatment with adequate laser parameters. Simultaneously, the behavior of dislocations was also studied for different laser parameters. The rapid slipping, accumulation, annihilation, and rearrangement of dislocations under the laser-induced shock waves contributed greatly to the surface nanocrystallization. In addition, a 10 nm-thick amorphous structure layer was found through HRTEM in the top surface and the formation mechanism was attributed to the local temperature rising to the melting point, followed by its subsequent fast cooling. PMID:29642379

Surface Nanocrystallization and Amorphization of Dual-Phase TC11 Titanium Alloys under Laser Induced Ultrahigh Strain-Rate Plastic Deformation.

PubMed

Luo, Sihai; Zhou, Liucheng; Wang, Xuede; Cao, Xin; Nie, Xiangfan; He, Weifeng

2018-04-06

As an innovative surface technology for ultrahigh strain-rate plastic deformation, laser shock peening (LSP) was applied to the dual-phase TC11 titanium alloy to fabricate an amorphous and nanocrystalline surface layer at room temperature. X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy (HRTEM) were used to investigate the microstructural evolution, and the deformation mechanism was discussed. The results showed that a surface nanostructured surface layer was synthesized after LSP treatment with adequate laser parameters. Simultaneously, the behavior of dislocations was also studied for different laser parameters. The rapid slipping, accumulation, annihilation, and rearrangement of dislocations under the laser-induced shock waves contributed greatly to the surface nanocrystallization. In addition, a 10 nm-thick amorphous structure layer was found through HRTEM in the top surface and the formation mechanism was attributed to the local temperature rising to the melting point, followed by its subsequent fast cooling.

Bank accretion and the development of vegetated depositional surfaces along modified alluvial channels

USGS Publications Warehouse

Hupp, C.R.; Simon, A.

1991-01-01

This paper describes the recovery of stable bank form and development of vegetated depositional surfaces along the banks of channelized West Tennessee streams. Most perennial streams in West Tennessee were straightened and dredged since the turn of the century. Patterns of fluvial ecological responses to channelization have previously been described by a six-stage model. Dendrogeomorphic (tree-ring) techniques allowed the determination of location, timing, amount, and rate of bank-sediment deposition. Channel cross sections and ecological analyses made at 101 locations along 12 streams, encompassing bends and straight reaches, show that channel and bank processes initially react vertically to channelization through downcutting. A depositional surface forms on banks once bed-degradation and heightened bank mass wasting processes have eased or slowed. The formation of this depositional surface marks the beginning of bank recovery from channelization. Dominating lateral processes, characteristic of stable or natural channels, return during the formation and expansion of the depositional surface, suggesting a relation with thalweg deflection, point-bar development, and meanderloop extension. Characteristic woody riparian vegetation begins to grow as this depositional surface develops and becomes part of the process and form of restabilizing banks. The depositional surface initially forms low on the bank and tends to maintain a slope of about 24??. Mean accretion rates ranges from 5.9 cm/yr on inside bends to 0 cm/yr on most outside bends; straight reaches have a mean-accretion rate of 4.2 cm/yr. The relatively stable, convex upward, depositional surface expands and ultimately attaches to the flood plain. The time required for the recovery process to reach equilibrium averaged about 50 years. Indicative pioneer speccies of woody riparian vegetation include black willow, river birch, silver maple, and boxelder. Stem densities generally decrease with time after and initial flush of about 160 stems per 100 m2. Together bank accretion and vegetative regrowth appear to be the most important environmental processes involved in channel bank recovery from channelization or rejuvenation. ?? 1991.

Pahoehoe and aa in Hawaii: volumetric flow rate controls the lava structure

NASA Astrophysics Data System (ADS)

Rowland, Scott K.; Walker, George Pl

1990-11-01

The historical records of Kilauea and Mauna Loa volcanoes reveal that the rough-surfaced variety of basalt lava called aa forms when lava flows at a high volumetric rate (>5 10 m3/s), and the smooth-surfaced variety called pahoehoe forms at a low volumetric rate (<5 10 m3/s). This relationship is well illustrated by the 1983 1990 and 1969 1974 eruptions of Kilauea and the recent eruptions of Mauna Loa. It is also illustrated by the eruptions that produced the remarkable paired flows of Mauna Loa, in which aa formed during an initial short period of high discharge rate (associated with high fountaining) and was followed by the eruption of pahoehoe over a sustained period at a low discharge rate (with little or no fountaining). The finest examples of paired lava flows are those of 1859 and 1880 1881. We attribute aa formation to rapid and concentrated flow in open channels. There, rapid heat loss causes an increase in viscosity to a threshold value (that varies depending on the actual flow velocity) at which, when surface crust is torn by differential flow, the underlying lava is unable to move sufficiently fast to heal the tear. We attribute pahoehoe formation to the flowage of lava at a low volumetric rate, commonly in tubes that minimize heat loss. Flow units of pahoehoe are small (usually <1 m thick), move slowly, develop a chilled skin, and become virtually static before the viscosity has risen, to the threshold value. We infer that the high-discharge-rate eruptions that generate aa flows result from the rapid emptying of major or subsidiary magma chambers. Rapid near-surface vesiculation of gas-rich magma leads to eruptions with high discharge rates, high lava fountains, and fast-moving channelized flows. We also infer that long periods of sustained flow at a low discharge rate, which favor pahoehoe, result from the development of a free and unimpeded pathway from the deep plumbing system of the volcano and the separation of gases from the magma before eruption. Achievement of this condition requires one or more episodes of rapid magma excursion through the rift zone to establish a stable magma pathway.

Nanopatterning dynamics on Si(100) during oblique 40-keV Ar+ erosion with metal codeposition: Morphological and compositional correlation

NASA Astrophysics Data System (ADS)

Redondo-Cubero, A.; Gago, R.; Palomares, F. J.; Mücklich, A.; Vinnichenko, M.; Vázquez, L.

2012-08-01

The formation and dynamics of nanopatterns produced on Si(100) surfaces by 40-keV Ar+ oblique (α = 60°) bombardment with concurrent Fe codeposition have been studied. Morphological and chemical analysis has been performed by ex situ atomic force microscopy, Rutherford backscattering spectrometry, x-ray photoelectron spectroscopy, and scanning and transmission electron microscopies. During irradiation, Fe atoms incorporated into the target surface react with Si to form silicides, a process enhanced at this medium-ion energy range. The silicides segregate at the nanoscale from the early irradiation stages. As the irradiation proceeds, a ripple pattern is formed without any correlation with silicide segregation. From the comparison with the pattern dynamics reported previously for metal-free conditions, it is demonstrated that the metal incorporation alters both the pattern dynamics and the morphology. Although the pattern formation and dynamics are delayed for decreasing metal content, once ripples emerge, the same qualitative pattern of morphological evolution is observed for different metal content, resulting in an asymptotic saw-tooth-like facetted surface pattern. Despite the medium ion energy employed, the nanopatterning process with concurrent Fe deposition can be explained by those mechanisms proposed for low-ion energy irradiations such as shadowing, height fluctuations, silicide formation and segregation, ensuing composition dependent sputter rate, and ion sculpting effects. In particular, the interplay between the ion irradiation and metal flux geometries, differences in sputtering rates, and the surface pattern morphology produces a dynamic compositional patterning correlated with the evolving morphological one.

Hurricanes and Climate: The U.S. CLIVAR Working Group on Hurricanes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walsh, Kevin J. E.; Camargo, Suzana J.; Vecchi, Gabriel A.

While a quantitative climate theory of tropical cyclone formation remains elusive, considerable progress has been made recently in our ability to simulate tropical cyclone climatologies and to understand the relationship between climate and tropical cyclone formation. Climate models are now able to simulate a realistic rate of global tropical cyclone formation, although simulation of the Atlantic tropical cyclone climatology remains challenging unless horizontal resolutions finer than 50 km are employed. This article summarizes published research from the idealized experiments of the Hurricane Working Group of U.S. Climate and Ocean: Variability, Predictability and Change (CLIVAR). This work, combined with results frommore » other model simulations, has strengthened relationships between tropical cyclone formation rates and climate variables such as midtropospheric vertical velocity, with decreased climatological vertical velocities leading to decreased tropical cyclone formation. Systematic differences are shown between experiments in which only sea surface temperature is increased compared with experiments where only atmospheric carbon dioxide is increased. Experiments where only carbon dioxide is increased are more likely to demonstrate a decrease in tropical cyclone numbers, similar to the decreases simulated by many climate models for a future, warmer climate. Experiments where the two effects are combined also show decreases in numbers, but these tend to be less for models that demonstrate a strong tropical cyclone response to increased sea surface temperatures. Lastly, further experiments are proposed that may improve our understanding of the relationship between climate and tropical cyclone formation, including experiments with two-way interaction between the ocean and the atmosphere and variations in atmospheric aerosols.« less

Hurricanes and Climate: The U.S. CLIVAR Working Group on Hurricanes

DOE PAGES

Walsh, Kevin J. E.; Camargo, Suzana J.; Vecchi, Gabriel A.; ...

2015-06-01

While a quantitative climate theory of tropical cyclone formation remains elusive, considerable progress has been made recently in our ability to simulate tropical cyclone climatologies and to understand the relationship between climate and tropical cyclone formation. Climate models are now able to simulate a realistic rate of global tropical cyclone formation, although simulation of the Atlantic tropical cyclone climatology remains challenging unless horizontal resolutions finer than 50 km are employed. This article summarizes published research from the idealized experiments of the Hurricane Working Group of U.S. Climate and Ocean: Variability, Predictability and Change (CLIVAR). This work, combined with results frommore » other model simulations, has strengthened relationships between tropical cyclone formation rates and climate variables such as midtropospheric vertical velocity, with decreased climatological vertical velocities leading to decreased tropical cyclone formation. Systematic differences are shown between experiments in which only sea surface temperature is increased compared with experiments where only atmospheric carbon dioxide is increased. Experiments where only carbon dioxide is increased are more likely to demonstrate a decrease in tropical cyclone numbers, similar to the decreases simulated by many climate models for a future, warmer climate. Experiments where the two effects are combined also show decreases in numbers, but these tend to be less for models that demonstrate a strong tropical cyclone response to increased sea surface temperatures. Lastly, further experiments are proposed that may improve our understanding of the relationship between climate and tropical cyclone formation, including experiments with two-way interaction between the ocean and the atmosphere and variations in atmospheric aerosols.« less

Surface ages and rates of erosion at the Calico Archaeological Site in the Mojave Desert, Southern California

NASA Astrophysics Data System (ADS)

Owen, Lewis A.; Davis, Teresa; Caffee, Marc W.; Budinger, Fred; Nash, David

2011-01-01

Erosion rates and surface exposure ages were determined at the Calico Archaeological Site in the Calico Hills of the Mojave Desert, California, using 10Be terrestrial cosmogenic nuclides (TCN) methods. The Calico Hills are composed of Miocene lacustrine deposits of the Barstow Formation and fanglomerates/debris flows of the Pleistocene Yermo Deposits. These deposits are highly denuded and dissected by arroyos that have surfaces armored with chert. Surface erosion rates based on cosmogenic 10Be concentrations in stream sediments range from 19 to 39 m/Ma, with an average of 30.5 ± 6.2 m/Ma. Surface boulders have 10Be TCN ages that range from 27 ka to 198 ka, reflecting significant erosion of the Calico Hills. The oldest boulder age (197 ± 20 ka) places a minimum limit on the age of Yermo deposits. Depth profile ages at four locations within the study area have minimum ages that range from 31 to 84 ka and erosion rate-corrected surface exposure ages ranging from 43 to 139 ka. These surface exposure ages support the view that the surfaces in Yermo deposits formed during the Late Pleistocene to latest Middle Pleistocene. This chronology has important implications for interpreting the context of possible artifacts/geofacts at the site that might provide evidence for early human occupation of North America, and for reconstructing paleoenvironment change and landscape evolution in the region.

Synthetic peptides derived from salivary proteins and the control of surface charge densities of dental surfaces improve the inhibition of dental calculus formation.

PubMed

Grohe, Bernd

2017-08-01

Peptides descended from the salivary proteins statherin and histatin were recently identified in saliva and the acquired enamel pellicle (AEP), a proteomic layer coated on enamel. In particular, the statherin phosphopeptide DpSpSEEKFLR (DSS) was found to adsorb to enamel-like hydroxyapatite and inhibit plaque-related crystal formation. To determine the mechanism of these processes, we studied peptide-crystal interactions based on the sequences DSS and RKFHEKHHSHRGYR (RKF). The latter is a basic histatin sequence showing antimicrobial effects. To initiate crystallization we used calcium oxalate monohydrate (COM), a rather secondary phase in the oral environment, however highly amenable to experimental analyses of nucleation and growth processes. Using electron microscopy we found that the peptides DSS, DSS-RKF and DSS-DSS all inhibit crystal formation; with DSS-DSS showing the strongest effects while RKF showed no effect. In addition, using either enamel-like or mica substrates, we found that the ratio of the substrate's surface charge densities was directly correlated with the ratio of COM nucleation rates on theses surfaces. The findings suggest that mineralization processes on enamel/AEP-films are controllable by the degree of peptide phosphorylation/acidity and the level of the enamel surface charge density. Both parameters can, when well adjusted, help to overcome periodontal disease and dental calculus formation. In addition, the presence of antimicrobial RKF will reduce the buildup of bacterial plaque. Copyright © 2017 Elsevier B.V. All rights reserved.

The dynamic nature of crystal growth in pores

DOE PAGES

Godinho, Jose R. A.; Gerke, Kirill M.; Stack, Andrew G.; ...

2016-09-12

We report that the kinetics of crystal growth in porous media controls a variety of natural processes such as ore genesis and crystallization induced fracturing that can trigger earthquakes and weathering, as well as, sequestration of CO 2 and toxic metals into geological formations. Progress on understanding those processes has been limited by experimental difficulties of dynamically studying the reactive surface area and permeability during pore occlusion. Here, we show that these variables cause a time-dependency of barite growth rates in microporous silica. The rate is approximately constant and similar to that observed on free surfaces if fast flow velocitiesmore » predominate and if the time-dependent reactive surface area is accounted for. As the narrower flow paths clog, local flow velocities decrease, which causes the progressive slowing of growth rates. We conclude that mineral growth in a microporous media can be estimated based on free surface studies when a) the growth rate is normalized to the time-dependent surface area of the growing crystals, and b) the local flow velocities are above the limit at which growth is transport-limited. Lastly, accounting for the dynamic relation between microstructure, flow velocity and growth rate is shown to be crucial towards understanding and predicting precipitation in porous rocks.« less

Assessing Hydrogen Assisted Cracking Modes in High Strength Steel Welds

DTIC Science & Technology

1988-12-01

posed theoretical hydrogen assisted cracking mechanisms. It was found that the microplasticity theory of Beachem can best describe how the stress...precludes an internal pressure gradient as the driv- ing force for crack growth. The adsorption theory of Petch and Stables3 and further modifications4...the adsorption theory. In addition, fracture surfaces indicate rapid void formation and coales- cence at low temperatures where the rate of surface

Density-functional theory study of dimethyl carbonate synthesis by methanol oxidative carbonylation on single-atom Cu1/graphene catalyst

NASA Astrophysics Data System (ADS)

Sun, Wei; Shi, Ruina; Wang, Xuhui; Liu, Shusen; Han, Xiaoxia; Zhao, Chaofan; Li, Zhong; Ren, Jun

2017-12-01

The mechanism for dimethyl carbonate (DMC) synthesis by oxidation carbonylation of methanol on a single-atom Cu1/graphene catalyst was investigated by density-functional theory calculations. Carbon vacancies in graphene can significantly enhance the interaction between Cu atoms and graphene supports, and provide an increased transfer of electrons from Cu atoms to the graphene sheet. Compared with Cu-doped divacancy graphene (Cu/DG), Cu-doped monovacancy graphene (Cu/MG) provides a stronger interaction between adsorbents and the catalyst surface. Among the reaction processes over Cu1/graphene catalysts, CO insertion into methoxide was more favorable than dimethoxide. The rate-limiting step on the Cu/DG surface is the carbomethoxide reaction with methoxide, which is exothermic by 164.6 kJ mol-1 and has an activation barrier of 190.9 kJ mol-1 energy. Compared with that on the Cu crystal surface, Cu4 and Cu3Rh clusters, and the Cu2O(111) surface, the rate-determining step for DMC formation on Cu/MG, which is CO insertion into methoxide, needs to overcome the lowest barrier of 73.5 kJ mol-1 and is exothermic by 44.6 kJ mol-1. Therefore, Cu/MG was beneficial to the formation of DMC as a single-atom catalyst.

Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

NASA Astrophysics Data System (ADS)

van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

2014-06-01

The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater to surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than one week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilisation of dissolved P during the initial stage of the Fe(II) oxidation proces which results in P-depleted water before Fe(II) is competly depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

Ice nucleation on nanotextured surfaces: the influence of surface fraction, pillar height and wetting states.

PubMed

Metya, Atanu K; Singh, Jayant K; Müller-Plathe, Florian

2016-09-29

In this work, we address the nucleation behavior of a supercooled monatomic cylindrical water droplet on nanoscale textured surfaces using molecular dynamics simulations. The ice nucleation rate at 203 K on graphite based textured surfaces with nanoscale roughness is evaluated using the mean fast-passage time method. The simulation results show that the nucleation rate depends on the surface fraction as well as the wetting states. The nucleation rate enhances with increasing surface fraction for water in the Cassie-Baxter state, while contrary behavior is observed for the case of Wenzel state. Based on the spatial histogram distribution of ice formation, we observed two pathways for ice nucleation. Heterogeneous nucleation is observed at a high surface fraction. However, the probability of homogeneous ice nucleation events increases with decreasing surface fraction. We further investigate the role of the nanopillar height in ice nucleation. The nucleation rate is enhanced with increasing nanopillar height. This is attributed to the enhanced contact area with increasing nanopillar height and the shift in nucleation events towards the three-phase contact line associated with the nanotextured surface. The ice-surface work of adhesion for the Wenzel state is found to be 1-2 times higher than that in the Cassie-Baxter state. Furthermore, the work of adhesion of ice in the Wenzel state is found to be linearly dependent on the contour length of the droplet, which is in line with that reported for liquid droplets.

Effect of Repetition Rate on Femtosecond Laser-Induced Homogenous Microstructures

PubMed Central

Biswas, Sanchari; Karthikeyan, Adya; Kietzig, Anne-Marie

2016-01-01

We report on the effect of repetition rate on the formation and surface texture of the laser induced homogenous microstructures. Different microstructures were micromachined on copper (Cu) and titanium (Ti) using femtosecond pulses at 1 and 10 kHz. We studied the effect of the repetition rate on structure formation by comparing the threshold accumulated pulse (FΣpulse) values and the effect on the surface texture through lacunarity analysis. Machining both metals at low FΣpulse resulted in microstructures with higher lacunarity at 10 kHz compared to 1 kHz. On increasing FΣpulse, the microstructures showed higher lacunarity at 1 kHz. The effect of the repetition rate on the threshold FΣpulse values were, however, considerably different on the two metals. With an increase in repetition rate, we observed a decrease in the threshold FΣpulse on Cu, while on Ti we observed an increase. These differences were successfully allied to the respective material characteristics and the resulting melt dynamics. While machining Ti at 10 kHz, the melt layer induced by one laser pulse persists until the next pulse arrives, acting as a dielectric for the subsequent pulse, thereby increasing FΣpulse. However, on Cu, the melt layer quickly resolidifies and no such dielectric like phase is observed. Our study contributes to the current knowledge on the effect of the repetition rate as an irradiation parameter. PMID:28774143

Optimization of Surface Roughness and Wall Thickness in Dieless Incremental Forming Of Aluminum Sheet Using Taguchi

NASA Astrophysics Data System (ADS)

Hamedon, Zamzuri; Kuang, Shea Cheng; Jaafar, Hasnulhadi; Azhari, Azmir

2018-03-01

Incremental sheet forming is a versatile sheet metal forming process where a sheet metal is formed into its final shape by a series of localized deformation without a specialised die. However, it still has many shortcomings that need to be overcome such as geometric accuracy, surface roughness, formability, forming speed, and so on. This project focus on minimising the surface roughness of aluminium sheet and improving its thickness uniformity in incremental sheet forming via optimisation of wall angle, feed rate, and step size. Besides, the effect of wall angle, feed rate, and step size to the surface roughness and thickness uniformity of aluminium sheet was investigated in this project. From the results, it was observed that surface roughness and thickness uniformity were inversely varied due to the formation of surface waviness. Increase in feed rate and decrease in step size will produce a lower surface roughness, while uniform thickness reduction was obtained by reducing the wall angle and step size. By using Taguchi analysis, the optimum parameters for minimum surface roughness and uniform thickness reduction of aluminium sheet were determined. The finding of this project helps to reduce the time in optimising the surface roughness and thickness uniformity in incremental sheet forming.

Sub ablative Er: YAG laser irradiation on surface roughness of eroded dental enamel.

PubMed

Curylofo-Zotti, Fabiana Almeida; Lepri, Taísa Penazzo; Colucci, Vivian; Turssi, Cecília Pedroso; Corona, Silmara Aparecida Milori

2015-11-01

This study evaluated the effects of Er:YAG laser irradiation applied at varying pulse repetition rate on the surface roughness of eroded enamel. Bovine enamel slabs (n = 10) were embedded in polyester resin, ground, and polished. To erosive challenges, specimens were immersed two times per day in 20mL of concentrated orange juice (pH = 3.84) under agitation, during a two-day period. Specimens were randomly assigned to irradiation with the Er:YAG laser (focused mode, pulse energy of 60 mJ and energy density of 3.79 J/cm(2) ) operating at 1, 2, 3, or 4 Hz. The control group was left nonirradiated. Surface roughness measurements were recorded post erosion-like formation and further erosive episodes by a profilometer and observed through atomic force microscopy (AFM). Analysis of variance revealed that the control group showed the lowest surface roughness, while laser-irradiated substrates did not differ from each other following post erosion-like lesion formation. According to analysis of covariance, at further erosive episodes, the control group demonstrated lower surface roughness (P > 0.05), than any of the irradiated groups (P < 0.05). The pulse repetition rate of the Er:YAG laser did not affect roughness of dental enamel eroded. The AFM images showed that the specimens irradiated by the Er:YAG laser at 1 Hz presented a less rough surface than those irradiated at 2, 3, and 4 Hz. © 2015 Wiley Periodicals, Inc.

Interactions of silicate glasses with aqueous environments under conditions of prolonged contact and flow

NASA Technical Reports Server (NTRS)

Barkatt, Aaron; Saad, E. E.; Adiga, R. B.; Sousanpour, W.; Barkatt, AL.; Feng, X.; O'Keefe, J. A.; Alterescu, S.

1988-01-01

This paper discusses mechanisms involving saturation and reactions that lead to the formation of altered phases in silicate glasses considered for use in geologic repositories for nuclear waste. It is shown that the rate of dissolution of silicate glasses exposed to a broad range of contact times, leachant compositions, and surface-to-volume ratios is strongly affected by the presence of reactive species such as Al, Mg, and Fe. The reactive materials may originate in the leachant or, under conditions of high surface-to-volume ratio, in the glass itself. The effects of glass composition on the course of the corrosion process can be viewed in terms of the formation of a surface layer on the leached glass; the type, composition, and structure of this layer control the dissolution behavior of the glass.

Quantification of Marangoni flows and film morphology during solid film formation by inkjet printing

NASA Astrophysics Data System (ADS)

Ishizuka, Hirotaka; Fukai, Jun

2018-01-01

We visualized experimentally the internal flow inside inkjet droplets of polystyrene-anisole solution during solid film formation on substrates at room temperature. The effects of contact angle and evaporation rate on the internal flow and film morphology were quantitatively investigated. The transport process during film formation was examined by measuring the relationship between internal flow and film morphology, which provided three remarkable findings. First, self-pinning and the strength of outward flow on the free surface under 2.3 Pa s determined film morphology. The solute distribution, corresponding to rim areas in ring-like films and a convex trough in dot-like films, had already developed at self-pinning. Second, the mass fraction at self-pinning close to the contact line converged to one, regardless of the film morphology. This implies that self-pinning is independent of parameters such as the contact angle and evaporation rate. Third, at room temperature, the solutal Marangoni numbers were 20-30 times larger than the thermal ones. Thus, the outward flow on the free surface caused by the solutal Marangoni effect dominates in droplets before self-pinning. The solutal Marangoni number at self-pinning and thickness variation at the center of the film displayed a good relationship for droplets with different contact angles and evaporation rates. This suggests that film morphology can be technically controlled by solutal Marangoni number at room temperature.

Regional Landscape Response to Wedge-Top Basin Formation

NASA Astrophysics Data System (ADS)

Ruetenik, G.; Moucha, R.; Hoke, G. D.; Val, P.

2017-12-01

Wedge-top basins are the result of regionally variable uplift along thrust faults downstream of a mountain range and provide an ideal environment to study the regional stream and surface response to local variations in rock uplift. In this study, we simulate the formation and evolution of a wedge-top basin using a landscape evolution model. In line with a previous study, we find that during deformation in the fold-and-thrust belt adjacent to a wedge-top basin, both channel slope and erosion rates are reduced, and these changes propagate as a wave of low erosion into the uplands. For a uniform background uplift rate, this reduced rate of erosion results in a net surface uplift and a decreased slope within and upstream of the wedge-top basin. Following the eventual breach of the basin's bounding thrust belt, a wave of high erosion propagates through the basin and increases the channel slope. We expand upon previous studies by testing our model against a wide range of model parameters, although in general we find that the onset of increased erosion can be delayed by up to several million years. The amount of surface uplift is highly dependent on flexural isostasy and therefore it is heavily influenced by the elastic thickness and erodbility parameters. Observed paleoerosion rates in a paired wedge-top foreland sequence in the Argentine Precordillera reveal similar histories of paleo-erosion, and present day stream profiles show evidence that support model outcomes.

The role of electronic mechanisms in surface erosion and glow phenomena

NASA Technical Reports Server (NTRS)

Haglund, Richard F., Jr.

1987-01-01

Experimental studies of desorption induced by electronic transitions (DIET) are described. Such studies are producing an increasingly complete picture of the dynamical pathways through which incident electronic energy is absorbed and rechanneled to produce macroscopic erosion and glow. These mechanistic studies can determine rate constants for erosion and glow processes in model materials and provide valuable guidance in materials selection and development. Extensive experiments with electron, photon, and heavy particle irradiation of alkali halides and other simple model materials have produced evidence showing that: (1) surface erosion, consisting primarily in the ejection or desorption of ground-state neutral atoms, occurs with large efficiencies for all irradiated species; (2) surface glow, resulting from the radiative decay of desorbed atoms, likewise occurs for all irradiating species; (3) the typical mechanism for ground-state neutral desorption is exciton formation, followed by relaxation to a permanent, mobile electronic defect which is the precursor to bond-breaking in the surface or near-surface bulk of the material; and (4) the mechanisms for excited atom formation may include curve crossing in atomic collisions, interactions with surface defect or impurity states, or defect diffusion.

Dynamics of drinking water biofilm in flow/non-flow conditions.

PubMed

Manuel, C M; Nunes, O C; Melo, L F

2007-02-01

Drinking water biofilm formation on polyvinyl chloride (PVC), cross-linked polyethylene (PEX), high density polyethylene (HDPE) and polypropylene (PP) was followed in three different reactors operating under stagnant or continuous flow regimes. After one week, a quasi-steady state was achieved where biofilm total cell numbers per unit surface area were not affected by fluctuations in the concentration of suspended cells. Metabolically active cells in biofilms were around 17-35% of the total cells and 6-18% were able to form colony units in R(2)A medium. Microbiological analysis showed that the adhesion material and reactor design did not affect significantly the biofilm growth. However, operating under continuous flow (0.8-1.9 Pa) or stagnant water had a significant effect on biofilm formation: in stagnant waters, biofilm grew to a less extent. By applying mass balances and an asymptotic biofilm formation model to data from biofilms grown on PVC and HDPE surfaces under turbulent flow, specific growth rates of bacteria in the biofilm were found to be similar for both materials (around 0.15 day(-1)) and much lower than the specific growth rates of suspended bacteria (around 1.8 day(-1)).

Molecule formation and infrared emission in fast interstellar shocks. I Physical processes

NASA Technical Reports Server (NTRS)

Hollenbach, D.; Mckee, C. F.

1979-01-01

The paper analyzes the structure of fast shocks incident upon interstellar gas of ambient density from 10 to the 7th per cu cm, while focusing on the problems of formation and destruction of molecules and infrared emission in the cooling, neutral post shock gas. It is noted that such fast shocks initially dissociate almost all preexisting molecules. Discussion covers the physical processes which determine the post shock structure between 10 to the 4 and 10 to the 2 K. It is shown that the chemistry of important molecular coolants H2, CO, OH, and H2O, as well as HD and CH, is reduced to a relatively small set of gas phase and grain surface reactions. Also, the chemistry follows the slow conversion of atomic hydrogen into H2, which primarily occurs on grain surfaces. The dependence of this H2 formation rate on grain and gas temperatures is examined and the survival of grains behind fast shocks is discussed. Post shock heating and cooling rates are calculated and an appropriate, analytic, universal cooling function is developed for molecules other than hydrogen which includes opacities from both the dust and the lines.

How to generate and interpret fire characteristics charts for the U.S. fire danger rating system

Treesearch

Faith Ann Heinsch; Patricia L. Andrews; Deb Tirmenstein

2017-01-01

The fire characteristics chart is a graphical method of presenting U.S. National Fire Danger Rating System (NFDRS) indexes and components as well as primary surface or crown fire behavior characteristics. Computer software has been developed to produce fire characteristics charts for both fire danger and fire behavior in a format suitable for inclusion in reports and...

Impact of surface processes and climate variability on clumped isotope thermometry of soil carbonates, southern Central Andes, Argentina (Invited)

NASA Astrophysics Data System (ADS)

Huntington, K. W.; Peters, N.; Roe, G.; Hoke, G. D.; Eiler, J.

2010-12-01

Soil carbonates archive a potentially rich record of past climate, but rates of pedogenic carbonate formation, erosion, and deposition impact how the isotopic composition and formation temperature of carbonate-bearing paleosols reflect the local environmental conditions under which they form. We investigate these processes using conventional stable isotope (δ18O and δ13C) and clumped isotope thermometry data for Quaternary pedogenic carbonates from the southern Central Andes at ~33°S, Argentina. The study area spans over 2 km of relief in the Río Mendoza and Río de las Cuevas valleys, accessing a range of mean annual temperature conditions and vegetative cover and exhibiting large seasonal variations in temperature, precipitation, and soil moisture. Variations in soil conditions influence carbonate precipitation and dissolution reactions and the rate and depth of pedogenic carbonate formation. Because soil temperature varies predictably as a function of depth in the soil and seasonal and secular variations in air temperature, clumped isotope thermometry of samples collected in soil pits offers a direct way to estimate the seasonality of pedogenic carbonate formation and potential biases in the long-term climate record. We explore potential complications due to the effects of radiative solar heating on the relationship between air and soil temperatures by examining clumped isotope thermometry results in the context of site-to-site variations in vegetative cover. Temperature estimates from clumped isotope thermometry of pedogenic carbonate collected 5-110 cm below geomorphically stable soil surfaces from 1200-3400 m a.s.l. are compared to temperature profiles predicted by simple rule-based models of soil carbonate formation. The models use climate reanalysis daily diagnostic data (soil temperature, soil moisture, and latent heat flux as a proxy for evaporation) and weather station data as input to assess how varying rates of pedogenic carbonate formation integrated over millennial timescales might impact the geologic record of temperature and isotopic composition.

Oxidation of Cr(III)-Fe(III) Mixed-phase Hydroxides by Chlorine: Implications on the Control of Hexavalent Chromium in Drinking Water.

PubMed

Chebeir, Michelle; Liu, Haizhou

2018-05-17

The occurrence of chromium (Cr) as an inorganic contaminant in drinking water is widely reported. One source of Cr is its accumulation in iron-containing corrosion scales of drinking water distribution systems as Cr(III)-Fe(III) hydroxide, i.e., FexCr(1-x)(OH)3(s), where x represents the Fe(III) molar content and typically varies between 0.25 and 0.75. This study investigated the kinetics of inadvertent hexavalent chromium Cr(VI) formation via the oxidation of FexCr(1-x)(OH)3(s) by chlorine as a residual disinfectant in drinking water, and examined the impacts of Fe(III) content and drinking water chemical parameters including pH, bromide and bicarbonate on the rate of Cr(VI) formation. Data showed that an increase in Fe(III) molar content resulted in a significant decrease in the stoichiometric Cr(VI) yield and the rate of Cr(VI) formation, mainly due to chlorine decay induced by Fe(III) surface sites. An increase in bicarbonate enhanced the rate of Cr(VI) formation, likely due to the formation of Fe(III)-carbonato surface complexes that slowed down the scavenging reaction with chlorine. The presence of bromide significantly accelerated the oxidation of FexCr(1-x)(OH)3(s) by chlorine, resulting from the catalytic effect of bromide acting as an electron shuttle. A higher solution pH between 6 and 8.5 slowed down the oxidation of Cr(III) by chlorine. These findings suggested that the oxidative conversion of chromium-containing iron corrosion products in drinking water distribution systems can lead to the occurrence of Cr(VI) at the tap, and the abundance of iron, and a careful control of pH, bicarbonate and bromide levels can assist the control of Cr(VI) formation.

Rate of Homogenous Nucleation of Ice in Supercooled Water.

PubMed

Atkinson, James D; Murray, Benjamin J; O'Sullivan, Daniel

2016-08-25

The homogeneous freezing of water is of fundamental importance to a number of fields, including that of cloud formation. However, there is considerable scatter in homogeneous nucleation rate coefficients reported in the literature. Using a cold stage droplet system designed to minimize uncertainties in temperature measurements, we examined the freezing of over 1500 pure water droplets with diameters between 4 and 24 μm. Under the assumption that nucleation occurs within the bulk of the droplet, nucleation rate coefficients fall within the spread of literature data and are in good agreement with a subset of more recent measurements. To quantify the relative importance of surface and volume nucleation in our experiments, where droplets are supported by a hydrophobic surface and surrounded by oil, comparison of droplets with different surface area to volume ratios was performed. From our experiments it is shown that in droplets larger than 6 μm diameter (between 234.6 and 236.5 K), nucleation in the interior is more important than nucleation at the surface. At smaller sizes we cannot rule out a significant contribution of surface nucleation, and in order to further constrain surface nucleation, experiments with smaller droplets are necessary. Nevertheless, in our experiments, it is dominantly volume nucleation controlling the observed nucleation rate.

The effect of zero-point energy differences on the isotope dependence of the formation of ozone: a classical trajectory study.

PubMed

Schinke, Reinhard; Fleurat-Lessard, Paul

2005-03-01

The effect of zero-point energy differences (DeltaZPE) between the possible fragmentation channels of highly excited O(3) complexes on the isotope dependence of the formation of ozone is investigated by means of classical trajectory calculations and a strong-collision model. DeltaZPE is incorporated in the calculations in a phenomenological way by adjusting the potential energy surface in the product channels so that the correct exothermicities and endothermicities are matched. The model contains two parameters, the frequency of stabilizing collisions omega and an energy dependent parameter Delta(damp), which favors the lower energies in the Maxwell-Boltzmann distribution. The stabilization frequency is used to adjust the pressure dependence of the absolute formation rate while Delta(damp) is utilized to control its isotope dependence. The calculations for several isotope combinations of oxygen atoms show a clear dependence of relative formation rates on DeltaZPE. The results are similar to those of Gao and Marcus [J. Chem. Phys. 116, 137 (2002)] obtained within a statistical model. In particular, like in the statistical approach an ad hoc parameter eta approximately 1.14, which effectively reduces the formation rates of the symmetric ABA ozone molecules, has to be introduced in order to obtain good agreement with the measured relative rates of Janssen et al. [Phys. Chem. Chem. Phys. 3, 4718 (2001)]. The temperature dependence of the recombination rate is also addressed.

Influence of nanohydroxyapatite surface properties on Staphylococcus epidermidis biofilm formation.

PubMed

Barros, J; Grenho, L; Manuel, C M; Ferreira, C; Melo, L; Nunes, O C; Monteiro, F J; Ferraz, M P

2014-05-01

Nanohydroxyapatite (nanoHA), due to its chemical properties, has appeared as an exceptionally promising bioceramic to be used as bone regeneration material. Staphylococcus epidermidis have emerged as major nosocomial pathogens associated with infections of implanted medical devices. In this work, the purpose was to study the influence of the nanoHA surface characteristics on S. epidermidis RP62A biofilm formation. Therefore, two different initial inoculum concentrations (Ci) were used in order to check if these would affect the biofilm formed on the nanoHA surfaces. Biofilm formation was followed by the enumeration of cultivable cells and by scanning electron microscopy. Surface topography, contact angle, total surface area and porosimetry of the biomaterials were studied and correlated with the biofilm data. The surface of nanoHA sintered at 830 (nanoHA830) showed to be more resistant to S. epidermidis attachment and accumulation than that of nanoHA sintered at 1000 (nanoHA1000). The biofilm formed on nanoHA830 presented differences in terms of structure, surface coverage and EPS production when compared to the one formed on nanoHA1000 surface. It was observed that topography and surface area of nanoHA surfaces had influence on the bacterial attachment and accumulation. Ci influenced bacteria attachment and accumulation on nanoHA surfaces over time. The choice of the initial inoculum concentration was relevant proving to have an effect on the extent of adherence thus being a critical point for human health if these materials are used in implantable devices. This study showed that the initial inoculum concentration and surface material properties determine the rate of microbial attachment to substrata and consequently are related to biofilm-associated infections in biomaterials.

Influence of nanoporosity on biological response of sol-gel-derived 70S30C bioactive glass monoliths

NASA Astrophysics Data System (ADS)

Thamma, Ukrit

In the field of bioactive glasses for hard tissue regeneration, the bioactivity of a material is measured by its ability to induce the formation of hydroxyapatite (HA), Ca10(PO4)6(OH)2, under physiological conditions. Due to its close chemical crystallographic resemblance to natural bones, the newly formed HA layer has been shown to be critical for the biological interaction and bonding between the surfaces of bioactive glasses and osteoblast (bone) cells. Since the formation mechanism of HA is dependent on the dissolution behavior of the bioactive glass substrate, the characteristics of HA layer are dominated by the glass composition and structure. By introducing nanoporosity into glass structure, the dissolution rate and HA growth rate on nanoporous sol-gel-derived glasses are drastically enhanced compared to that of non-porous melt-quench glasses with the same composition. While enhanced HA growth on nanoporous glass, compared to non-porous glass, was hypothesized to be associated with greater specific surface area (SSA), other studies argued that growth rate of HA layer on nanoporous glass is dominated by nanopore size distribution, and minimally affected by the bulk SSA of the underlying glass. In order to decouple the influence of nanopore size and SSA on HA formation, we have successfully fabricated homogeneous 70S30C bioactive glass monoliths with different nanopore sizes, yet similar SSA via sol-gel process. After 3-day PBS incubation of 70S30C nanoporous glass monoliths, the presence of hydroxyapatite and Type-B carbonated hydroxyapatite (HA/B-CHA) was confirmed by XPS and FTIR. Here, we report the influence of nanopore size on HA/CHA formation pathway, growth rate, and its microstructure. Due to pore-size limited diffusion of PO43-, two HA/CHA formation pathways were observed: HA/CHA surface deposition and/or HA/CHA incorporation into nanopores. HA/CHA growth rate on the surface of a nanoporous glass monolith is dominated by the pore-size limited transport of Ca2+ ions dissolved from nanoporous glass substrates. Furthermore, with rising overall growth rate controlled by nanopore size, HA/CHA microstructures evolved from needle-like, plate-like, and flower-like, respectively. Furthermore, the levels of initial cell attachment and protein adsorption on HA/CHA microstructures formed on different nanopore sizes were investigated. The initial cell attachment was quantified by measuring the density and average size of attached MC3T3-E1 cells after 2-hour seeding period. The amounts and conformation of adsorbed proteins after 2-hour incubation with HA/CHA were characterized by Western blot and FTIR, respectively. It was shown that the amounts of protein adsorption on various HA/CHA microstructures do not correlate with the initial MC3T3-E1 attachment, while the beta-sheet/alpha-helix ratios in Amide I of bovine albumin serum (BSA) adsorbed on HA/CHA microstructures do correlate to the level of initial cell attachment. This result suggests that the beta-sheet structure in BSA interacts with and activates the RGD sequence of adhesion proteins, such as fibronectin, upon adsorption, thus significantly enhancing the initial attachment of MC3T3-E1 cells. These findings provide new insights that can lead to a more detailed fundamental understanding of protein-surface and protein-protein interactions, which are crucial for the further development of bioactive material.

Faster proton transfer dynamics of water on SnO2 compared to TiO2.

PubMed

Kumar, Nitin; Kent, Paul R C; Bandura, Andrei V; Kubicki, James D; Wesolowski, David J; Cole, David R; Sofo, Jorge O

2011-01-28

Proton jump processes in the hydration layer on the iso-structural TiO(2) rutile (110) and SnO(2) cassiterite (110) surfaces were studied with density functional theory molecular dynamics. We find that the proton jump rate is more than three times faster on cassiterite compared with rutile. A local analysis based on the correlation between the stretching band of the O-H vibrations and the strength of H-bonds indicates that the faster proton jump activity on cassiterite is produced by a stronger H-bond formation between the surface and the hydration layer above the surface. The origin of the increased H-bond strength on cassiterite is a combined effect of stronger covalent bonding and stronger electrostatic interactions due to differences of its electronic structure. The bridging oxygens form the strongest H-bonds between the surface and the hydration layer. This higher proton jump rate is likely to affect reactivity and catalytic activity on the surface. A better understanding of its origins will enable methods to control these rates.

The influence of various cooling rates during laser alloying on nodular iron surface layer

NASA Astrophysics Data System (ADS)

Paczkowska, Marta; Makuch, Natalia; Kulka, Michał

2018-06-01

The results of research referring to modification of the nodular iron surface layer by laser alloying with cobalt were presented. The aim of this study was to analyze the possibilities of cobalt implementation into the surface layer of nodular iron in various laser heat treatment conditions (by generating different cooling rates of melted surface layer). The modified surface layer of nodular iron was analyzed with OM, SEM, TEM, XRD, EDS and Vickers microhardness tester. The modified surface layer of nodular iron after laser alloying consisted of: the alloyed zone (melted with cobalt), the transition zone and the hardened zone from solid state. The alloyed zone was characterized by higher microstructure homogeneity - in contrast to the transition and the hardened zones. All the alloyed zones contained a dendritic microstructure. Dendrites consisted of martensite needles and retained austenite. Cementite was also detected. It was stated, that due to similar dimension of iron and cobalt atoms, their mutual replacement in the crystal lattice could occur. Thus, formation of phases based on α solution: Co-Fe (44-1433) could not be excluded. Although cobalt should be mostly diluted in solid solutions (because of its content in the alloyed zone), the other newly formed phases as Co (ε-hex.), FeC and cobalt carbides: Co3C, CoC0.25 could be present in the alloyed zones as a result of unique microstructure creation during laser treatment. Pearlite grains were observed in the zone, formed using lower power density of the laser beam and its longer exposition time. Simply, such conditions resulted in the cooling rate which was lower than critical cooling rate. The alloyed zones, produced at a higher cooling rate, were characterized by better microstructure homogeneity. Dendrites were finer in this case. This could result from a greater amount of crystal nuclei appearing at higher cooling rate. Simultaneously, the increased amount of γ-Fe and Fe3C precipitates was expected in the alloyed zone formed at higher cooling rates. The hardness of nodular iron surface layer, alloyed with cobalt, was up to 4-times higher than the hardness of core material. The hardness of alloyed zones strongly depended on laser treatment conditions. In the case of lower cooling rate, lower hardness was observed due to more coarse-grained microstructure and a presence of pearlite. The hardness of the alloyed zone increased (from 850 to 950HV0.1) together with the increasing cooling rate (from 2 · 103 to nearly 9 · 103 °C/s). Laser treatment enabled a formation of surface layers on nodular iron, alloyed with cobalt. The microstructure of such a surface layer could be controlled by the laser processing parameters. High hardness and fine microstructure of the laser-alloyed nodular iron with cobalt should result in higher resistance to wear, corrosion and even (due to effect of cobalt addition) elevated temperatures during operation conditions of machine parts.

Engineering Glass Passivation Layers -Model Results

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skorski, Daniel C.; Ryan, Joseph V.; Strachan, Denis M.

2011-08-08

The immobilization of radioactive waste into glass waste forms is a baseline process of nuclear waste management not only in the United States, but worldwide. The rate of radionuclide release from these glasses is a critical measure of the quality of the waste form. Over long-term tests and using extrapolations of ancient analogues, it has been shown that well designed glasses exhibit a dissolution rate that quickly decreases to a slow residual rate for the lifetime of the glass. The mechanistic cause of this decreased corrosion rate is a subject of debate, with one of the major theories suggesting thatmore » the decrease is caused by the formation of corrosion products in such a manner as to present a diffusion barrier on the surface of the glass. Although there is much evidence of this type of mechanism, there has been no attempt to engineer the effect to maximize the passivating qualities of the corrosion products. This study represents the first attempt to engineer the creation of passivating phases on the surface of glasses. Our approach utilizes interactions between the dissolving glass and elements from the disposal environment to create impermeable capping layers. By drawing from other corrosion studies in areas where passivation layers have been successfully engineered to protect the bulk material, we present here a report on mineral phases that are likely have a morphological tendency to encrust the surface of the glass. Our modeling has focused on using the AFCI glass system in a carbonate, sulfate, and phosphate rich environment. We evaluate the minerals predicted to form to determine the likelihood of the formation of a protective layer on the surface of the glass. We have also modeled individual ions in solutions vs. pH and the addition of aluminum and silicon. These results allow us to understand the pH and ion concentration dependence of mineral formation. We have determined that iron minerals are likely to form a complete incrustation layer and we plan to look more closely at Vivianite [Fe3(PO4)2-8(H2O)] and Siderite [FeCO3] in the next stage of the project.« less

The evolution of tectonic features on Ganymede

NASA Technical Reports Server (NTRS)

Squyres, S. W.

1982-01-01

The bands of bright resurfaced terrain on Ganymede are probably broad grabens formed by global expansion and filled with deposits of ice. Grooves within the bands are thought to be extensional features formed during the same episode of expansion. The crust of Ganymede is modeled as a viscoelastic material subjected to extensional strain. With sufficiently high strain rates and stresses, deep normal faulting will occur, creating broad grabens that may then be filled. Continuing deformation at high strain rates and stresses will cause propagation of deep faults up into the flood deposits and normal faulting at the surface, while lower strain rates and stresses will cause formation of open extension fractures or, if the crustal strength is very low, grabens at the surface. The spacing between adjacent fractures may reflect the geothermal gradient at the time of deformation. Surface topography resulting from fracturing and normal faulting will decay with time as a result of viscous relaxation and mass-wasting.

Star Formation in Merging Galaxies Using FIRE

NASA Astrophysics Data System (ADS)

Perez, Adrianna; Hung, Chao-Ling; Naiman, Jill; Moreno, Jorge; Hopkins, Philip

2018-01-01

Galaxy interactions and mergers are efficient mechanisms to birth stars at rates that are significantly higher than found in our Milky Way galaxy. The Kennicut-Schmidt (KS) relation is an empirical relationship between the star-forming rate and gas surface densities of galaxies (Schmidt 1959; Kennicutt 1998). Although most galaxies follow the KS relation, the high levels of star formation in galaxy mergers places them outside of this otherwise tight relationship. The goal of this research is to analyze the gas content and star formation of simulated merging galaxies. Our work utilizes the Feedback In Realistic Environments (FIRE) model (Hopkins et al., 2014). The FIRE project is a high-resolution cosmological simulation that resolves star-forming regions and incorporates stellar feedback in a physically realistic way. In this work, we have noticed a significant increase in the star formation rate at first and second passage, when the two black holes of each galaxy approach one other. Next, we will analyze spatially resolved star-forming regions over the course of the interacting system. Then, we can study when and how the rates that gas converts into stars deviate from the standard KS. These analyses will provide important insights into the physical mechanisms that regulate star formation of normal and merging galaxies and valuable theoretical predictions that can be used to compare with current and future observations from ALMA or the James Webb Space Telescope.

Fusion of vesicles with the air-water interface: the influence of polar head group, salt concentration, and vesicle size.

PubMed

Gugliotti, M; Chaimovich, H; Politi, M J

2000-02-15

Fusion of vesicles with the air-water interface and consequent monolayer formation has been studied as a function of temperature. Unilamellar vesicles of DMPC, DPPC, and DODAX (X=Cl(-), Br(-)) were injected into a subphase containing NaCl, and the surface pressure (tension) was recorded on a Langmuir Balance (Tensiometer) using the Wilhelmy plate (Ring) method. For the zwitterionic vesicles, plots of the initial surface pressure increase rate (surface tension decrease rate) as a function of temperature show a peak at the phase transition temperature (T(m)) of the vesicles, whereas for ionic ones they show a sharp rise. At high concentrations of NaCl, ionic DODA(Cl) vesicles seem to behave like zwitterionic ones, and the rate of fusion is higher at the T(m). The influence of size was studied comparing large DODA(Cl) vesicles with small sonicated ones, and no significant changes were found regarding the rate of fusion with the air-water interface.

Cooling and crystallization of lava in open channels, and the transition of Pāhoehoe Lava to 'A'ā

NASA Astrophysics Data System (ADS)

Cashman, Katharine V.; Thornber, Carl; Kauahikaua, James P.

Samples collected from a lava channel active at Kīlauea Volcano during May 1997 are used to constrain rates of lava cooling and crystallization during early stages of flow. Lava erupted at near-liquidus temperatures ( 1150 °C) cooled and crystallized rapidly in upper parts of the channel. Glass geothermometry indicates cooling by 12-14 °C over the first 2km of transport. At flow velocities of 1-2m/s, this translates to cooling rates of 22-50 °C/h. Cooling rates this high can be explained by radiative cooling of a well-stirred flow, consistent with observations of non-steady flow in proximal regions of the channel. Crystallization of plagioclase and pyroxene microlites occurred in response to cooling, with crystallization rates of 20-50% per hour. Crystallization proceeded primarily by nucleation of new crystals, and nucleation rates of 104/cm3s are similar to those measured in the 1984 open channel flow from Mauna Loa Volcano. There is no evidence for the large nucleation delays commonly assumed for plagioclase crystallization in basaltic melts, possibly a reflection of enhanced nucleation due to stirring of the flow. The transition of the flow surface morphology from pāhoehoe to 'a'ā occurred at a distance of 1.9km from the vent. At this point, the flow was thermally stratified, with an interior temperature of 1137 °C and crystallinity of 15%, and a flow surface temperature of 1100 °C and crystallinity of 45%. 'A'ā formation initiated along channel margins, where crust was continuously disrupted, and involved tearing and clotting of the flow surface. Both observations suggest that the transition involved crossing of a rheological threshold. We suggest this threshold to be the development of a lava yield strength sufficient to prevent viscous flow of lava at the channel margin. We use this concept to propose that 'a'ā formation in open channels requires both sufficiently high strain rates for continued disruption of surface crusts and sufficient groundmass crystallinity to generate a yield strength equivalent to the imposed stress. In Hawai'i, where lava is typically microlite poor on eruption, these combined requirements help to explain two common observations on 'a'ā formation: (a) 'a'ā flow fields are generated when effusion rates are high (thus promoting crustal disruption); and (b) under most eruption conditions, lava issues from the vent as pāhoehoe and changes to 'a'ā only after flowing some distance, thus permitting sufficient crystallization.

Formation of extracellular polymeric substances from acidogenic sludge in H2-producing process.

PubMed

Sheng, Guo-Ping; Yu, Han-Qing

2007-02-01

In this study, the formation of extracellular polymeric substances (EPS) and surface characteristics of an acidogenic sludge in anaerobic H(2)-producing process was investigated. Results show that carbohydrates, proteins, and humic substances were the dominant components in bound EPS (BEPS), while in soluble EPS (SEPS), carbohydrates were the main component. The total content of BEPS initially increased but then kept almost unchanged during fermentation from 25 to 35 h; after that, it slightly decreased. The total content of SEPS increased to 172.5 +/- 0.05 mg C g(-1) volatile suspended solid with the time that increased to 23.5 h, and then rapidly decreased until 43 h; thereafter, it kept almost unchanged. The SEPS had good correlations with the specific H(2) production rate, substrate degradation rate, and specific aqueous products formation rate, but the BEPS seemed to have no such correlations with these specific rates. Results also confirm that part of EPS could be utilized by the H(2)-producing sludge. As the substrate was in short supply, the EPS would be hydrolyzed to sever as carbon and energy source.

Soil sealing and vesicular layer formation as initial structure development and its effect on infiltration

NASA Astrophysics Data System (ADS)

Badorreck, A.; Gerke, H. H.; Weller, U.; Vontobel, P.

2009-04-01

In the Lusatia mining district (NE-Germany) an artificial catchment was constructed to study initial ecosystem development and runoff generation. As a key process in this early stage, we investigate the surface structure dynamics as it strongly influences erosion, infiltration, matter dynamics, and vegetation establishment. The presented work focuses on observations of soil pore structure formation at the surface at five sites in the catchment and in an adjacent "younger" area composed of comparable sediments. Moreover we've conducted infiltration experiments in the lab and field to relate the soil pore structure to the hydraulic properties. The surface soil was sampled in cylindrical rings (10 cm³) down to 2 cm depth from which bulk density profiles were obtained using X-ray computed tomography (CT) (at UFZ- Halle, Germany) with a resolution of 0.084 mm. The influence of structure on infiltration was investigated using neutron radiography (at the NEUTRA facility of the Paul-Scherrer-Institut, Villigen, Switzerland) to visualise two-dimensional (2D) infiltration patterns. The slab-type samples were equilibrated to different initial water contents and then exposed to drip irrigation (to simulate rainfall) while a series of neutron radiographs were taken. In addition, field measurements with a miniature tension infiltrometer were conduced. The micro-tomographies exhibit formation of surface sealing whose thickness and intensity vary with silt and clay content. The CT images show several coarser- and finer-textured micro-layers at the sample surfaces that were formed as a consequence of repeated washing in of finer particles in underlying coarser sediment. In micro-depressions, the uppermost layers consist of sorted fine sand and silt due to wind erosion. Similar as for desert pavements, a vesicular pore structure developed in these sediments on top, but also scattered in fine sand- and silt-enriched micro-layers. The infiltration rates were severely affected by the surface crusts; however, the rates were independent of the vesicular pore layer.

Synthesis of uniformly distributed single- and double-sided zinc oxide (ZnO) nanocombs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Altintas Yildirim, Ozlem; Liu, Yuzi; Petford-Long, Amanda K.

Uniformly distributed single- and double-sided zinc oxide (ZnO) nanocomb structures have been prepared by a vapor-liquid-solid technique from a mixture of ZnO nanoparticles and graphene nanoplatelets. The ZnO seed nanoparticles were synthesized via a simple precipitation method. The structure of the ZnO nanocombs could easily be controlled by tuning the carrier-gas flow rate during growth. Higher flow rate resulted in the formation of uniformly-distributed single-sided comb structures with nanonail-shaped teeth, as a result of the self-catalysis effect of the catalytically active Zn-terminated polar (0001) surface. Lower gas flow rate was favorable for production of double-sided comb structures with the twomore » sets of teeth at an angle of similar to 110 degrees to each other along the comb ribbon, which was attributed to the formation of a bicrystal nanocomb ribbon. Lastly, the formation of such a double-sided structure with nanonail-shaped teeth has not previously been reported.« less

Synthesis of uniformly distributed single- and double-sided zinc oxide (ZnO) nanocombs

DOE PAGES

Altintas Yildirim, Ozlem; Liu, Yuzi; Petford-Long, Amanda K.

2015-08-21

Uniformly distributed single- and double-sided zinc oxide (ZnO) nanocomb structures have been prepared by a vapor-liquid-solid technique from a mixture of ZnO nanoparticles and graphene nanoplatelets. The ZnO seed nanoparticles were synthesized via a simple precipitation method. The structure of the ZnO nanocombs could easily be controlled by tuning the carrier-gas flow rate during growth. Higher flow rate resulted in the formation of uniformly-distributed single-sided comb structures with nanonail-shaped teeth, as a result of the self-catalysis effect of the catalytically active Zn-terminated polar (0001) surface. Lower gas flow rate was favorable for production of double-sided comb structures with the twomore » sets of teeth at an angle of similar to 110 degrees to each other along the comb ribbon, which was attributed to the formation of a bicrystal nanocomb ribbon. Lastly, the formation of such a double-sided structure with nanonail-shaped teeth has not previously been reported.« less

Condensation Temperature in Non-Equilibrium Condensation.

NASA Astrophysics Data System (ADS)

Tanaka, K. K.; Tanaka, H.; Nakazawa, K.

1999-09-01

In investigation of the origins of the presolar grains, it is important to clear the formation process of grains in ejecta of AGB stars or supernovae, where most presolar grains are suggested to be formed. The grain formation has been investigated based on the classical nucleation theory in many previous studies. On the other hand it has been pointed out that the classical nucleation rate is significantly different from that obtained by experiments, and should not be applied to grain formation in astrophysical environments (Donn and Nuth, 1985, ApJ 288, 187-190). Recently Dillmann and Meier (1991, J. Chem. Phys. 94, 3872-3884) proposed new semi-phenomological nucleation model, which achieved excellent agreements with experiments. In this study we applied the nucleation rate in the semi-phenomological model to the grain formation in astrophysical environment in order to make it clear how the grain formation changes due to the new nucleation rate. For various parameters determined by surface energy of grain and cooling time of vapor, we solved equations describing the grain formation. From the comparison between the results obtained by new nucleation rate and that by classical one we found that there is no significant difference in grain number density and grain size, but the condensation temperature is considerably different from the previous one. For example in carbon rich AGB star the condensation temperature of graphite is lower than that obtained by classical one by a few hundreds Kelvin: this means the condensation temperature is lower than the equilibrium condensation temperature by about 500 Kelvin. Furthermore we investigated the condensation of vapor in which grain impurities are already present. We obtained the condition for formation of core-mantle type grains. Our obtained condition would give constraint on the formation of core-mantle type presolar grains.

Formation mechanism and mechanics of dip-pen nanolithography using molecular dynamics.

PubMed

Wu, Cheng-Da; Fang, Te-Hua; Lin, Jen-Fin

2010-03-02

Molecular dynamics simulations are used to investigate the mechanisms of molecular transference, pattern formation, and mechanical behavior in the dip-pen nanolithography (DPN) process. The effects of deposition temperature were studied using molecular trajectories, the meniscus characteristic, surface absorbed energy, and pattern formation analysis. At the first transferred stage (at the initial indentation depth), the conformation of SAM molecules lies almost on the substrate surface. The molecules start to stand on the substrate due to the pull and drag forces at the second transferred stage (after the tip is pulled up). According to the absorbed energy behavior, the second transferred stage has larger transferred amounts and the transfer rate is strongly related to temperature. When molecules were deposited at low temperature (e.g., room temperature), the pattern shape was more highly concentrated. The pattern shape at high temperatures expanded and the area increased because of good molecular diffusion.

High resolution radio and optical observations of the central starburst in the low-metallicity dwarf galaxy II Zw 40

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kepley, Amanda A.; Reines, Amy E.; Johnson, Kelsey E.

2014-02-01

The extent to which star formation varies in galaxies with low masses, low metallicities, and high star formation rate surface densities is not well constrained. To gain insight into star formation under these physical conditions, this paper estimates the ionizing photon fluxes, masses, and ages for young massive clusters in the central region of II Zw 40—the prototypical low-metallicity dwarf starburst galaxy—from radio continuum and optical observations. Discrete, cluster-sized sources only account for half the total radio continuum emission; the remainder is diffuse. The young (≲ 5 Myr) central burst has a star formation rate surface density that significantly exceedsmore » that of the Milky Way. Three of the 13 sources have ionizing photon fluxes (and thus masses) greater than R136 in 30 Doradus. Although isolating the effects of galaxy mass and metallicity is difficult, the H II region luminosity function and the internal extinction in the center of II Zw 40 appear to be primarily driven by a merger-related starburst. The relatively flat H II region luminosity function may be the result of an increase in interstellar medium pressure during the merger and the internal extinction is similar to that generated by the clumpy and porous dust in other starburst galaxies.« less

Reaction Mechanisms for the Electrochemical Reduction of CO 2 to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water

DOE PAGES

Cheng, Tao; Xiao, Hai; Goddard, William A.

2016-10-11

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions is not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or to carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). We carry out QM calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO 2 reduction reaction conditions) to examine the initial reaction pathways to form CO and formatemore » (HCOO –) from CO 2 through free energy calculations at 298 K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ-), with a free energy barrier of ΔG ‡ = 0.43 eV, the rate-determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 and 0.30 eV, respectively. HCOO– formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO – formation occurs in the first electron-transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Therefore, to alter the product distribution, we need to control this first step of CO 2 binding, which might involve controlling pH, alloying, or changing the structure at the nanoscale.« less

Influence of Cutting Parameters and Tool Wear on the Surface Integrity of Cobalt-Based Stellite 6 Alloy When Machined Under a Dry Cutting Environment

NASA Astrophysics Data System (ADS)

Yingfei, Ge; de Escalona, Patricia Muñoz; Galloway, Alexander

2017-01-01

The efficiency of a machining process can be measured by evaluating the quality of the machined surface and the tool wear rate. The research reported herein is mainly focused on the effect of cutting parameters and tool wear on the machined surface defects, surface roughness, deformation layer and residual stresses when dry milling Stellite 6, deposited by overlay on a carbon steel surface. The results showed that under the selected cutting conditions, abrasion, diffusion, peeling, chipping and breakage were the main tool wear mechanisms presented. Also the feed rate was the primary factor affecting the tool wear with an influence of 83%. With regard to the influence of cutting parameters on the surface roughness, the primary factors were feed rate and cutting speed with 57 and 38%, respectively. In addition, in general, as tool wear increased, the surface roughness increased and the deformation layer was found to be influenced more by the cutting parameters rather than the tool wear. Compressive residual stresses were observed in the un-machined surface, and when machining longer than 5 min, residual stress changed 100% from compression to tension. Finally, results showed that micro-crack initiation was the main mechanism for chip formation.

Dust devil track survey at Elysium Planitia, Mars: Implications for the InSight landing sites

NASA Astrophysics Data System (ADS)

Reiss, Dennis; Lorenz, Ralph D.

2016-03-01

The InSight (Interior Exploration using Seismic Investigations, Geodesy and Heat Transport) robotic lander is scheduled to land in Elysium Planitia on Mars in September 2016. InSight will perform the first comprehensive surface-based geophysical investigation including seismic measurements. Knowledge about encounter rates of dust devils with the InSight lander are important for two main reasons: (1) dust devils will affect the scientific measurements, i.e., wind-induced seismic noise, and (2) the power-supply of the InSight lander and instruments is provided by solar arrays and previous landers and rovers on Mars were affected by a steady decline in electrical power output due to atmospheric dust deposition on the solar panels. Long term science operations were only made possible by dust clearing events of the solar arrays caused by wind gusts and dust devils. In this study we analyzed dust devil tracks (DDTs) at the final InSight landing site region in Elysium Planitia. Formation of DDTs is caused by the removal of a layer of dust by passing dust devils, hence in principle the same process as clearing of dust from solar panels. We mapped the number, size (width and length), and orientation of DDTs in repeat observations using High Resolution Imaging Science Experiment (HiRISE) images covering the exact same surface area acquired within a relatively short time span (<90 martian days). In total, we analyzed 557 newly formed dust devil tracks in 8 study areas. DDTs are morphologically relatively straight with a low mean sinuosity of 1.03 and only reach maximum widths of 30 m. The mean DDT width is 4 m, indicating that the dust devil size population is dominated by small dust devils with a diameter <10 m. The size-frequency distribution of DDTs follows a -2 power law. The mean lengths of DDTs are 0.62 km and 1.23 km for complete (tracks which are visible from their start to end point) and incomplete DDTs (tracks running across the HiRISE footprint), respectively. The alignment of DDTs in combination with Mars Climate Database (MCD) predicted wind directions imply that dust devils are moving from SE to NW until early northern autumn with a reversal to NW-SE directions of movement at LS = 200° consistent with the seasonal reversal in direction of the Hadley circulation. DDT formation rates vary between 0.002 and 0.08 ddt km-2 sol-1. DDT area formation rates using the measured DDT widths, lengths, and formation rates are in the range of 0.0003-0.00006 km2 km-2 sol-1, implying that a given spot on the surface may be cleared of dust only once between ∼3000 and 16,000 sols (i.e. every ∼5-24 Mars years). Measured DDT formation rates were used to find a scaling factor to the seasonal DDA index, and then integrated over the year to estimate a mean annual DDT formation rate of 0.046 ddt km-2 sol-1. This translates into a solar panel clearing recurrence interval estimate of ∼11 Mars years using the mean annual DDT formation rate, and the mean DDT width and length from all measured DDTs. Due to several uncertainties this solar panel clearing recurrence interval for the InSight landing should be seen as an upper limit estimate.

HOW UNIVERSAL IS THE {Sigma}{sub SFR}-{Sigma}{sub H{sub 2}} RELATION?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feldmann, R.; Gnedin, N. Y.; Kravtsov, A. V., E-mail: feldmann@fnal.gov

It is a well-established empirical fact that the surface density of the star formation rate, {Sigma}{sub SFR}, strongly correlates with the surface density of molecular hydrogen, {Sigma}{sub H{sub 2}}, at least when averaged over large ({approx}kpc) scales. Much less is known, however, about whether (and how) the {Sigma}{sub SFR}-{Sigma}{sub H{sub 2}} relation depends on environmental parameters, such as the metallicity or the UV radiation field in the interstellar medium (ISM). Furthermore, observations indicate that the scatter in the {Sigma}{sub SFR}-{Sigma}{sub H{sub 2}} relation increases rapidly with decreasing averaging scale. How the scale-dependent scatter is generated and how one recovers amore » tight {approx} kpc scale {Sigma}{sub SFR}-{Sigma}{sub 2} relation in the first place is still largely debated. Here, these questions are explored with hydrodynamical simulations that follow the formation and destruction of H{sub 2}, include radiative transfer of UV radiation, and resolve the ISM on {approx}60 pc scales. We find that within the considered range of H{sub 2} surface densities (10-100 M{sub sun} pc{sup -2}), the {Sigma}{sub SFR}-{Sigma}{sub H{sub 2}} relation is steeper in environments of low-metallicity and/or high-radiation fields (compared to the Galaxy), that the star formation rate (SFR) at a given H{sub 2} surface density is larger, and the scatter is increased. Deviations from a 'universal' {Sigma}{sub SFR}-{Sigma}{sub H{sub 2}} relation should be particularly relevant for high-redshift galaxies or for low-metallicity dwarfs at z {approx} 0. We also find that the use of time-averaged SFRs produces a large, scale-dependent scatter in the {Sigma}{sub SFR}-{Sigma}{sub H{sub 2}} relation. Given the plethora of observational data expected from upcoming surveys such as ALMA, the scale-scatter relation may indeed become a valuable tool for determining the physical mechanisms connecting star formation and H{sub 2} formation.« less

Theory of structure formation in snowfields motivated by penitentes, suncups, and dirt cones.

PubMed

Betterton, M D

2001-05-01

Penitentes and suncups are structures formed as snow melts, typically high in the mountains. When the snow is dirty, dirt cones and other structures can form instead. Building on previous field observations and experiments, this paper presents a theory of ablation morphologies, and the role of surface dirt in determining the structures formed. The glaciological literature indicates that sunlight, heating from air, and dirt all play a role in the formation of structure on an ablating snow surface. The present paper formulates a minimal model for the formation of ablation morphologies as a function of measurable parameters and considers the linear stability of this model. The dependence of ablation morphologies on weather conditions and initial dirt thickness is studied, focusing on the initial growth of perturbations away from a flat surface. We derive a single-parameter expression for the melting rate as a function of dirt thickness, which agrees well with a set of measurements by Driedger. An interesting result is the prediction of a dirt-induced traveling instability for a range of parameters.

The effect of butterfly-scale inspired patterning on leading-edge vortex growth

NASA Astrophysics Data System (ADS)

Wilroy, Jacob; Lang, Amy; Wahidi, Redha

2014-11-01

Leading edge vortices (LEVs) are important for generating thrust and lift in flapping flight, and the surface patterning (scales) on butterfly wings is hypothesized to play a role in the vortex formation of the LEV. To simplify this complex flow problem, we designed an experiment to focus on the alteration of 2-D vortex development with a variation in surface patterning. Specifically we are interested in the secondary vorticity generated by the LEV interacting at the patterned surface and how this can affect the growth rate of the circulation in the LEV. For this experiment we used rapid-prototyped longitudinal and transverse square grooves attached to a flat plate and compared the vortex formation as the plate moved vertically. The plate is impulsively started in quiescent water and flow fields at Re = 1500, 3000, and 6000 are examined using Digital Particle Image Velocimetry (DPIV). The vortex formation time is 0.6 and is based on the flat plate travel length and chord length. Support for this research came from NSF REU Grant 1358991 and CBET 1335848.

The effect of butterfly-scale inspired patterning on leading-edge vortex growth

NASA Astrophysics Data System (ADS)

Wilroy, Jacob; Lang, Amy

2015-11-01

Leading edge vortices (LEVs) are important for generating thrust and lift in flapping flight, and the surface patterning (scales) on butterfly wings is hypothesized to play a role in the vortex formation of the LEV. To simplify this complex flow problem, an experiment was designed to focus on the alteration of 2-D vortex development with a variation in surface patterning. Specifically, the secondary vorticity generated by the LEV interacting at the patterned surface was studied and the subsequent affect on the growth rate of the circulation in the LEV. For this experiment we used butterfly inspired grooves attached to a flat plate and compared the vortex formation to a smooth plate case as the plate moved vertically. The plate is impulsively started in quiescent water and flow fields at Re = 1500, 3000, and 6000 are examined using Digital Particle Image Velocimetry (DPIV). The vortex formation time is 3.0 and is based on the flat plate travel length and chord length. We would like to thank the National Science Foundation REU Site Award 1358991 for funding this research.

A model for foam formation, stability, and breakdown in glass-melting furnaces.

PubMed

van der Schaaf, John; Beerkens, Ruud G C

2006-03-01

A dynamic model for describing the build-up and breakdown of a glass-melt foam is presented. The foam height is determined by the gas flux to the glass-melt surface and the drainage rate of the liquid lamellae between the gas bubbles. The drainage rate is determined by the average gas bubble radius and the physical properties of the glass melt: density, viscosity, surface tension, and interfacial mobility. Neither the assumption of a fully mobile nor the assumption of a fully immobile glass-melt interface describe the observed foam formation on glass melts adequately. The glass-melt interface appears partially mobile due to the presence of surface active species, e.g., sodium sulfate and silanol groups. The partial mobility can be represented by a single, glass-melt composition specific parameter psi. The value of psi can be estimated from gas bubble lifetime experiments under furnace conditions. With this parameter, laboratory experiments of foam build-up and breakdown in a glass melt are adequately described, qualitatively and quantitatively by a set of ordinary differential equations. An approximate explicit relationship for the prediction of the steady-state foam height is derived from the fundamental model.

Surface Modification and Surface - Subsurface Exchange Processes on Europa

NASA Astrophysics Data System (ADS)

Phillips, Cynthia B.; Molaro, Jamie; Hand, Kevin P.

2017-10-01

The surface of Jupiter’s moon Europa is modified by exogenic processes such as sputtering, gardening, radiolysis, sulfur ion implantation, and thermal processing, as well as endogenic processes including tidal shaking, mass wasting, and the effects of subsurface tectonic and perhaps cryovolcanic activity. New materials are created or deposited on the surface (radiolysis, micrometeorite impacts, sulfur ion implantation, cryovolcanic plume deposits), modified in place (thermal segregation, sintering), transported either vertically or horizontally (sputtering, gardening, mass wasting, tectonic and cryovolcanic activity), or lost from Europa completely (sputtering, plumes, larger impacts). Some of these processes vary spatially, as visible in Europa’s leading-trailing hemisphere brightness asymmetry.Endogenic geologic processes also vary spatially, depending on terrain type. The surface can be classified into general landform categories that include tectonic features (ridges, bands, cracks); disrupted “chaos-type” terrain (chaos blocks, matrix, domes, pits, spots); and impact craters (simple, complex, multi-ring). The spatial distribution of these terrain types is relatively random, with some differences in apex-antiapex cratering rates and latitudinal variation in chaos vs. tectonic features.In this work, we extrapolate surface processes and rates from the top meter of the surface in conjunction with global estimates of transport and resurfacing rates. We combine near-surface modification with an estimate of surface-subsurface (and vice versa) transport rates for various geologic terrains based on an average of proposed formation mechanisms, and a spatial distribution of each landform type over Europa’s surface area.Understanding the rates and mass balance for each of these processes, as well as their spatial and temporal variability, allows us to estimate surface - subsurface exchange rates over the average surface age (~50myr) of Europa. Quantifying the timescale and volume of transported material will yield insight on whether such a process may provide fuel to sustain a biosphere in Europa’s subsurface ocean, which is relevant to searches for life by a future mission such as a potential Europa Lander.

Surface Modification and Surface - Subsurface Exchange Processes on Europa

NASA Astrophysics Data System (ADS)

Phillips, C. B.; Molaro, J.; Hand, K. P.

2017-12-01

The surface of Jupiter's moon Europa is modified by exogenic processes such as sputtering, gardening, radiolysis, sulfur ion implantation, and thermal processing, as well as endogenic processes including tidal shaking, mass wasting, and the effects of subsurface tectonic and perhaps cryovolcanic activity. New materials are created or deposited on the surface (radiolysis, micrometeorite impacts, sulfur ion implantation, cryovolcanic plume deposits), modified in place (thermal segregation, sintering), transported either vertically or horizontally (sputtering, gardening, mass wasting, tectonic and cryovolcanic activity), or lost from Europa completely (sputtering, plumes, larger impacts). Some of these processes vary spatially, as visible in Europa's leading-trailing hemisphere brightness asymmetry. Endogenic geologic processes also vary spatially, depending on terrain type. The surface can be classified into general landform categories that include tectonic features (ridges, bands, cracks); disrupted "chaos-type" terrain (chaos blocks, matrix, domes, pits, spots); and impact craters (simple, complex, multi-ring). The spatial distribution of these terrain types is relatively random, with some differences in apex-antiapex cratering rates and latitudinal variation in chaos vs. tectonic features. In this work, we extrapolate surface processes and rates from the top meter of the surface in conjunction with global estimates of transport and resurfacing rates. We combine near-surface modification with an estimate of surface-subsurface (and vice versa) transport rates for various geologic terrains based on an average of proposed formation mechanisms, and a spatial distribution of each landform type over Europa's surface area. Understanding the rates and mass balance for each of these processes, as well as their spatial and temporal variability, allows us to estimate surface - subsurface exchange rates over the average surface age ( 50myr) of Europa. Quantifying the timescale and volume of transported material will yield insight on whether such a process may provide fuel to sustain a biosphere in Europa's subsurface ocean, which is relevant to searches for life by a future mission such as a potential Europa Lander.

Process and kinetics of bonelike apatite formation on sintered hydroxyapatite in a simulated body fluid.

PubMed

Kim, Hyun-Min; Himeno, Teruyuki; Kokubo, Tadashi; Nakamura, Takashi

2005-07-01

The surfaces of two hydroxyapatites (HA), which have been sintered at different temperatures of 800 and 1200 degrees C, was investigated as a function of soaking time in simulated body fluid (SBF) using transmission electron microscopy (TEM) attached with energy-dispersive spectrometry (EDX) and laser electrophoresis spectroscopy. The TEM-EDX indicated that after soaking in SBF, both the HAs form bonelike apatite by undergoing the same surface structural change, i.e., formations of a Ca-rich amorphous or nano-crystalline calcium phosphate (ACP) and a Ca-poor ACP, which eventually crystallized into bonelike apatite. Zeta potential characterized by the electrophoresis indicated that during exposure to SBF, the HA surfaces reveal negative surface charge, thereby interacting with the positive calcium ions in the fluid to form the Ca-rich ACP, which gains positive surface charge. The Ca-rich ACP on the HAs then interacts with the negative phosphate ions in the fluid to form the Ca-poor ACP, which stabilizes by being crystallized into bonelike apatite with a low solubility in the SBF. The exposure times for formations of these phases of the Ca-rich ACP, the Ca-poor ACP as well as the apatite were, however, all late on HA sintered at 1200 degrees C, compared with the HA sintered at 800 degrees C. This phenomenon was attributed to a lower initial negative surface charge of the HA sintered at 800 degrees C than of that one sintered at 1200 degrees C, owing to poverty in surface hydroxyl and phosphate groups which are responsible for the surface negativity of the HA. These indicate that sintered temperature of HA might influence not in terms of the process but in terms of the rate of formation of biologically active bonelike apatite on its surface, through which the HA integrates with living bone.

Reduced Heat Flux Through Preferential Surface Reactions Leading to Vibrationally and Electronically Excited Product States

DTIC Science & Technology

2016-03-04

release. 13. SUPPLEMENTARY NOTES 14. ABSTRACT Instead of characterizing a hypersonic flight environment and then selecting an appropriate thermal ...Instead of characterizing a hypersonic flight environment and then selecting an appropriate thermal protection system (TPS) that can survive the...than the O2(a1Δg) production rate on the surface. It is also interesting to note that the ground state formation seems to approach a constant

Star cluster formation in cosmological simulations. I. Properties of young clusters

DOE PAGES

Li, Hui; Gnedin, Oleg Y.; Gnedin, Nickolay Y.; ...

2017-01-03

We present a new implementation of star formation in cosmological simulations by considering star clusters as a unit of star formation. Cluster particles grow in mass over several million years at the rate determined by local gas properties, with high time resolution. The particle growth is terminated by its own energy and momentum feedback on the interstellar medium. We test this implementation for Milky Way-sized galaxies at high redshift by comparing the properties of model clusters with observations of young star clusters. We find that the cluster initial mass function is best described by a Schechter function rather than a single power law. In agreement with observations, at low masses the logarithmic slope ismore » $$\\alpha \\approx 1.8\\mbox{–}2$$, while the cutoff at high mass scales with the star formation rate (SFR). A related trend is a positive correlation between the surface density of the SFR and fraction of stars contained in massive clusters. Both trends indicate that the formation of massive star clusters is preferred during bursts of star formation. These bursts are often associated with major-merger events. We also find that the median timescale for cluster formation ranges from 0.5 to 4 Myr and decreases systematically with increasing star formation efficiency. Local variations in the gas density and cluster accretion rate naturally lead to the scatter of the overall formation efficiency by an order of magnitude, even when the instantaneous efficiency is kept constant. As a result, comparison of the formation timescale with the observed age spread of young star clusters provides an additional important constraint on the modeling of star formation and feedback schemes.« less

Star cluster formation in cosmological simulations. I. Properties of young clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Hui; Gnedin, Oleg Y.; Gnedin, Nickolay Y.

We present a new implementation of star formation in cosmological simulations by considering star clusters as a unit of star formation. Cluster particles grow in mass over several million years at the rate determined by local gas properties, with high time resolution. The particle growth is terminated by its own energy and momentum feedback on the interstellar medium. We test this implementation for Milky Way-sized galaxies at high redshift by comparing the properties of model clusters with observations of young star clusters. We find that the cluster initial mass function is best described by a Schechter function rather than a single power law. In agreement with observations, at low masses the logarithmic slope ismore » $$\\alpha \\approx 1.8\\mbox{–}2$$, while the cutoff at high mass scales with the star formation rate (SFR). A related trend is a positive correlation between the surface density of the SFR and fraction of stars contained in massive clusters. Both trends indicate that the formation of massive star clusters is preferred during bursts of star formation. These bursts are often associated with major-merger events. We also find that the median timescale for cluster formation ranges from 0.5 to 4 Myr and decreases systematically with increasing star formation efficiency. Local variations in the gas density and cluster accretion rate naturally lead to the scatter of the overall formation efficiency by an order of magnitude, even when the instantaneous efficiency is kept constant. As a result, comparison of the formation timescale with the observed age spread of young star clusters provides an additional important constraint on the modeling of star formation and feedback schemes.« less

The Generation of Barriers to Melt Ascent in the Martian Lithosphere

NASA Astrophysics Data System (ADS)

Schools, Joe W.; Montési, Laurent G. J.

2018-01-01

Planetary mantles can be regarded as an aggregate of two phases: a solid, porous matrix and a liquid melt. Melt travels rapidly upward through the matrix due to its buoyancy. When this melt enters the colder lithosphere, it begins to crystallize. If crystallization happens at a high rate, the newly formed crystals can clog the pore space, reducing its permeability to essentially zero. This zone of zero permeability is the permeability barrier. We use the MELTS family of thermodynamic calculators to determine melt compositions and the crystallization sequence of ascending melt throughout Martian history and simulate the formation of permeability barriers. At lower strain rates (10-17-10-15 s-1) permeability barriers form deep in the lithosphere, possibly contributing to the formation of localized volcanic edifices on the Martian surface once fracturing or thermal erosion enables melt to traverse the lithosphere. Higher strain rates (10-13 s-1) yield shallower permeability barriers, perhaps producing extensive lava flows. Permeability barrier formation is investigated using an anhydrous mantle source or mantle sources that include up to 1,000 ppm H2O. Introducing even small amounts of water (25 ppm H2O) reduces mantle viscosity in a manner similar to increasing the strain rate and results in a shallower barrier than in the anhydrous case. Large amounts of water (1,000 ppm H2O) yield very shallow weak barriers or no barriers at all. The depth of the permeability barrier has evolved through time, likely resulting in a progression in the style of surface volcanism from widespread flows to massive, singular volcanoes.

Gas Hydrate Storage of Natural Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudy Rogers; John Etheridge

2006-03-31

Environmental and economic benefits could accrue from a safe, above-ground, natural-gas storage process allowing electric power plants to utilize natural gas for peak load demands; numerous other applications of a gas storage process exist. A laboratory study conducted in 1999 to determine the feasibility of a gas-hydrates storage process looked promising. The subsequent scale-up of the process was designed to preserve important features of the laboratory apparatus: (1) symmetry of hydrate accumulation, (2) favorable surface area to volume ratio, (3) heat exchanger surfaces serving as hydrate adsorption surfaces, (4) refrigeration system to remove heat liberated from bulk hydrate formation, (5)more » rapid hydrate formation in a non-stirred system, (6) hydrate self-packing, and (7) heat-exchanger/adsorption plates serving dual purposes to add or extract energy for hydrate formation or decomposition. The hydrate formation/storage/decomposition Proof-of-Concept (POC) pressure vessel and supporting equipment were designed, constructed, and tested. This final report details the design of the scaled POC gas-hydrate storage process, some comments on its fabrication and installation, checkout of the equipment, procedures for conducting the experimental tests, and the test results. The design, construction, and installation of the equipment were on budget target, as was the tests that were subsequently conducted. The budget proposed was met. The primary goal of storing 5000-scf of natural gas in the gas hydrates was exceeded in the final test, as 5289-scf of gas storage was achieved in 54.33 hours. After this 54.33-hour period, as pressure in the formation vessel declined, additional gas went into the hydrates until equilibrium pressure/temperature was reached, so that ultimately more than the 5289-scf storage was achieved. The time required to store the 5000-scf (48.1 hours of operating time) was longer than designed. The lower gas hydrate formation rate is attributed to a lower heat transfer rate in the internal heat exchanger than was designed. It is believed that the fins on the heat-exchanger tubes did not make proper contact with the tubes transporting the chilled glycol, and pairs of fins were too close for interior areas of fins to serve as hydrate collection sites. A correction of the fabrication fault in the heat exchanger fin attachments could be easily made to provide faster formation rates. The storage success with the POC process provides valuable information for making the process an economically viable process for safe, aboveground natural-gas storage.« less

On the validity of specific rate constants (kSA) in Fe0/H2O systems.

PubMed

Noubactep, C

2009-05-30

The validity of the specific reaction rate constants (k(SA)) in modelling contaminant removal in Fe(0)/H(2)O systems is questioned. It is shown that the current k(SA)-model does not consider the large reactive surface area provided by the in-situ formed oxide film, and thus the adsorptive interactions between contaminants and film materials. Furthermore, neither the dynamic nature of film formation nor the fact that the Fe(0) surface is shielded by the film is considered. Suggestions are made how the k(SA)-model could be further developed to meet its original goal.

Adsorption behavior of bisphenol A on CTAB-modified graphite

NASA Astrophysics Data System (ADS)

Wang, Li-Cong; Ni, Xin-jiong; Cao, Yu-Hua; Cao, Guang-qun

2018-01-01

In this work, the adsorption behavior of BPA on CTAB-modified graphite was investigated thoroughly to develop a novel absorbent material. Atomic force microscopy revealed that conical admicelles formed on the surface of graphite. The surface area of graphite decreased significantly from 1.46 to 0.95 m2 g-1, which confirmed the formation of the larger size admicelle instead of the original smaller particle on the surface. CTAB concentration and incubation time affected the progress of admicelle formation on the surface of graphite. Adsolubilization is key in BPA adsorption by CTAB-modified graphite. An extraordinary cation-π electron interaction between CTAB and BPA, revealed by a red-shift in the ultraviolet spectrum, as well as a hydrophobic interaction contribute substantially to BPA adsolubilization. The equilibrium adsorption capacity of the modified graphite for BPA was 125.01 mg g-1. The adsorption kinetic curves of BPA on modified graphite were shown to follow a pseudosecond-order rate. The adsorption process was observed to be both spontaneous and exothermic complied with the Freundlich model.

A new model for in situ nitrogen incorporation into 4H-SiC during epitaxy

PubMed Central

Ferro, Gabriel; Chaussende, Didier

2017-01-01

Nitrogen doping of 4H-SiC during vapor phase epitaxy is still lacking of a general model explaining the apparently contradictory trends obtained by different teams. In this paper, the evolutions of nitrogen incorporation (on both polar Si and C faces) as a function of the main growth parameters (C/Si ratio, temperature, pressure and growth rate) are reviewed and explained using a model based on surface exchanges between the gas phase and the uppermost 4H-SiC atomic layers. In this model, N incorporation is driven mainly by the transient formation of C vacancies, due to H2 etching, at the surface or near the surface. It is shown that all the growth parameters are influencing the probability of C vacancies formation in a similar manner as they do for N incorporation. The surface exchange model proposes a new framework for explaining the experimental results even beyond the commonly accepted reactor type dependency. PMID:28211528

Active Pacific meridional overturning circulation (PMOC) during the warm Pliocene.

PubMed

Burls, Natalie J; Fedorov, Alexey V; Sigman, Daniel M; Jaccard, Samuel L; Tiedemann, Ralf; Haug, Gerald H

2017-09-01

An essential element of modern ocean circulation and climate is the Atlantic meridional overturning circulation (AMOC), which includes deep-water formation in the subarctic North Atlantic. However, a comparable overturning circulation is absent in the Pacific, the world's largest ocean, where relatively fresh surface waters inhibit North Pacific deep convection. We present complementary measurement and modeling evidence that the warm, ~400-ppmv (parts per million by volume) CO 2 world of the Pliocene supported subarctic North Pacific deep-water formation and a Pacific meridional overturning circulation (PMOC) cell. In Pliocene subarctic North Pacific sediments, we report orbitally paced maxima in calcium carbonate accumulation rate, with accompanying pigment and total organic carbon measurements supporting deep-ocean ventilation-driven preservation as their cause. Together with high accumulation rates of biogenic opal, these findings require vigorous bidirectional communication between surface waters and interior waters down to ~3 km in the western subarctic North Pacific, implying deep convection. Redox-sensitive trace metal data provide further evidence of higher Pliocene deep-ocean ventilation before the 2.73-Ma (million years) transition. This observational analysis is supported by climate modeling results, demonstrating that atmospheric moisture transport changes, in response to the reduced meridional sea surface temperature gradients of the Pliocene, were capable of eroding the halocline, leading to deep-water formation in the western subarctic Pacific and a strong PMOC. This second Northern Hemisphere overturning cell has important implications for heat transport, the ocean/atmosphere cycle of carbon, and potentially the equilibrium response of the Pacific to global warming.

Effect of selected organic and inorganic snow and cloud components on the photochemical generation of nitrite by nitrate irradiation.

PubMed

Minero, Claudio; Maurino, Valter; Bono, Francesca; Pelizzetti, Ezio; Marinoni, Angela; Mailhot, Gilles; Carlotti, Maria Eugenia; Vione, Davide

2007-08-01

The effect of selected organic and inorganic compounds, present in snow and cloudwater was studied. Photolysis of solutions of nitrate to nitrite was carried out in the laboratory using a UVB light source. The photolysis and other reactions were then modelled. It is shown that formate, formaldehyde, methanesulphonate, and chloride to a lesser extent, can increase the initial formation rate of nitrite. The effect, particularly significant for formate and formaldehyde, is unlikely to be caused by scavenging of hydroxyl radicals. The experimental data obtained in this work suggest that possible causes are the reduction of nitrogen dioxide and nitrate by radical species formed on photooxidation of the organic compounds. Hydroxyl scavenging by organic and inorganic compounds would not affect the initial formation rate of nitrite, but would protect it from oxidation, therefore, increasing the concentration values reached at long irradiation times. The described processes can be relevant to cloudwater and the quasi-liquid layer on the surface of ice and snow, considering that in the polar regions irradiated snow layers are important sources of nitrous acid to the atmosphere. Formate and (at a lesser extent) formaldehyde are the compounds that play the major role in the described processes of nitrite/nitrous acid photoformation by initial rate enhancement and hydroxyl scavenging.

DLC Film Formation Technologies by Applying Pulse Voltage Coupled with RF Voltage to Complicated 3-dimensional Substrates and Industrial Application

NASA Astrophysics Data System (ADS)

Suzuki, Yasuo

A uniform plasma-based ion implantation and DLC film formation technologies on the surface of complicated 3-dimensional substrates have been developed by applying pulse voltage coupled with RF voltage to the substrates such as plastics, rubber as well as metals with the similar deposition rate. These technologies are widely applicable to both ion implantation and DLC film formation onto the automobile parts, mechanical parts and metal molds. A problem to be solved is reducing cost. The deposition rate of DLC films is expected to increase to around 10μm/hr, which is ten times larger than that of the conventional method, by hybridizing the ICP (Induction Coupling Plasma) with a plus-minus voltage source. This epoch-making technology will be able to substitute for the electro-plating method in the near future. In this paper, the DLC film formation technology by applying both RF and pulse voltage, its applications and its prospect are presented.

The diskmass survey. VIII. On the relationship between disk stability and star formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Westfall, Kyle B.; Verheijen, Marc A. W.; Andersen, David R.

2014-04-10

We study the relationship between the stability level of late-type galaxy disks and their star-formation activity using integral-field gaseous and stellar kinematic data. Specifically, we compare the two-component (gas+stars) stability parameter from Romeo and Wiegert (Q {sub RW}), incorporating stellar kinematic data for the first time, and the star-formation rate estimated from 21 cm continuum emission. We determine the stability level of each disk probabilistically using a Bayesian analysis of our data and a simple dynamical model. Our method incorporates the shape of the stellar velocity ellipsoid (SVE) and yields robust SVE measurements for over 90% of our sample. Averagingmore » over this subsample, we find a meridional shape of σ{sub z}/σ{sub R}=0.51{sub −0.25}{sup +0.36} for the SVE and, at 1.5 disk scale lengths, a stability parameter of Q {sub RW} = 2.0 ± 0.9. We also find that the disk-averaged star-formation-rate surface density ( Σ-dot {sub e,∗}) is correlated with the disk-averaged gas and stellar mass surface densities (Σ {sub e,} {sub g} and Σ {sub e,} {sub *}) and anti-correlated with Q {sub RW}. We show that an anti-correlation between Σ-dot {sub e,∗} and Q {sub RW} can be predicted using empirical scaling relations, such that this outcome is consistent with well-established statistical properties of star-forming galaxies. Interestingly, Σ-dot {sub e,∗} is not correlated with the gas-only or star-only Toomre parameters, demonstrating the merit of calculating a multi-component stability parameter when comparing to star-formation activity. Finally, our results are consistent with the Ostriker et al. model of self-regulated star-formation, which predicts Σ-dot {sub e,∗}/Σ{sub e,g}∝Σ{sub e,∗}{sup 1/2}. Based on this and other theoretical expectations, we discuss the possibility of a physical link between disk stability level and star-formation rate in light of our empirical results.« less

Hurricanes and Climate: the U.S. CLIVAR Working Group on Hurricanes

NASA Technical Reports Server (NTRS)

Walsh, Kevin; Camargo, Suzana J.; Vecchi, Gabriel A.; Daloz, Anne Sophie; Elsner, James; Emanuel, Kerry; Horn, Michael; Lim, Young-Kwon; Roberts, Malcolm; Patricola, Christina;

Surface Morphology of Vapor-Deposited Chitosan: Evidence of Solid-State Dewetting during the Formation of Biopolymer Films.

PubMed

Retamal, Maria Jose; Corrales, Tomas P; Cisternas, Marcelo A; Moraga, Nicolas H; Diaz, Diego I; Catalan, Rodrigo E; Seifert, Birger; Huber, Patrick; Volkmann, Ulrich G

2016-03-14

Chitosan is a useful and versatile biopolymer with several industrial and biological applications. Whereas its physical and physicochemical bulk properties have been explored quite intensively in the past, there is a lack of studies regarding the morphology and growth mechanisms of thin films of this biopolymer. Of particular interest for applications in bionanotechnology are ultrathin films with thicknesses under 500 Å. Here, we present a study of thin chitosan films prepared in a dry process using physical vapor deposition and in situ ellipsometric monitoring. The prepared films were analyzed with atomic force microscopy in order to correlate surface morphology with evaporation parameters. We find that the surface morphology of our final thin films depends on both the optical thickness, i.e., measured with ellipsometry, and the deposition rate. Our work shows that ultrathin biopolymer films can undergo dewetting during film formation, even in the absence of solvents and thermal annealing.

Nucleation and Growth of Insulin Fibrils in Bulk Solution and at Hydrophobic Polystyrene Surfaces

PubMed Central

Smith, M. I.; Sharp, J. S.; Roberts, C. J.

2007-01-01

A technique was developed for studying the nucleation and growth of fibrillar protein aggregates. Fourier transform infrared and attenuated total reflection spectroscopy were used to measure changes in the intermolecular β-sheet content of bovine pancreatic insulin in bulk solution and on model polystyrene (PS) surfaces at pH 1. The kinetics of β-sheet formation were shown to evolve in two stages. Combined Fourier transform infrared, dynamic light scattering, atomic force microscopy, and thioflavin-T fluorescence measurements confirmed that the first stage in the kinetics was related to the formation of nonfibrillar aggregates that have a radius of 13 ± 1 nm. The second stage was found to be associated with the growth of insulin fibrils. The β-sheet kinetics in this second stage were used to determine the nucleation and growth rates of fibrils over a range of temperatures between 60°C and 80°C. The nucleation and growth rates were shown to display Arrhenius kinetics, and the associated energy barriers were extracted for fibrils formed in bulk solution and at PS surfaces. These experiments showed that fibrils are nucleated more quickly in the presence of hydrophobic PS surfaces but that the corresponding fibril growth rates decrease. These observations are interpreted in terms of the differences in the attempt frequencies and energy barriers associated with the nucleation and growth of fibrils. They are also discussed in the context of differences in protein concentration, mobility, and conformational and colloidal stability that exist between insulin molecules in bulk solution and those that are localized at hydrophobic PS interfaces. PMID:17496011

Periodic disruptions induced by high repetition rate femtosecond pulses on magnesium-oxide-doped lithium niobate surfaces

NASA Astrophysics Data System (ADS)

Zhang, Shuanggen; Kan, Hongli; Zhai, Kaili; Ma, Xiurong; Luo, Yiming; Hu, Minglie; Wang, Qingyue

2017-02-01

In this paper, we demonstrate the periodic disruption formation on magnesium-oxide-doped lithium niobate surfaces by a femtosecond fiber laser system with wavelength and repetition rate of 1040 nm and 52 MHz, respectively. Three main experimental conditions, laser average power, scanning speed, and orientation of sample were systematically studied. In particular, the ablation morphologies of periodic disruptions under different crystal orientations were specifically researched. The result shows that such disruptions consisting of a bamboo-like inner structure appears periodically for focusing on the surface of X-, Y- and Z-cut wafers, which are formed by a rapid quenching of the material. Meanwhile, due to the anisotropic property, the bamboo-like inner structures consist of a cavity only arise from X- and Z-cut orientation.

Electroless Plated Nanodiamond Coating for Stainless Steel Passivation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, D.; Korinko, P.; Spencer, W.

Tritium gas sample bottles and manifold components require passivation surface treatments to minimize the interaction of the hydrogen isotopes with surface contamination on the stainless steel containment materials. This document summarizes the effort to evaluate electroless plated nanodiamond coatings as a passivation layer for stainless steel. In this work, we developed an electroless nanodiamond (ND)-copper (Cu) coating process to deposit ND on stainless steel parts with the diamond loadings of 0%, 25% and 50% v/v in a Cu matrix. The coated Conflat Flanged Vessel Assemblies (CFVAs) were evaluated on surface morphology, composition, ND distribution, residual hydrogen release, and surface reactivitymore » with deuterium. For as-received Cu and ND-Cu coated CFVAs, hydrogen off-gassing is rapid, and the off-gas rates of H 2 was one to two orders of magnitude higher than that for both untreated and electropolished stainless steel CFVAs, and hydrogen and deuterium reacted to form HD as well. These results indicated that residual H 2 was entrapped in the Cu and ND-Cu coated CFVAs during the coating process, and moisture was adsorbed on the surface, and ND and/or Cu might facilitate catalytic isotope exchange reaction for HD formation. However, hydrocarbons (i.e., CH 3) did not form, and did not appear to be an issue for the Cu and ND-Cu coated CFVAs. After vacuum heating, residual H 2 and adsorbed H 2O in the Cu and ND-Cu coated CFVAs were dramatically reduced. The H 2 off-gassing rate after the vacuum treatment of Cu and 50% ND-Cu coated CFVAs was on the level of 10 -14 l mbar/s cm 2, while H 2O off-gas rate was on the level of 10 -15 l mbar/s cm 2, consistent with the untreated or electropolished stainless steel CFVA, but the HD formation remained. The Restek EP bottle was used as a reference for this work. The Restek Electro-Polished (EP) bottle and their SilTek coated bottles tested under a different research project exhibited very little hydrogen off-gassing and unmeasurable HD formation. ND and Cu were initially chosen to develop improved passivation technology, because Cu has a lower permeability of hydrogen, and diamond is more inert than other materials under a hydrogen atmosphere. However, our tests demonstrated that even after an 8-18 day vacuum extraction heat treatment, the electroless plated Cu and ND-Cu coated stainless steel CFVAs exhibited H 2 off-gassing rates that were just comparable to those for the untreated or electropolished stainless steel CFVA, and the HD formation was still observed. Thus, the Restek Electro-Polished (EP) bottle outperformed the electroless plated Cu and ND-Cu coated stainless steel CFVAs, and the electroless plated nanodiamond coating is not promising as a surface passivation technology. However, the ND-Cu coating may be beneficial to another application in which catalyzing the H 2-D 2 exchange reaction is desired.« less

Understanding the barriers to crystal growth: dynamical simulation of the dissolution and growth of urea from aqueous solution.

PubMed

Piana, Stefano; Gale, Julian D

2005-02-16

Both the dissolution and growth of a molecular crystalline material, urea, has been studied using dynamical atomistic simulation. The kinetic steps of dissolution and growth are clearly identified, and the activation energies for each possible step are calculated. Our molecular dynamics simulations indicate that crystal growth on the [001] face is characterized by a nucleation and growth mechanism. Nucleation on the [001] urea crystal face is predicted to occur at a very high rate, followed by rapid propagation of the steps. The rate-limiting step for crystallization is actually found to be the removal of surface defects, rather than the initial formation of the next surface layer. Through kinetic Monte Carlo modeling of the surface growth, it is found that this crystal face evolves via a rough surface topography, rather than a clean layer-by-layer mechanism.

A simple model for remineralization of subsurface lesions in tooth enamel

NASA Astrophysics Data System (ADS)

Christoffersen, J.; Christoffersen, M. R.; Arends, J.

1982-12-01

A model for remineralization of subsurface lesions in tooth enamel is presented. The important assumption on which the model is based is that the rate-controlling process is the crystal surface process by which ions are incorporated in the crystallites; that is, the transport of ions through small holes in the so-called intact surface layer does not influence the rate of mineral uptake at the crystal surface. Further, the density of mineral in the lesion is assumed to increase down the lesion, when the remineralization process is started. It is shown that the dimension of the initial holes in the enamel surface layer must be larger than the dimension of the individual crystallites in order to prevent the formation of arrested lesions. Theoretical expressions for the progress of remineralization are given. The suggested model emphasizes the need for measurements of mineral densities in the lesion, prior to, and during the lesion repair.

A kinetic model for the characteristic surface morphologies of thin films by directional vapor deposition

NASA Astrophysics Data System (ADS)

Li, Kun-Dar; Huang, Po-Yu

2017-12-01

In order to simulate a process of directional vapor deposition, in this study, a numerical approach was applied to model the growth and evolution of surface morphologies for the crystallographic structures of thin films. The critical factors affecting the surface morphologies in a deposition process, such as the crystallographic symmetry, anisotropic interfacial energy, shadowing effect, and deposition rate, were all enclosed in the theoretical model. By altering the parameters of crystallographic symmetry in the structures, the faceted nano-columns with rectangular and hexagonal shapes were established in the simulation results. Furthermore, for revealing the influences of the anisotropic strength and the deposition rate theoretically on the crystallographic structure formations, various parameters adjusted in the numerical calculations were also investigated. Not only the morphologies but also the surface roughnesses for different processing conditions were distinctly demonstrated with the quantitative analysis of the simulations.

Formation and mechanics of granular waves in gravity and shallow overland flow

USDA-ARS?s Scientific Manuscript database

Sediment transport in overland flow is a highly complex process involving many properties relative to the flow regime characteristics, soil surface conditions, and type of sediment. From a practical standpoint, most sediment transport studies are concerned with developing relationships of rates of s...

Surface density: a new parameter in the fundamental metallicity relation of star-forming galaxies

NASA Astrophysics Data System (ADS)

Hashimoto, Tetsuya; Goto, Tomotsugu; Momose, Rieko

2018-04-01

Star-forming galaxies display a close relation among stellar mass, metallicity, and star formation rate (or molecular-gas mass). This is known as the fundamental metallicity relation (FMR) (or molecular-gas FMR), and it has a profound implication on models of galaxy evolution. However, there still remains a significant residual scatter around the FMR. We show here that a fourth parameter, the surface density of stellar mass, reduces the dispersion around the molecular-gas FMR. In a principal component analysis of 29 physical parameters of 41 338 star-forming galaxies, the surface density of stellar mass is found to be the fourth most important parameter. The new 4D fundamental relation forms a tighter hypersurface that reduces the metallicity dispersion to 50 per cent of that of the molecular-gas FMR. We suggest that future analyses and models of galaxy evolution should consider the FMR in a 4D space that includes surface density. The dilution time-scale of gas inflow and the star-formation efficiency could explain the observational dependence on surface density of stellar mass.

An Ultraviolet and Near-Infrared View of NGC 4214: A Starbursting Core Embedded in a Low Surface Brightness Disk

NASA Astrophysics Data System (ADS)

Fanelli, Michael N.; Waller, William W.; Smith, Denise A.; Freedman, Wendy L.; Madore, Barry; Neff, Susan G.; O'Connell, Robert W.; Roberts, Morton S.; Bohlin, Ralph; Smith, Andrew M.; Stecher, Theodore P.

1997-05-01

During the Astro-2 Spacelab mission in 1995 March, the Ultraviolet Imaging Telescope (UIT) obtained far-UV (λ = 1500 Å) imagery of the nearby Sm/Im galaxy NGC 4214. The UIT images have a spatial resolution of ~3" and a limiting surface brightness, μ1500 > 25 mag arcsec-2, permitting detailed investigation of the intensity and spatial distribution of the young, high-mass stellar component. These data provide the first far-UV imagery covering the full spatial extent of NGC 4214. Comparison with a corresponding I-band image reveals the presence of a starbursting core embedded in an extensive low surface brightness disk. In the far-UV (FUV), NGC 4214 is resolved into several components: a luminous, central knot; an inner region (r <~ 2.5 kpc) with ~15 resolved sources embedded in bright, diffuse emission; and a population of fainter knots extending to the edge of the optically defined disk (r ~ 5 kpc). The FUV light, which traces recent massive star formation, is observed to be more centrally concentrated than the I-band light, which traces the global stellar population. The FUV radial light profile is remarkably well represented by an R1/4 law, providing evidence that the centrally concentrated massive star formation in NGC 4214 is the result of an interaction, possibly a tidal encounter, with a dwarf companion(s). The brightest FUV source produces ~8% of the global FUV luminosity. This unresolved source, corresponding to the Wolf-Rayet knot described by Sargent & Filippenko, is located at the center of the FUV light distribution, giving NGC 4214 an active galactic nucleus-like morphology. Another strong source is present in the I band, located 19" west, 10" north of the central starburst knot, with no FUV counterpart. The I-band source may be the previously unrecognized nucleus of NGC 4214 or an evolved star cluster with an age greater than ~200 Myr. The global star formation rate derived from the total FUV flux is consistent with rates derived using data at other wavelengths and lends support to the scenario of roughly constant star formation during the last few hundred million years at a level significantly enhanced relative to the lifetime averaged star formation rate. The hybrid disk/starburst-irregular morphology evident in NGC 4214 emphasizes the danger of classifying galaxies based on their high surface brightness components at any particular wavelength.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Zhaobing

Ni-Cr-Co-Ti-V-Al high-entropy alloy coating on Ti-6Al-4V was synthesized by laser surface alloying. The coating is composed of a B2 matrix and (Co, Ni)Ti{sub 2} compounds with few β-Ti phases. Focused ion beam technique was utilized to prepare TEM sample and TEM observations agree well with XRD and SEM results. The formation of HEA phases is due to high temperature and rapid cooling rate during laser surface alloying. The thermodynamic parameters, ΔH{sub mix}, ΔS{sub mix}and δ as well as Δχ, should be used to predict the formation of the BCC solid solution, but they are not the strict criteria. Especially whenmore » Δχ reaches a high value (≥ 10%), BCC HEA will be partially decomposed, leading to the formation of (Co, Ni)Ti{sub 2} compound phases. - Highlights: •Preparing HEA coating on Ti-6Al-4V by laser surface alloying is successful. •The synthesized HEA coating mainly consists of BCC HEA and (Co, Ni)Ti{sub 2} compounds. •FIB technology was used to prepare the sample for TEM analysis. • ΔH{sub mix}, ΔS{sub mix}and δ as well as Δχ, should be all used to predict the formation of solid solution.« less

Calcium carbonate scale control, effect of material and inhibitors.

PubMed

Macadam, J; Parsons, S A

2004-01-01

This paper focuses on developing a reproducible method for reducing calcium carbonate scale formation on heated surfaces where scaling can cause serious problems. It is known that calcium carbonate precipitation is sensitive to impurity ions, such as iron and zinc, even at trace concentration levels. In this paper two sets of experiments are reported. The first experiments were undertaken to investigate the effect of zinc, copper and iron dosing on CaCO3 nucleation and precipitation. Results from the experiments showed that the most effective inhibitor of CaCO3 precipitation was zinc and the effect was linked to dose levels and temperature. Copper and iron had little effect on precipitation in the dose range investigated. The second trial was undertaken to translate the precipitation data to scale formation. These tests were undertaken at 70 degrees C. 5 mg x L(-1) zinc dose reduced the scale formation by 35%. The effect of iron on calcium carbonate scaling rate was not significant. The physical nature of the material on which the scale is formed also influences the scaling. The scaling experiment was also used to investigate the effect of different surface material (stainless steel, copper and aluminium) on CaCO3 scale formation. Copper surface scaled the most.

Collisional and dynamical processes in moon and planet formation

NASA Technical Reports Server (NTRS)

1979-01-01

The collisional and dynamical processes in moon and planet formation are discussed. A hydrodynamic code of collision calculations, the orbital element changes due to gravitational scattering, a validation of the mass shifting algorithm, a theory of rotations, and the origin of asteroids are studied. A numerical model of planet growth is discussed and a methodology to evaluate the rate at which megaregolith increases its depth as a function of total accumulate number of impacts on an initially smooth, coherent surface is described.

On the Appearance of Thresholds in the Dynamical Model of Star Formation

NASA Astrophysics Data System (ADS)

Elmegreen, Bruce G.

2018-02-01

The Kennicutt–Schmidt (KS) relationship between the surface density of the star formation rate (SFR) and the gas surface density has three distinct power laws that may result from one model in which gas collapses at a fixed fraction of the dynamical rate. The power-law slope is 1 when the observed gas has a characteristic density for detection, 1.5 for total gas when the thickness is about constant as in the main disks of galaxies, and 2 for total gas when the thickness is regulated by self-gravity and the velocity dispersion is about constant, as in the outer parts of spirals, dwarf irregulars, and giant molecular clouds. The observed scaling of the star formation efficiency (SFR per unit CO) with the dense gas fraction (HCN/CO) is derived from the KS relationship when one tracer (HCN) is on the linear part and the other (CO) is on the 1.5 part. Observations of a threshold density or column density with a constant SFR per unit gas mass above the threshold are proposed to be selection effects, as are observations of star formation in only the dense parts of clouds. The model allows a derivation of all three KS relations using the probability distribution function of density with no thresholds for star formation. Failed galaxies and systems with sub-KS SFRs are predicted to have gas that is dominated by an equilibrium warm phase where the thermal Jeans length exceeds the Toomre length. A squared relation is predicted for molecular gas-dominated young galaxies.

Biofunctionalization of silicone rubber with microgroove-patterned surface and carbon-ion implantation to enhance biocompatibility and reduce capsule formation.

PubMed

Lei, Ze-Yuan; Liu, Ting; Li, Wei-Juan; Shi, Xiao-Hua; Fan, Dong-Li

Silicone rubber implants have been widely used to repair soft tissue defects and deformities. However, poor biocompatibility can elicit capsule formation, usually resulting in prosthesis contracture and displacement in long-term usage. To overcome this problem, this study investigated the properties of silicone rubber materials with or without a microgroove-patterned surface and with or without carbon (C)-ion implantation. Atomic force microscopy, X-ray photoelectron spectroscopy, and a water contact angle test were used to characterize surface morphology and physicochemical properties. Cytocompatibility was investigated by a cell adhesion experiment, immunofluorescence staining, a Cell Counting Kit-8 assay, and scanning electron microscopy in vitro. Histocompatibility was evaluated by studying the inflammatory response and fiber capsule formation that developed after subcutaneous implantation in rats for 7 days, 15 days, and 30 days in vivo. Parallel microgrooves were found on the surfaces of patterned silicone rubber (P-SR) and patterned C-ion-implanted silicone rubber (PC-SR). Irregular larger peaks and deeper valleys were present on the surface of silicone rubber implanted with C ions (C-SR). The silicone rubber surfaces with microgroove patterns had stable physical and chemical properties and exhibited moderate hydrophobicity. PC-SR exhibited moderately increased dermal fibroblast cell adhesion and growth, and its surface microstructure promoted orderly cell growth. Histocompatibility experiments on animals showed that both the anti-inflammatory and antifibrosis properties of PC-SR were slightly better than those of the other materials, and there was also a lower capsular contracture rate and less collagen deposition around implants made from PC-SR. Although the surface chemical properties, dermal fibroblast cell growth, and cell adhesion were not changed by microgroove pattern modification, a more orderly cell arrangement was obtained, leading to enhanced biocompatibility and reduced capsule formation. Thus, this approach to the modification of silicone rubber, in combination with C-ion implantation, should be considered for further investigation and application.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xiang; Shi, Hui; Szanyi, János

Catalytic CO2 conversion to energy carriers and intermediates is of utmost importance to energy and environmental goals. However, the lack of fundamental understanding of the reaction mechanism renders designing a selective catalyst inefficient. We performed operando FTIR/SSITKA experiments to understand the correlation between the kinetics of product formation and that of surface species conversion during CO2 reduction over Pd/Al2O3 catalysts. We found that the rate-determining step for CO formation is the conversion of adsorbed formate, while that for CH4 formation is the hydrogenation of adsorbed carbonyl. The balance of the hydrogenation kinetics between adsorbed formates and carbonyls governs the selectivitiesmore » to CH4 and CO. We demonstrated how this knowledge can be used to design catalysts to achieve high selectivities to desired products.« less

The Role of Vegetation and Mulch in Mitigating the Impact of Raindrops on Soils in Urban Vegetated Green Infrastructure Systems

NASA Astrophysics Data System (ADS)

Alizadehtazi, B.; Montalto, F. A.; Sjoblom, K.

2014-12-01

Raindrop impulses applied to soils can break up larger soil aggregates into smaller particles, dispersing them from their original position. The displaced particles can self-stratify, with finer particles at the top forming a crust. Occurrence of this phenomenon reduces the infiltration rate and increases runoff, contributing to downstream flooding, soil erosion, and non point source pollutant loads. Unprotected soil surfaces (e.g. without vegetation canopies, mulch, or other materials), are more susceptible to crust formation due to the higher kinetic energy associated with raindrop impact. By contrast, soil that is protected by vegetation canopies and mulch layers is less susceptible to crust formation, since these surfaces intercept raindrops, dissipating some of their kinetic energy prior to their impact with the soil. Within this context, this presentation presents preliminary laboratory work conducted using a rainfall simulator to determine the ability of new urban vegetation and mulch to minimize soil crust formation. Three different scenarios are compared: a) bare soil, b) soil with mulch cover, and c) soil protected by vegetation canopies. Soil moisture, surface penetration resistance, and physical measurements of the volume of infiltrate and runoff are made on all three surface treatments after simulated rainfall events. The results are used to develop recommendations regarding surface treatment in green infrastructure (GI) system designs, namely whether heavily vegetated GI facilities require mulching to maintain infiltration capacity.

Chip formation and surface integrity in high-speed machining of hardened steel

NASA Astrophysics Data System (ADS)

Kishawy, Hossam Eldeen A.

Increasing demands for high production rates as well as cost reduction have emphasized the potential for the industrial application of hard turning technology during the past few years. Machining instead of grinding hardened steel components reduces the machining sequence, the machining time, and the specific cutting energy. Hard turning Is characterized by the generation of high temperatures, the formation of saw toothed chips, and the high ratio of thrust to tangential cutting force components. Although a large volume of literature exists on hard turning, the change in machined surface physical properties represents a major challenge. Thus, a better understanding of the cutting mechanism in hard turning is still required. In particular, the chip formation process and the surface integrity of the machined surface are important issues which require further research. In this thesis, a mechanistic model for saw toothed chip formation is presented. This model is based on the concept of crack initiation on the free surface of the workpiece. The model presented explains the mechanism of chip formation. In addition, experimental investigation is conducted in order to study the chip morphology. The effect of process parameters, including edge preparation and tool wear on the chip morphology, is studied using Scanning Electron Microscopy (SEM). The dynamics of chip formation are also investigated. The surface integrity of the machined parts is also investigated. This investigation focusses on residual stresses as well as surface and sub-surface deformation. A three dimensional thermo-elasto-plastic finite element model is developed to predict the machining residual stresses. The effect of flank wear is introduced during the analysis. Although residual stresses have complicated origins and are introduced by many factors, in this model only the thermal and mechanical factors are considered. The finite element analysis demonstrates the significant effect of the heat generated during cutting on the residual stresses. The machined specimens are also examined using x-ray diffraction technique to clarify the effect of different speeds, feeds and depths of cut as well as different edge preparations on the residual stress distribution beneath the machined surface. A reasonable agreement between the predicted and measured residual stress is obtained. The results obtained demonstrate the possibility of eliminating the existence of high tensile residual stresses in the workpiece surface by selecting the proper cutting conditions. The machined surfaces are examined using SEM to study the effect of different process parameters and edge preparations on the quality of the machined surface. The phenomenon of material side flow is investigated to clarify the mechanism of this phenomenon. The effect of process parameters and edge preparations on sub-surface deformation is also investigated.

Diffusion of microspheres in shear flow near a wall: use to measure binding rates between attached molecules.

PubMed Central

Pierres, A; Benoliel, A M; Zhu, C; Bongrand, P

2001-01-01

The rate and distance-dependence of association between surface-attached molecules may be determined by monitoring the motion of receptor-bearing spheres along ligand-coated surfaces in a flow chamber (Pierres et al., Proc. Natl. Acad. Sci. U.S.A. 95:9256-9261, 1998). Particle arrests reveal bond formation, and the particle-to-surface distance may be estimated from the ratio between the velocity and the wall shear rate. However, several problems are raised. First, data interpretation requires extensive computer simulations. Second, the relevance of standard results from fluid mechanics to micrometer-size particles separated from surfaces by nanometer distances is not fully demonstrated. Third, the wall shear rate must be known with high accuracy. Here we present a simple derivation of an algorithm permitting one to simulate the motion of spheres near a plane in shear flow. We check that theoretical predictions are consistent with the experimental dependence of motion on medium viscosity or particle size, and the requirement for equilibrium particle height distribution to follow Boltzman's law. The determination of the statistical relationship between particle velocity and acceleration allows one to derive the wall shear rate with 1-s(-1) accuracy and the Hamaker constant of interaction between the particle and the wall with a sensitivity better than 10(-21) J. It is demonstrated that the correlation between particle height and mean velocity during a time interval Deltat is maximal when Deltat is about 0.1-0.2 s for a particle of 1.4-microm radius. When the particle-to-surface distance ranges between 10 and 40 nm, the particle height distribution may be obtained with a standard deviation ranging between 8 and 25 nm, provided the average velocity during a 160-ms period of time is determined with 10% accuracy. It is concluded that the flow chamber allows one to detect the formation of individual bonds with a minimal lifetime of 40 ms in presence of a disruptive force of approximately 5 pN and to assess the distance dependence within the tens of nanometer range. PMID:11423392

Ignition technique for an in situ oil shale retort

DOEpatents

Cha, Chang Y.

1983-01-01

A generally flat combustion zone is formed across the entire horizontal cross-section of a fragmented permeable mass of formation particles formed in an in situ oil shale retort. The flat combustion zone is formed by either sequentially igniting regions of the surface of the fragmented permeable mass at successively lower elevations or by igniting the entire surface of the fragmented permeable mass and controlling the rate of advance of various portions of the combustion zone.

Application of conjugated heparin-albumin microparticles with laser-balloon angioplasty: a potential method for reducing adverse biologic reactivity after angioplasty

NASA Astrophysics Data System (ADS)

Kundu, Sourav K.; McMath, Linda P.; Zaidan, Jonathan T.; Spears, J. Richard

1991-05-01

Laser-balloon angioplasty (LBA) may potentially be used for local application of pharmacologically active agents which will reduce thrombogenic and proliferative responses after the angioplasty. In this study, the feasibility of applying covalently conjugated heparin- albumin microparticles onto arterial luminal surface was demonstrated. The covalent linkages were formed by reaction with 1-ethyl-3-dimethyl-aminopropyl-carbodiimide (EDC), and the resultant conjugates were used for preparation of microparticles by employing standard emulsification and heat-crosslinking techniques. The heparin release rate from the microparticles was found to be dependent upon the degree of crosslinking. When a thin coagulum of a suspension of microparticles was formed with heat on a glass surface, the treated surface demonstrated resistance to clot formation in contact with non-anticoagulated blood. A suspension of the microparticles applied during laser-balloon angioplasty onto the luminal surface of dog carotid and femoral arteries showed persistence for up to one week without thrombus formation or occlusion of the vessel. Since the rate of biodegradation is primarily dictated by the extent of crosslinking, an optimal degree of thermal denaturation will permit longer persistence of the carrier while allowing adequate release of the entrapped pharmacologic agent. A variety of antithrombotic and antiinflammatory agents are being considered as candidate bioprotective materials for local application after angioplasty.

The Influence of Local Geometric Effects on Mars Polar Processes

NASA Technical Reports Server (NTRS)

Hecht, M. H.

2005-01-01

Using simple, qualitative heat balance models, this paper addresses textures and structures that will result from the evolution of volatile layers by accretion and by ablation. Such phenomena may have global implications that are not apparent when only flat or sloped surfaces are modeled. In general, structures such as mounds or depressions formed out of volatile materials will evolve in shape such that the growth or retreat of any particular surface will be maximized. It can be shown that the local radius of curvature is proportional to the growth or retreat rate. For example, icy surfaces will tend to form facets that face the dominant sun direction. Two such cases are evaluated: a) Features associated with condensation of volatiles, include cold-trapping and redistribution, such as the concentration of frost around the Viking 2 lander [1]. Here I will focus on textures that likely result from the formation of seasonal CO2 deposits. b) Features associated with sublimation of volatiles, such as those described by Ingersoll et. al. [2] result in textured surfaces that affect both the apparent emissivity and albedo. Similar calculations have been performed with respect to the "Swiss cheese" features on the South Polar Cap [3]. Here, I evaluate the likely sublimation rates from optimal ice scarp structures and their implications for the long-term evolution of the polar caps and formation of layered terrain.

Direct formation of (CH sub 3 ) sub 2 HSiCl from silicon and CH sub 3 Cl

DOE Office of Scientific and Technical Information (OSTI.GOV)

Magrini, K.A.; Falconer, J.L.; Koel, B.E.

1989-07-13

A Cu-catalyzed reaction procedure was found for the selective formation of dimethylchlorosilane ((CH{sub 3}){sub 2}HSiCl) from the direct reaction of CH{sub 3}Cl with solid Si. The new procedure is a two-step process. A Cu/Si sample is prepared by evaporating Cu onto clean polycrystalline Si under ultrahigh vacuum, and the Cu/Si surface is first activated by exposure to 10% HSiCl{sub 3}/CH{sub 3}Cl at 598 K. After the HSiCl{sub 3}CH{sub 3}Cl mixture is evacuated from the reactor, the activated Cu/Si surface is reacted in fresh CH{sub 3}Cl. For low surface concentrations of Cu, the partially hydrogenated silane, (CH{sub 3}){sub 2}HSiCl, is selectivelymore » produced. Trichlorosilane was also found to activate polycrystalline Si (in the absence of Cu) for production of highly chlorinated methylchlorosilanes at a much higher rate than on the Cu/Si surface but with poor selectively to (CH{sub 3}){sub 2}HSiCl. All reactions are carried out at atmospheric pressure in a reactor that is attached to an ultrahigh-vacuum chamber. This allows surface analysis of Auger electron spectroscopy, which detected SiCl{sub x} on reacted surfaces. These SiCl{sub x} sites, which appear necessary for methylchlorosilane formation, are apparently formed during activation by HSiCl{sub 3}.« less

The Design of 3D-Printed Lattice-Reinforced Thickness-Varying Shell Molds for Castings.

PubMed

Shangguan, Haolong; Kang, Jinwu; Yi, Jihao; Zhang, Xiaochuan; Wang, Xiang; Wang, Haibin; Huang, Tao

2018-03-30

3D printing technologies have been used gradually for the fabrication of sand molds and cores for castings, even though these molds and cores are dense structures. In this paper, a generation method for lattice-reinforced thickness-varying shell molds is proposed and presented. The first step is the discretization of the STL (Stereo Lithography) model of a casting into finite difference meshes. After this, a shell is formed by surrounding the casting with varying thickness, which is roughly proportional to the surface temperature distribution of the casting that is acquired by virtually cooling it in the environment. A regular lattice is subsequently constructed to support the shell. The outside surface of the shell and lattice in the cubic mesh format is then converted to STL format to serve as the external surface of the new shell mold. The internal surface of the new mold is the casting's surface with the normals of all of the triangles in STL format reversed. Experimental verification was performed on an Al alloy wheel hub casting. Its lattice-reinforced thickness-varying shell mold was generated by the proposed method and fabricated by the binder jetting 3D printing. The poured wheel hub casting was sound and of good surface smoothness. The cooling rate of the wheel hub casting was greatly increased due to the shell mold structure. This lattice-reinforced thickness-varying shell mold generation method is of great significance for mold design for castings to achieve cooling control.

The Design of 3D-Printed Lattice-Reinforced Thickness-Varying Shell Molds for Castings

PubMed Central

Shangguan, Haolong; Kang, Jinwu; Yi, Jihao; Zhang, Xiaochuan; Wang, Xiang; Wang, Haibin; Huang, Tao

2018-01-01

3D printing technologies have been used gradually for the fabrication of sand molds and cores for castings, even though these molds and cores are dense structures. In this paper, a generation method for lattice-reinforced thickness-varying shell molds is proposed and presented. The first step is the discretization of the STL (Stereo Lithography) model of a casting into finite difference meshes. After this, a shell is formed by surrounding the casting with varying thickness, which is roughly proportional to the surface temperature distribution of the casting that is acquired by virtually cooling it in the environment. A regular lattice is subsequently constructed to support the shell. The outside surface of the shell and lattice in the cubic mesh format is then converted to STL format to serve as the external surface of the new shell mold. The internal surface of the new mold is the casting’s surface with the normals of all of the triangles in STL format reversed. Experimental verification was performed on an Al alloy wheel hub casting. Its lattice-reinforced thickness-varying shell mold was generated by the proposed method and fabricated by the binder jetting 3D printing. The poured wheel hub casting was sound and of good surface smoothness. The cooling rate of the wheel hub casting was greatly increased due to the shell mold structure. This lattice-reinforced thickness-varying shell mold generation method is of great significance for mold design for castings to achieve cooling control. PMID:29601543

The tensile effect on crack formation in single crystal silicon irradiated by intense pulsed ion beam

NASA Astrophysics Data System (ADS)

Liang, Guoying; Shen, Jie; Zhang, Jie; Zhong, Haowen; Cui, Xiaojun; Yan, Sha; Zhang, Xiaofu; Yu, Xiao; Le, Xiaoyun

2017-10-01

Improving antifatigue performance of silicon substrate is very important for the development of semiconductor industry. The cracking behavior of silicon under intense pulsed ion beam irradiation was studied by numerical simulation in order to understand the mechanism of induced surface peeling observed by experimental means. Using molecular dynamics simulation based on Stillinger Weber potential, tensile effect on crack growth and propagation in single crystal silicon was investigated. Simulation results reveal that stress-strain curves of single crystal silicon at a constant strain rate can be divided into three stages, which are not similar to metal stress-strain curves; different tensile load velocities induce difference of single silicon crack formation speed; the layered stress results in crack formation in single crystal silicon. It is concluded that the crack growth and propagation is more sensitive to strain rate, tensile load velocity, stress distribution in single crystal silicon.

Equilibrium star formation in a constant Q disc: model optimization and initial tests

NASA Astrophysics Data System (ADS)

Zheng, Zheng; Meurer, Gerhardt R.; Heckman, Timothy M.; Thilker, David A.; Zwaan, Martin A.

2013-10-01

We develop a model for the distribution of the interstellar medium (ISM) and star formation in galaxies based on recent studies that indicate that galactic discs stabilize to a constant stability parameter, which we combine with prescriptions of how the phases of the ISM are determined and for the star formation law (SFL). The model predicts the gas surface mass density and star formation intensity of a galaxy given its rotation curve, stellar surface mass density and the gas velocity dispersion. This model is tested on radial profiles of neutral and molecular ISM surface mass density and star formation intensity of 12 galaxies selected from the H I Nearby Galaxy Survey sample. Our tests focus on intermediate radii (0.3 to 1 times the optical radius) because there are insufficient data to test the outer discs and the fits are less accurate in detail in the centre. Nevertheless, the model produces reasonable agreement with the ISM mass and star formation rate integrated over the central region in all but one case. To optimize the model, we evaluate four recipes for the stability parameter, three recipes for apportioning the ISM into molecular and neutral components, and eight versions of the SFL. We find no clear-cut best prescription for the two-fluid (gas and stars) stability parameter Q2f and therefore for simplicity, we use the Wang and Silk approximation (QWS). We found that an empirical scaling between the molecular-to-neutral ISM ratio (Rmol) and the stellar surface mass density proposed by Leroy et al. works marginally better than the other two prescriptions for this ratio in predicting the ISM profiles, and noticeably better in predicting the star formation intensity from the ISM profiles produced by our model with the SFLs we tested. Thus, in the context of our modelled ISM profiles, the linear molecular SFL and the two-component SFL work better than the other prescriptions we tested. We incorporate these relations into our `constant Q disc' model.

Analysis of the osseointegrative force of a hyperhydrophilic and nanostructured surface refinement for TPS surfaces in a gap healing model with the Göttingen minipig.

PubMed

Seidling, Roland; Lehmann, Lars J; Lingner, Manuel; Mauermann, Eckhard; Obertacke, Udo; Schwarz, Markus L R

2016-10-17

A lot of advantages can result in a high wettability as well as a nanostructure at a titanium surface on bone implants. Thus, the aim of this study was to evaluate the osseointegrative potential of a titan plasma-sprayed (TPS) surface refinement by acid-etching with chromosulfuric acid. This results in a hyperhydrophilic surface with a nanostructure and an extreme high wetting rate. In total, 72 dumbbell shape titan implants were inserted in the spongy bone of the femora of 18 Göttingen minipigs in a conservative gap model. Thirty-six titan implants were coated with a standard TPS surface and 36 with the hyperhydrophilic chromosulfuric acid (CSA) surface. After a healing period of 4, 8, and 12 weeks, the animals were killed. The chronological healing process was histomorphometrically analyzed. The de novo bone formation, represented by the bone area (BA), is increased by approximately 1.5 times after 12 weeks with little additional benefit by use of the CSA surface. The bone-to-implant contact (BIC), which represents osseoconductive forces, shows results with a highly increased osteoid production in the CSA implants beginning at 8 and 12 weeks compared to TPS. This culminates in a 17-fold increase in BIC after a healing period of 12 weeks. After 4 weeks, significantly more osteoid was seen in the gap as de novo formation in the CSA group (p = 0.0062). Osteoid was also found more frequently after 12 weeks at the CSA-treated surface (p = 0.0355). The site of implantation, intertrochanteric or intercondylar, may influence on the de novo bone formation in the gap. There is a benefit by the CSA surface treatment of the TPS layer for osseointegration over an observation time up to 12 weeks. Significant differences were able to be shown in two direct comparisons between the CSA and the TPS surface for osteoid formation in the gap model. Further trials may reveal the benefit of the CSA treatment of the TPS layer involving mechanical tests if possible.

Assimilation of GOES Land Surface Data Within a Rapid Update Cycle Format: Impact on MM5 Warm Season QPF

NASA Technical Reports Server (NTRS)

Lapenta, William M.; Suggs, Ron; Jedlovec, Gary; McNider, Richard T.; Dembek, Scott; Arnold, James E. (Technical Monitor)

2001-01-01

A technique has been developed for assimilating GOES-derived skin temperature tendencies and insolation into the surface energy budget equation of a mesoscale model so that the simulated rate of temperature change closely agrees with the satellite observations. A critical assumption of the technique is that the availability of moisture (either from the soil or vegetation) is the least known term in the model's surface energy budget. Therefore, the simulated latent heat flux, which is a function of surface moisture availability, is adjusted based upon differences between the modeled and satellite-observed skin temperature tendencies. An advantage of this technique is that satellite temperature tendencies are assimilated in an energetically consistent manner that avoids energy imbalances and surface stability problems that arise from direct assimilation of surface shelter temperatures. The fact that the rate of change of the satellite skin temperature is used rather than the absolute temperature means that sensor calibration is not as critical. The focus of this paper is to examine how the satellite assimilation technique impacts simulations of near-surface meteorology on the 0-to 12-hour time scale when implemented within a local rapid update cycle (LRUC) format. The PSU/NCAR MM5 V34 is used and configured with a 36-km CONUS domain and a 12-km nest centered over the southeastern US. The LRUC format consists of a sequence of 12-hour forecasts initialized every hour between 12 and 18 UTC seven days a week. GOES skin temperature tendencies and solar insolation are assimilated in a 1-hour period prior to the start of each twelve-hour forecast. A unique aspect of the LRUC is the satellite assimilation and the continuous recycling of the adjusted moisture availability field from one forecast cycle to the next. Preliminary results for a seven-day trial period indicate that hourly LST tendencies assimilated in a 1 hour LRUC showed improved simulated air and dewpoint temperatures for all cycles on each day. The LRUC will be used during the 2001 summer months to identify the impact of the assimilation on warm season QPF Results will be presented at the meeting.

An Hα Imaging Survey of the Low-surface-brightness Galaxies Selected from the Fall Sky Region of the 40% ALFALFA H I Survey

NASA Astrophysics Data System (ADS)

Lei, Feng-Jie; Wu, Hong; Du, Wei; Zhu, Yi-Nan; Lam, Man-I.; Zhou, Zhi-Min; He, Min; Jin, Jun-Jie; Cao, Tian-Wen; Zhao, Pin-Song; Yang, Fan; Wu, Chao-Jian; Li, Hong-Bin; Ren, Juan-Juan

2018-03-01

We present the observed Hα flux and derived star formation rates (SFRs) for a fall sample of low-surface-brightness galaxies (LSBGs). The sample is selected from the fall sky region of the 40% ALFALFA H I Survey–SDSS DR7 photometric data, and all the Hα images were obtained using the 2.16 m telescope, operated by the National Astronomy Observatories, Chinese Academy of Sciences. A total of 111 LSBGs were observed and Hα flux was measured in 92 of them. Though almost all the LSBGs in our sample are H I-rich, their SFRs, derived from the extinction and filter-transmission-corrected Hα flux, are less than 1 M ⊙ yr‑1. LSBGs and star-forming galaxies have similar H I surface densities, but LSBGs have much lower SFRs and SFR surface densities than star-forming galaxies. Our results show that LSBGs deviate from the Kennicutt–Schmidt law significantly, which indicates that they have low star formation efficiency. The SFRs of LSBGs are close to average SFRs in Hubble time and support previous arguments that most of the LSBGs are stable systems and they tend to seldom contain strong interactions or major mergers in their star formation histories.

Methane Conversion to Ethylene and Aromatics on PtSn Catalysts

DOE PAGES

Gerceker, Duygu; Motagamwala, Ali Hussain; Rivera-Dones, Keishla R.; ...

2017-02-03

Pt and PtSn catalysts supported on SiO 2 and H-ZSM-5 were studied for methane conversion under nonoxidative conditions. Addition of Sn to Pt/SiO 2 increased the turnover frequency for production of ethylene by a factor of 3, and pretreatment of the catalyst at 1123 K reduced the extent of coke formation. Pt and PtSn catalysts supported on H-ZSM-5 zeolite were prepared to improve the activity and selectivity to non-coke products. Ethylene formation rates were 20 times faster over a PtSn(1:3)/H-ZSM-5 catalyst with SiO 2:Al 2O 3 = 280 in comparison to those over PtSn(3:1)/SiO 2. H-ZSM-5-supported catalysts were also activemore » for the formation of aromatics, and the rates of benzene and naphthalene formation were increased by using more acidic H-ZSM-5 supports. These catalysts operate through a bifunctional mechanism, in which ethylene is first produced on highly dispersed PtSn nanoparticles and then is subsequently converted to benzene and naphthalene on Brønsted acid sites within the zeolite support. The most active and stable PtSn catalyst forms carbon products at a rate, 2.5 mmol of C/((mol of Pt) s), which is comparable to that of state-of-the-art Mo/H-ZSM-5 catalysts with same metal loading operated under similar conditions (1.8 mmol of C/((mol of Mo) s)). Scanning transmission electron microscopy measurements suggest the presence of smaller Pt nanoparticles on H-ZSM-5-supported catalysts, in comparison to SiO 2-supported catalysts, as a possible source of their high activity. As a result, a microkinetic model of methane conversion on Pt and PtSn surfaces, built using results from density functional theory calculations, predicts higher coupling rates on bimetallic and stepped surfaces, supporting the experimental observations that relate the high catalytic activity to small PtSn particles.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerceker, Duygu; Motagamwala, Ali Hussain; Rivera-Dones, Keishla R.

Pt and PtSn catalysts supported on SiO 2 and H-ZSM-5 were studied for methane conversion under nonoxidative conditions. Addition of Sn to Pt/SiO 2 increased the turnover frequency for production of ethylene by a factor of 3, and pretreatment of the catalyst at 1123 K reduced the extent of coke formation. Pt and PtSn catalysts supported on H-ZSM-5 zeolite were prepared to improve the activity and selectivity to non-coke products. Ethylene formation rates were 20 times faster over a PtSn(1:3)/H-ZSM-5 catalyst with SiO 2:Al 2O 3 = 280 in comparison to those over PtSn(3:1)/SiO 2. H-ZSM-5-supported catalysts were also activemore » for the formation of aromatics, and the rates of benzene and naphthalene formation were increased by using more acidic H-ZSM-5 supports. These catalysts operate through a bifunctional mechanism, in which ethylene is first produced on highly dispersed PtSn nanoparticles and then is subsequently converted to benzene and naphthalene on Brønsted acid sites within the zeolite support. The most active and stable PtSn catalyst forms carbon products at a rate, 2.5 mmol of C/((mol of Pt) s), which is comparable to that of state-of-the-art Mo/H-ZSM-5 catalysts with same metal loading operated under similar conditions (1.8 mmol of C/((mol of Mo) s)). Scanning transmission electron microscopy measurements suggest the presence of smaller Pt nanoparticles on H-ZSM-5-supported catalysts, in comparison to SiO 2-supported catalysts, as a possible source of their high activity. As a result, a microkinetic model of methane conversion on Pt and PtSn surfaces, built using results from density functional theory calculations, predicts higher coupling rates on bimetallic and stepped surfaces, supporting the experimental observations that relate the high catalytic activity to small PtSn particles.« less

Role of Vegetation and Mulch in Mitigating the Effects of Raindrop Impact on Runoff and Infiltration from Urban Vegetated Green Infrastructure

NASA Astrophysics Data System (ADS)

Alizadehtazi, B.; Montalto, F. A.

2013-12-01

Rain drop impact causes soil crust formation which, in turn, reduces infiltration rates and increases runoff, contributing to soil erosion, downstream flooding and non point source pollutant loads. Unprotected soil surfaces (e.g. without vegetation canopies, mulch, or other materials), are more susceptible to crust formation due to the higher kinetic energy associated with raindrop impact. This impulse breaks larger soil aggregates into smaller particles and disperses soil from its original position. The displaced soil particles self-stratify, with finer particles at the top forming the crust. By contrast, soil that is protected by vegetation canopies and mulch layers is less susceptible to crust formation, since these surfaces intercept raindrops, dissipating some of their kinetic energy prior to their impact with the soil. Very little research has sought to quantify the effect that canopies and mulch can have on this phenomenon. This presentation presents preliminary findings from ongoing study conducted using rainfall simulator to determine the ability of new urban vegetation and mulch to minimize soil crust formation. Three different scenarios are compared: a) bare soil, b) soil with mulch cover, and c) soil protected by vegetation canopies. Soil moisture, surface penetration resistance, and physical measurements of the volume of infiltrate and runoff are made on all three surface treatments after simulated rainfall events. The results are used to discuss green infrastructure facility maintenance and design strategies, namely whether heavily vegetated GI facilities require mulching to maintain infiltration capacity.

Trace gas measurements from tethered balloon platforms

NASA Technical Reports Server (NTRS)

Bandy, Alan R.; Bandy, Terese L.; Youngbluth, Otto; Owens, Thomas L.

1987-01-01

Instrumentation and chemical sampling and analysis procedures are described for making measurements of atmospheric carbon disulfide in the concentration range 1-1000 pptv from tethered balloon platforms. Results of a study on the CS2 composition of air downward of a saltwater marsh are reported. A method for obtaining the necessary data for solving the budget equations for surface fluxes, chemical formation rates and chemical destruction rates using data acquired from tethered balloon platforms is presented.

Hydrolysis of VX on Concrete: Rate of Degradation by Direct Surface Interrogation using an Ion Trap Secondary Ion Mass Spectrometer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Groenewold, Gary Steven; Appelhans, Anthony David; Gresham, Garold Linn

2002-09-01

The nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate) is lethal at very low levels of exposure, which can occur by dermal contact with contaminated surfaces. Hence, behavior of VX in contact with common urban or industrial surfaces is a subject of acute interest. In the present study, VX was found to undergo complete degradation when in contact with concrete surfaces. The degradation was directly interrogated at submonolayer concentrations by periodically performing secondary ion mass spectrometry (SIMS) analyses after exposure of the concrete to VX. The abundance of the [VX + H]+ ion in the SIMS spectra was observed to decrease inmore » an exponential fashion, consistent with first-order or pseudo-first-order behavior. This phenomenon enabled the rate constant to be determined at 0.005 min-1 at 25 C, which corresponds to a half-life of about 3 h on the concrete surface. The decrease in [VX + H]+ was accompanied by an increase in the abundance of the principal degradation product diisopropylaminoethanethiol (DESH), which arises by cleavage of the P-S bond. Degradation to form DESH is accompanied by the formation of ethyl methylphosphonic acid, which is observable only in the negative ion spectrum. A second degradation product was also implicated, which corresponded to a diisopropylvinylamine isomer (perhaps N,N-diisopropyl aziridinium) that arose via cleavage of the S-C bond. No evidence was observed for the formation of the toxic S-2-diisopropylaminoethyl methylphosphonothioic acid. The degradation rate constants were measured at four different temperatures (24-50 C), which resulted in a linear Arrhenius relationship and an activation energy of 52 kJ mol-1. This value agrees with previous values observed for VX hydrolysis in alkaline solutions, which suggests that the degradation of submonolayer VX is dominated by alkaline hydrolysis within the adventitious water film on the concrete surface.« less

Hydrolysis of VX on concrete: rate of degradation by direct surface interrogation using an ion trap secondary ion mass spectrometer.

PubMed

Groenewold, Gary S; Williams, John M; Appelhans, Anthony D; Gresham, Garold L; Olson, John E; Jeffery, Mark T; Rowland, Brad

2002-11-15

The nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate) is lethal at very low levels of exposure, which can occur by dermal contact with contaminated surfaces. Hence, behavior of VX in contact with common urban or industrial surfaces is a subject of acute interest. In the present study, VX was found to undergo complete degradation when in contact with concrete surfaces. The degradation was directly interrogated at submonolayer concentrations by periodically performing secondary ion mass spectrometry (SIMS) analyses after exposure of the concrete to VX. The abundance of the [VX + H]+ ion in the SIMS spectra was observed to decrease in an exponential fashion, consistent with first-order or pseudo-first-order behavior. This phenomenon enabled the rate constant to be determined at 0.005 min(-1) at 25 degrees C, which corresponds to a half-life of about 3 h on the concrete surface. The decrease in [VX + H]+ was accompanied by an increase in the abundance of the principal degradation product diisopropylaminoethanethiol (DESH), which arises by cleavage of the P-S bond. Degradation to form DESH is accompanied by the formation of ethyl methylphosphonic acid, which is observable only in the negative ion spectrum. A second degradation product was also implicated, which corresponded to a diisopropylvinylamine isomer (perhaps N,N-diisopropyl aziridinium) that arose via cleavage of the S-C bond. No evidence was observed for the formation of the toxic S-2-diisopropylaminoethyl methylphosphonothioic acid. The degradation rate constants were measured at four different temperatures (24-50 degrees C), which resulted in a linear Arrhenius relationship and an activation energy of 52 kJ mol(-1). This value agrees with previous values observed for VX hydrolysis in alkaline solutions, which suggests that the degradation of submonolayer VX is dominated by alkaline hydrolysis within the adventitious water film on the concrete surface.

Assessing processes and timescales of sandstone 'peak forest' formation at Wulingyuan (Hunan, China)

NASA Astrophysics Data System (ADS)

Fink, David; May, Henne; Huang, He-quing; Fujioka, Toshiyuki; Wray, Robert

2013-04-01

Sandstone landscapes around the globe exhibit a surprising variety in terms of their landforms and formative processes. Ultimately, this reflects the wide range of geomorphic controls that dominate on regional scales, such as lithology, physical and chemical weathering, tectonics, and climate . At Wulingyuan, Hunan Province, China, a unique landscape has developed in Devonian sandstone over an area of ~400 km2, the "Wulingyuan peak forest", which is characterized by sheer vertical sandstone pillars over 3000 m in relief, overlayed with a substructure of peaks and walls of up to 350 m height. Due to these spectacular features, the area has become a major tourist attraction, and has recently been declared an UNESCO Global Geopark. Uplift, a densely spaced joint pattern, and the uniformity of sandstone beds have been suggested as major prerequisites for the formation and preservation of the unique morphology around Wulingyuan. We aim to investigate the underlying processes and controls responsible for the "peak forest" by determining a chronological framework for its age, rate of formation and rates of surface erosion. The initiation of uplift ~ 1 Ma ago and subsequent stepwise evolution of the "peak forest" has been inferred from cave sediments and surrounding alluvial terraces. No direct information, however, is available on the shorter-term evolution of the vertical sandstone walls, peaks and pillars. In this study , we (i) consider sampling strategies for applying surface exposure dating (SED) in this challenging morphological setting. (ii) present some first results, and (iii) discuss their significance in providing first estimates on rates of catchment-wide denudation, weathering, retreat of the vertical sandstone walls, and bedrock incision. In combination with a GIS-based assessment of sediment volumes stored in and eroded from the catchment, our data will help to elucidate the relative roles of fluvial, mass-wasting, and weathering processes in the longer-term, late Quaternary formation of the "peak forest".

Combinatorial Characterization of TiO2 Chemical Vapor Deposition Utilizing Titanium Isopropoxide.

PubMed

Reinke, Michael; Ponomarev, Evgeniy; Kuzminykh, Yury; Hoffmann, Patrik

2015-07-13

The combinatorial characterization of the growth kinetics in chemical vapor deposition processes is challenging because precise information about the local precursor flow is usually difficult to access. In consequence, combinatorial chemical vapor deposition techniques are utilized more to study functional properties of thin films as a function of chemical composition, growth rate or crystallinity than to study the growth process itself. We present an experimental procedure which allows the combinatorial study of precursor surface kinetics during the film growth using high vacuum chemical vapor deposition. As consequence of the high vacuum environment, the precursor transport takes place in the molecular flow regime, which allows predicting and modifying precursor impinging rates on the substrate with comparatively little experimental effort. In this contribution, we study the surface kinetics of titanium dioxide formation using titanium tetraisopropoxide as precursor molecule over a large parameter range. We discuss precursor flux and temperature dependent morphology, crystallinity, growth rates, and precursor deposition efficiency. We conclude that the surface reaction of the adsorbed precursor molecules comprises a higher order reaction component with respect to precursor surface coverage.

Rate estimates for lateral bedrock erosion based on radiocarbon ages, Duck River, Tennessee

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brakenridge, G.R.

Rates of bedrock erosion in ingrown meandering rivers can be inferred from the location of buried relict flood-plain and river-bank surfaces, associated paleosols, and radiocarbon dates. Two independent methods are used to evaluate the long-term rates of limestone bedrock erosion by the Duck River. Radiocarbon dates on samples retrieved from buried Holocene flood-plain and bank surfaces indicate lateral migration of the river bank at average rates of 0.6-1.9 m/100 yr. Such rates agree with lateral bedrock cliff erosion rates of 0.5-1.4 m/100 yr, as determined from a comparison of late Pleistocene and modern bedrock cliff and terrace scarp positions. Thesemore » results show that lateral bedrock erosion by this river could have occurred coevally with flood-plain and terrace formation and that the resulting evolution of valley meander bends carved into bedrock is similar in many respects to that of channel meanders cut into alluvium. 11 references, 5 figures.« less

Sea Ice Formation Rate and Temporal Variation of Temperature and Salinity at the Vicinity of Wilkins Ice Shelf from Data Collected by Southern Elephant Seals in 2008

NASA Astrophysics Data System (ADS)

Santini, M. F.; Souza, R.; Wainer, I.; Muelbert, M.; Hindell, M.

2013-05-01

The use of marine mammals as autonomous platforms for collecting oceanographic data has revolutionized the understanding of physical properties of low or non-sampled regions of the polar oceans. The use of these animals became possible due to advancements in the development of electronic devices, sensors and batteries carried by them. Oceanographic data collected by two southern elephant seals (Mirounga leonina) during the Fall of 2008 were used to infer the sea-ice formation rate in the region adjacent to the Wilkins Ice Shelf, west of the Antarctic Peninsula at that period. The sea-ice formation rate was estimated from the salt balance equation for the upper (100 m) ocean at a daily frequency for the period between 13 February and 20 June 2008. The oceanographic data collected by the animals were also used to present the temporal variation of the water temperature and salinity from surface to 300 m depth in the study area. Sea ice formation rate ranged between 0,087 m/day in early April and 0,008 m/day in late June. Temperature and salinity ranged from -1.84°C to 1.60°C and 32.85 to 34.85, respectively, for the upper 300 m of the water column in the analyzed period. The sea-ice formation rate estimations do not consider water advection, only temporal changes of the vertical profile of salinity. This may cause underestimates of the real sea-ice formation rate. The intense reduction of sea ice rate formation from April to June 2008 may be related to the intrusion of the Circumpolar Depth Water (CDW) into the study region. As a consequence of that we believe that this process can be partly responsible for the disintegration of the Wilkins Ice Shelf during the winter of 2008. The data presented here are considered a new frontier in physical and biological oceanography, providing a new approach for monitoring sea ice changes and oceanographic conditions in polar oceans. This is especially valid for regions covered by sea ice where traditional instruments deployed by research vessels cannot be used.

Lattice Gas Model Based Optimization of Plasma-Surface Processes for GaN-Based Compound Growth

NASA Astrophysics Data System (ADS)

Nonokawa, Kiyohide; Suzuki, Takuma; Kitamori, Kazutaka; Sawada, Takayuki

2001-10-01

Progress of the epitaxial growth technique for GaN-based compounds makes these materials attractive for applications in high temperature/high-power electronic devices as well as in short-wavelength optoelectronic devices. For MBE growth of GaN epilayer, atomic nitrogen is usually supplied from ECR-plasma while atomic Ga is supplied from conventional K-cell. To grow high-quality epilayer, fundamental knowledge of the detailed atomic process, such as adsorption, surface migration, incorporation, desorption and so forth, is required. We have studied the influence of growth conditions on the flatness of the growth front surface and the growth rate using Monte Carlo simulation based on the lattice gas model. Under the fixed Ga flux condition, the lower the nitrogen flux and/or the higher the growth temperature, the better the flatness of the front surface at the sacrifice of the growth rate of the epilayer. When the nitrogen flux is increased, the growth rate reaches saturation value determined from the Ga flux. At a fixed growth temperature, increasing of nitrogen to Ga flux ratio results in rough surface owing to 3-dimensional island formation. Other characteristics of MBE-GaN growth using ECR-plasma can be well reproduced.

Effect of surface Fe-S hybrid structure on the activity of the perfect and reduced α-Fe2O3(001) for chemical looping combustion

NASA Astrophysics Data System (ADS)

Xiao, Xianbin; Qin, Wu; Wang, Jianye; Li, Junhao; Dong, Changqing

2018-05-01

Sulfurization of the gradually reduced Fe2O3 surfaces is inevitable while Fe2O3 is used as an oxygen carrier (OC) for coal chemical looping combustion (CLC), which will result in formation of Fe-S hybrid structure on the surfaces. The Fe-S hybrid structure will directly alter the reactivity of the surfaces. Therefore, detailed properties of Fe-S hybrid structure over the perfect and reduced Fe2O3(001) surfaces, and its effect on the interfacial interactions, including CO oxidization and decomposition on the surfaces, were investigated by using density functional theory (DFT) calculations. The S atom prefers to chemically bind to Fe site with electron transfer from the surfaces to the S atom, and a deeper reduction of Fe2O3(001) leads to an increasing interaction between S and Fe. The formation of Fe-S hybrid structure alters the electronic properties of the gradually reduced Fe2O3(001) surfaces, promoting CO oxidation on the surfaces ranging from Fe2O3 to FeO, but depressing carbon deposition on the surfaces ranging from FeO to Fe. The sulfurized FeO acts as a watershed to realize relatively high CO oxidation rate and low carbon deposition. Results provided a fundamental understanding for controlling and optimizing the CLC processes.

Impact deformation behavior of duplex and superaustenitic stainless steels welds by split Hopkinson pressure bar

NASA Astrophysics Data System (ADS)

Wang, Shing-Hoa; Huang, Chih-Sheng; Lee, Woei-Shyan; Chen, Tao-Hsing; Wu, Chia-Chang; Lien, Charles; Tsai, Hung-Yin

2009-12-01

A considerable volume of γ phase increases in the fusion zone (weld metal) for two duplex stainless steels after a high-strain-rate impact. The strain-induced γ phase formation in the fusion zone results in local hardness variation depending on the strain rate. The α phase content in the fusion zone decreases as the impact strain rate increases for SAF 2205 DSS and SAF 2507 DSS. The results of the two-phase content measured by Ferritoscope correspond to that assessed by image analyses. In contrast, superaustenite stainless steel is unaffected by such an impact owing to its fully stable austenization. Impacted welds at a high strain rate of 5 × 103 s-1 reveal feather-like surface creases along the solidified curved columnar grain boundaries. The apparent surface creases are formed due to the presence of diffuse Lüders bands, which are caused by heavy plastic deformation in coarse-grain materials.

The natural emergence of the correlation between H2 and star formation rate surface densities in galaxy simulations

NASA Astrophysics Data System (ADS)

Lupi, Alessandro; Bovino, Stefano; Capelo, Pedro R.; Volonteri, Marta; Silk, Joseph

2018-03-01

In this study, we present a suite of high-resolution numerical simulations of an isolated galaxy to test a sub-grid framework to consistently follow the formation and dissociation of H2 with non-equilibrium chemistry. The latter is solved via the package KROME, coupled to the mesh-less hydrodynamic code GIZMO. We include the effect of star formation (SF), modelled with a physically motivated prescription independent of H2, supernova feedback and mass-losses from low-mass stars, extragalactic and local stellar radiation, and dust and H2 shielding, to investigate the emergence of the observed correlation between H2 and SF rate surface densities. We present two different sub-grid models and compare them with on-the-fly radiative transfer (RT) calculations, to assess the main differences and limits of the different approaches. We also discuss a sub-grid clumping factor model to enhance the H2 formation, consistent with our SF prescription, which is crucial, at the achieved resolution, to reproduce the correlation with H2. We find that both sub-grid models perform very well relative to the RT simulation, giving comparable results, with moderate differences, but at much lower computational cost. We also find that, while the Kennicutt-Schmidt relation for the total gas is not strongly affected by the different ingredients included in the simulations, the H2-based counterpart is much more sensitive, because of the crucial role played by the dissociating radiative flux and the gas shielding.

A model for prediction of fume formation rate in gas metal arc welding (GMAW), globular and spray modes, DC electrode positive.

PubMed

Dennis, J H; Hewitt, P J; Redding, C A; Workman, A D

2001-03-01

Prediction of fume formation rate during metal arc welding and the composition of the fume are of interest to occupational hygienists concerned with risk assessment and to manufacturers of welding consumables. A model for GMAW (DC electrode positive) is described based on the welder determined process parameters (current, wire feed rate and wire composition), on the surface area of molten metal in the arc and on the partial vapour pressures of the component metals of the alloy wire. The model is applicable to globular and spray welding transfer modes but not to dip mode. Metal evaporation from a droplet is evaluated for short time increments and total evaporation obtained by summation over the life of the droplet. The contribution of fume derived from the weld pool and spatter (particles of metal ejected from the arc) is discussed, as are limitations of the model. Calculated droplet temperatures are similar to values determined by other workers. A degree of relationship between predicted and measured fume formation rates is demonstrated but the model does not at this stage provide a reliable predictive tool.

Thermodynamic and Dynamic Aspects of Ice Nucleation

NASA Technical Reports Server (NTRS)

Barahona, Donifan

2018-01-01

It is known that ice nucleating particles (INP) immersed within supercooled droplets promote the formation of ice. Common theoretical models used to represent this process assume that the immersed particle lowers the work of ice nucleation without significantly affecting the dynamics of water in the vicinity of the particle. This is contrary to evidence showing that immersed surfaces significantly affect the viscosity and diffusivity of vicinal water. To study how this may affect ice formation this work introduces a model linking the ice nucleation rate to the modification of the dynamics and thermodynamics of vicinal water by immersed particles. It is shown that INP that significantly reduce the work of ice nucleation also pose strong limitations to the growth of the nascent ice germs. This leads to the onset of a new ice nucleation regime, called spinodal ice nucleation, where the dynamics of ice germ growth instead of the ice germ size determines the nucleation rate. Nucleation in this regime is characterized by an enhanced sensitivity to particle area and cooling rate. Comparison of the predicted ice nucleation rate against experimental measurements for a diverse set of species relevant to cloud formation suggests that spinodal ice nucleation may be common in nature.

The chemisorption and reactions of formic acid on Cu films on ZnO (000 overline1)-O

NASA Astrophysics Data System (ADS)

Ludviksson, A.; Zhang, R.; Campbell, Charles T.; Griffiths, K.

1994-06-01

The adsorption and reactions of formic acid (HCOOD : HCOOH = 3:1) on the oxygen-terminated ZnO(0001¯)-O surface and on thin Cu films deposited on the ZnO(0001¯)-O surface have been studied with temperature programmed desorption (TPD) and XPS. Small amounts of formic acid dissociate at defect sites on clean ZnO(0001¯)-O to yield surface formate (HCOO). The acid D(H) from this dissociation does not reappear in TPD, and is lost to the ZnO bulk, as confirmed by nuclear reaction analysis. The surface HCOO decomposes to yield nearly simultaneous CO 2 (37%), CO (63%) and H 2 TPD peaks at 560 K. Substantial amounts of D (˜ 20%) are incorporated in this hydrogen TPD peak resulting from formate decomposition at ZnO defects, indicating that bulk D is readily accessible. Submonolayer and multilayer Cu films that are deposited at 130 K and partially cover the ZnO surface as 2D and 3D islands adsorb formic acid and decompose it into formate and hydrogen much like the Cu(110) surface. The surface formate from the Cu film decomposes at 470-500 K to give primarily CO 2 and H 2, also much like Cu(110), although atom-thin Cu islands also give ˜ 40% CO. Annealed Cu films give formate decomposition peaks at 25-50 K lower in temperature, attributed to thickening and ordering of the Cu islands to form Cu(111)-like sites. The acid D(H) atom from the formic acid is partially lost by hydrogen spillover from the Cu islands into the ZnO substrate, especially for thin Cu films. This effect partially desorbs and is enhanced upon preannealing the Cu layers, due to increased H diffusion rates across the annealed Cu islands, and/or the decrease in island size. Bulk D(H) is slowly removed as D 2, HD and H 2 above 400 K in diffusion-limited desorption, catalyzed by Cu.

Atomic force microscopy investigation of growth process of organic TCNQ aggregates on SiO2 and mica substrates

NASA Astrophysics Data System (ADS)

Huan, Qing; Hu, Hao; Pan, Li-Da; Xiao, Jiang; Du, Shi-Xuan; Gao, Hong-Jun

2010-08-01

Deposition patterns of tetracyanoquinodimethane (TCNQ) molecules on different surfaces are investigated by atomic force microscopy. A homemade physical vapour deposition system allows the better control of molecule deposition. Taking advantage of this system, we investigate TCNQ thin film growth on both SiO2 and mica surfaces. It is found that dense island patterns form at a high deposition rate, and a unique seahorse-like pattern forms at a low deposition rate. Growth patterns on different substrates suggest that the fractal pattern formation is dominated by molecule-molecule interaction. Finally, a phenomenal “two-branch" model is proposed to simulate the growth process of the seahorse pattern.

Electrogenerative oxidation of lower alcohols to useful products

DOEpatents

Meshbesher, Thomas M.

1987-01-01

In the disclosed electrogenerative process for converting alcohols such as ethanol to aldehydes such as acetaldehyde, the alcohol starting material is an aqueous solution containing more than the azeotropic amount of water. Good first-pass conversions (<40% and more typically <50%) are obtained at operating cell voltages in the range of about 80 to about 350 millivolts at ordinary temperatures and pressures by using very high flow rates of alcohol to the exposed anode surface (i.e. the "gas" side of an anode whose other surface is in contact with the electrolyte). High molar flow rates of vaporized aqueous alcohol also help to keep formation of undesired byproducts at a low level.

Effects of different shear rates on the attachment and detachment of platelet thrombi.

PubMed

Shi, Xiaofeng; Yang, Jichun; Huang, Jiansong; Long, Zhangbiao; Ruan, Zheng; Xiao, Bing; Xi, Xiaodong

2016-03-01

Thrombosis and hemostasis take place in flowing blood, which generates shear forces. The effect of different shear rates, particularly pathological forces, on platelet thrombus formation remains to be fully elucidated. The present study observed the morphological characteristics and hierarchical structure of thrombi on the collagen surface at a wide range of wall shear rates (WSRs) and examined the underlying mechanisms. Calcein AM‑labeled whole blood was perfused over a collagen‑coated surface at different shear rates set by a Bioflux 200 microfluidic device and the thrombi formed were assessed for area coverage, the height and the hierarchical structure defined by the extent of platelet activation and packing density. The factors that affect thrombus formation were also investigated. Platelet thrombus formation varied under different WSRs, for example, dispersed platelet adhesion mixed with erythrocytes was observed at 125‑250 s(‑1), extensive and thin platelet thrombi were observed at 500‑1,500 s(‑1), and sporadic, thick thrombi were observed at pathological WSRs of 2,500‑5,000 s(‑1), which showed a tendency to be shed. With increasing WSRs, the height of the thrombi showed an increasing linear trend, whereas the total fluorescence intensity and area of the thrombi exhibited a parabolic curve‑like change, with a turning point at a WSR of 2,500 s(‑1). The number of thrombi, the average fluorescence intensity and the area per thrombus showed similar trends, with an initial upwards incline followed by a decline. The thrombi formed at higher WSRs had a thicker shell, which led to a more densely packed core. Platelet thrombus formation under shear‑flow was regulated by the adhesive strength, which was mediated by receptor‑ligand interaction, the platelet deposition induced by shear rates and the detachment by the dynamic force of flow. This resulted in a balance between thrombus attachment, including adhesion and aggregation, and detachment. Collectively, compared with physiological low WSRs, pathological high WSRs caused thicker and more easily shed thrombi with more condensed cores, which was regulated by an attachment‑detachment balance. These results provide novel insights into the properties of thrombus formation on collagen at different WSRs, and offers possible explanations for certain clinical physiopathological phenomena, including physical hemostasis and pathological thrombosis.

Ionic Strength Modulation of the Free Energy Landscape of Aβ40 Peptide Fibril Formation.

PubMed

Abelein, Axel; Jarvet, Jüri; Barth, Andreas; Gräslund, Astrid; Danielsson, Jens

2016-06-01

Protein misfolding and formation of cross-β structured amyloid fibrils are linked to many neurodegenerative disorders. Although recently developed quantitative approaches have started to reveal the molecular nature of self-assembly and fibril formation of proteins and peptides, it is yet unclear how these self-organization events are precisely modulated by microenvironmental factors, which are known to strongly affect the macroscopic aggregation properties. Here, we characterize the explicit effect of ionic strength on the microscopic aggregation rates of amyloid β peptide (Aβ40) self-association, implicated in Alzheimer's disease. We found that physiological ionic strength accelerates Aβ40 aggregation kinetics by promoting surface-catalyzed secondary nucleation reactions. This promoted catalytic effect can be assigned to shielding of electrostatic repulsion between monomers on the fibril surface or between the fibril surface itself and monomeric peptides. Furthermore, we observe the formation of two different β-structured states with similar but distinct spectroscopic features, which can be assigned to an off-pathway immature state (Fβ*) and a mature stable state (Fβ), where salt favors formation of the Fβ fibril morphology. Addition of salt to preformed Fβ* accelerates transition to Fβ, underlining the dynamic nature of Aβ40 fibrils in solution. On the basis of these results we suggest a model where salt decreases the free-energy barrier for Aβ40 folding to the Fβ state, favoring the buildup of the mature fibril morphology while omitting competing, energetically less favorable structural states.

Analyzing and improving surface texture by dual-rotation magnetorheological finishing

NASA Astrophysics Data System (ADS)

Wang, Yuyue; Zhang, Yun; Feng, Zhijing

2016-01-01

The main advantages of magnetorheological finishing (MRF) are its high convergence rate of surface error, the ability of polishing aspheric surfaces and nearly no subsurface damage. However, common MRF produces directional surface texture due to the constant flow direction of the magnetorheological (MR) polishing fluid. This paper studies the mechanism of surface texture formation by texture modeling. Dual-rotation magnetorheological finishing (DRMRF) is presented to suppress directional surface texture after analyzing the results of the texture model for common MRF. The results of the surface texture model for DRMRF and the proposed quantitative method based on mathematical statistics indicate the effective suppression of directional surface texture. An experimental setup is developed and experiments show directional surface texture and no directional surface texture in common MRF and DRMRF, respectively. As a result, the surface roughness of DRMRF is 0.578 nm (root-mean-square value) which is lower than 1.109 nm in common MRF.

Mechanism of CO 2 Hydrogenation on Pd/Al 2 O 3 Catalysts: Kinetics and Transient DRIFTS-MS Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xiang; Shi, Hui; Kwak, Ja Hun

The hydrogenation of CO 2 was investigated over a wide range of reaction conditions, using two Pd/γ-Al 2O 3 catalysts with different Pd loadings (5% and 0.5%) and dispersions (~11% and ~100%, respectively). Turnover rates for CO and CH 4 formation were both higher over 5% Pd/Al 2O 3 with a larger average Pd particle size than those over 0.5% Pd/Al 2O 3 with a smaller average particle size. The selectivity to methane (22-40%) on 5% Pd/Al 2O 3 was higher by a factor of 2-3 than that on 0.5% Pd/Al 2O 3. The drastically different rate expressions and apparentmore » energies of activation for CO and CH 4 formation lead us to conclude that reverse water gas shift and CO 2 methanation do not share the same rate-limiting step on Pd, and that the two pathways are probably catalyzed at different surface sites. Measured reaction orders in CO 2 and H 2 pressures were similar over the two catalysts, suggesting that the reaction mechanism for each pathway does not change with particle size. In accordance, the DRIFTS results reveal that the prevalent surface species and their evolution patterns are comparable on the two catalysts during transient and steady-state experiments, switching feed gases among CO 2, H 2 and CO 2+H 2. The DRIFTS and MS results also demonstrate that no direct dissociation of CO 2 takes place over the two catalysts, and that CO 2 has to first react with surface hydroxyls on the oxide support. The thus-formed bicarbonates react with dissociatively adsorbed hydrogen on Pd particles to produce adsorbed formate species (bifunctional catalyst: CO 2 activation on the oxide support, and H 2 dissociation on the metal particles). Formates near the Pd particles (most likely at the metal/oxide interface) can react rapidly with adsorbed H to produce CO, which then adsorbs on the metallic Pd particles. Two types of Pd sites are identified: one has a weak interaction with CO, which easily desorbs into gas phase at reaction temperatures, while the other interacts more strongly with CO, which is mainly in multi-bound forms and remains stable in He flow at high temperatures, but is reactive towards adsorbed H atoms on Pd leading eventually to CH 4 formation. 5% Pd/Al 2O 3 contains a larger fraction of terrace sites favorable for forming these more stable CO species than 0.5% Pd/Al 2O 3. Consequently, we propose that the difference in the formation rate and selectivity to CH 4 on different Pd particle sizes stems from the different concentrations of the reactive intermediate for the methanation pathway on the Pd surface. JS gratefully acknowledges the financial support of this work by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division.« less

Influence of the ablation plume on the removal process during ArF-excimer laser photoablation

NASA Astrophysics Data System (ADS)

Doerbecker, Christina; Lubatschowski, Holger; Lohmann, Stefan; Ruff, Christine; Kermani, Omid; Ertmer, Wolfgang

1996-01-01

Correction of myopia with the ArF-excimer laser (PRK) sometimes leads to a so called 'central island' formation on the anterior corneal surface. The attenuation of the laser beam by the ablation plume might be one reason for this phenomenon. The attenuation properties of the ablation plume were investigated by a probe beam parallel to the surface of the tissue probe. By varying the laser parameters (fluence, repetition rate, spot size) and the target tissue (cornea, PMMA) the attenuation of the probe beam was measured time and spatial resolved. As a result of this study, a significant influence of the removal process due to scattering and absorption within the ablation plume can be assumed as a function of repetition rate, spot size and air flow on the tissue surface.

Enthalpy of Formation for Cu–Zn–Sn–S (CZTS) Calculated from Surface Binding Energies Experimentally Measured by Ion Sputtering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baryshev, Sergey V.; Thimsen, Elijah

2015-04-14

Herein, we report an analytical procedure to calculate the enthalpy of formation for thin film multinary compounds from sputtering rates measured during ion bombardment. The method is based on Sigmunds sputtering theory and the BornHaber cycle. Using this procedure, an enthalpy of formation for a CZTS film of the composition Cu1.9Zn1.5Sn0.8S4 was measured as -930 +/- 98 kJ mol1. This value is much more negative than the sum of the enthalpies of formation for the constituent binary compounds, meaning the multinary formation reaction is predicted to be exothermic. The measured enthalpy of formation was used to estimate the temperature dependencemore » of the Gibbs free energy of reaction, which appears consistent with many experimental reports in the CZTS processing literature.« less

IMPACT OF SUPERNOVA AND COSMIC-RAY DRIVING ON THE SURFACE BRIGHTNESS OF THE GALACTIC HALO IN SOFT X-RAYS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, Thomas; Girichidis, Philipp; Gatto, Andrea

2015-11-10

The halo of the Milky Way contains a hot plasma with a surface brightness in soft X-rays of the order 10{sup −12} erg cm{sup −2} s{sup −1} deg{sup −2}. The origin of this gas is unclear, but so far numerical models of galactic star formation have failed to reproduce such a large surface brightness by several orders of magnitude. In this paper, we analyze simulations of the turbulent, magnetized, multi-phase interstellar medium including thermal feedback by supernova explosions as well as cosmic-ray feedback. We include a time-dependent chemical network, self-shielding by gas and dust, and self-gravity. Pure thermal feedback alonemore » is sufficient to produce the observed surface brightness, although it is very sensitive to the supernova rate. Cosmic rays suppress this sensitivity and reduce the surface brightness because they drive cooler outflows. Self-gravity has by far the largest effect because it accumulates the diffuse gas in the disk in dense clumps and filaments, so that supernovae exploding in voids can eject a large amount of hot gas into the halo. This can boost the surface brightness by several orders of magnitude. Although our simulations do not reach a steady state, all simulations produce surface brightness values of the same order of magnitude as the observations, with the exact value depending sensitively on the simulation parameters. We conclude that star formation feedback alone is sufficient to explain the origin of the hot halo gas, but measurements of the surface brightness alone do not provide useful diagnostics for the study of galactic star formation.« less

Reaction of gas phase OH with unsaturated self-assembled monolayers and relevance to atmospheric organic oxidations.

PubMed

Moussa, Samar G; Finlayson-Pitts, Barbara J

2010-08-28

The kinetics and mechanisms of the reaction of gas phase OH radicals with organics on surfaces are of fundamental chemical interest, as well as relevant to understanding the degradation of organics on tropospheric surfaces or when they are components of airborne particles. We report here studies of the oxidation of a terminal alkene self-assembled monolayer (7-octenyltrichlorosilane, C8= SAM) on a germanium attenuated total reflectance crystal by OH radicals at a concentration of 2.1 x 10(5) cm(-3) at 1 atm total pressure and 298 K in air. Loss of the reactant SAM and the formation of surface products were followed in real time using infrared spectroscopy. From the rate of loss of the C=C bond, a reaction probability within experimental error of unity was derived. The products formed on the surface include organic nitrates and carbonyl compounds, with yields of 10 +/- 4% and < or = 7 +/- 4%, respectively, and there is evidence for the formation of organic products with C-O bonds such as alcohols, ethers and/or alkyl peroxides and possibly peroxynitrates. The yield of organic nitrates relative to carbonyl compounds is higher than expected based on analogous gas phase mechanisms, suggesting that the branching ratio for the RO(2) + NO reaction is shifted to favor the formation of organic nitrates when the reaction occurs on a surface. Water uptake onto the surface was only slightly enhanced upon oxidation, suggesting that oxidation per se cannot be taken as a predictor of increased hydrophilicity of atmospheric organics. These experiments indicate that the mechanisms for the surface reactions are different from gas phase reactions, but the OH oxidation of surface species will still be a significant contributor to determining their lifetimes in air.

Evolution of the Copper Surface in the Course of Oxidation by CCl4-L (L=THF, Dmf, Dmso): Scanning Probe Microscope Study

NASA Astrophysics Data System (ADS)

Panteleev, S. V.; Maslennikov, S. V.; Ignatov, S. K.; Spirina, I. V.; Kruglova, M. V.; Gribkov, B. A.; Vdovichev, S. N.

2013-04-01

The evolution of compact surface of the 100 nm copper film deposited on the glass-ceramics doped with vanadium coating in the course of the oxidation by the CCl4-L (L = dimethylformamide (DMF), tetrahydrofuran (THF), dimethylsulfoxide (DMSO), CCl4 concentration ≈ 1 mol/L) was studied by atomic force microscopy (AFM) in contact mode. The dynamics of active centers formation and destruction was investigated in the course of the oxidation process. The metallic sample dissolution rate was estimated as a function of the coordinating solvent nature. The development of the metal surface oxidation was established to lead to a significant increase of surface roughness. This phenomenon can be explained by the fact that different parts of the surface react at different rates. Further course of the reaction leads to a significant decrease of the surface roughness of copper films. The amount of the metal reacted has an almost linear dependence on the reaction time. AFM scans indicate that there is the same mechanism of the reaction between copper and carbon tetrachloride for all solvents.

Dynamics of polyelectrolyte adsorption on surfaces: Applications in the detection of iron in water

NASA Astrophysics Data System (ADS)

Gammana, Madhira N.

Layer by layer (LbL) self assembly is a simple multilayer thin (nanometer scale) film fabricating technique. The mechanism of film growth remains a topic of much controversy. For example, several models have been proposed to explain the origin of linear and exponential film growth that are attributed to differences in the dynamic processes that occur at the molecular level during film formation. The problem is that there are no methods that directly measure the dynamics of polymer formation during LbL film formation. In this thesis, I describe the essential elements of an ATR-IR spectroscopic method that was developed to enable measurement of the dynamics of the mass adsorbed and polyelectrolyte conformation during the formation of PEM's. In particular, I followed the sequential adsorption of Sodium polyacrylate (NaPA) and Poly (diallyldimethylammonium) chloride (PDADMAC) from deionized (DI) water and as a function of ionic strength to show that polymer diffusion occurs between layers when adsorbed from DI water. In contrast, a denser layer occurs with no polymer interdiffusion for deposition from 0.02M ionic strength solutions of NaPA and PDADMAC. While the mass deposited increased with ionic strength, linear multilayer growth in films were observed in all cases. This finding disputes a common viewpoint that interdiffusion of polymer layers is a key feature of exponential film growth. The theme of polymer layer adsorption was used in the detection of Fe 3+ in seawater. A new approach, developed previously in Tripp's group, utilized "vertical amplification" in which a block copolymer assembled on membranes provided multiple anchoring points extending from the surface for attaching a siderophore, desferrioxamine B (DFB). The Fe3+ chelates with the siderophore producing a red color that can be quantified by visible spectroscopy. However, the rate of Fe3+ uptake was found to be dependent on flow rate. The origin of this flow rate dependence was identified by the work presented in this thesis. It was found that the amount and rate of Fe3+ uptake was dependent on the relative size of each block in the polymer and the degree of reaction of DFB with the adsorbed layer. In particular, higher amounts and higher rates were obtained when the density of DFB was lowered. This shows that the DFB was sterically hindered from forming a hexacoordinate complex with Fe3+ by the presence of neighboring DFB molecules. This is a key factor that needs to be considered in developing Fe3+ detection systems based on siderophores anchored to surfaces.

Eogenetic siderite as an indicator for fluctuations in sedimentation rate in the Oligocene Boom Clay Formation (Belgium)

NASA Astrophysics Data System (ADS)

Laenen, B.; De Craen, M.

2004-01-01

Horizons with septarian concretions are a salient feature of the marine Boom Clay Formation. At most horizons, the concretions consist of ferroan calcite with variable amounts of pyrite, but at stratigraphic level S60 they also contain siderite. S60 is situated at the centre of an intensely bioturbated zone that is underlain by a pyrite-rich layer. Furthermore, the enclosing clay is strongly enriched in iron, manganese and phosphorous. The sedimentological and chemical zoning is indicative for low sedimentation rates, which allowed the concentration of iron in the aerobic zone of the sediment. Concentration of iron was the prerequisite for the formation of the siderite-containing concretions. The co-precipitation with pyrite is an argument for a formation in the sulphate reduction zone, and is indicative for a high rate of iron-reduction. The latter was due to the rapid burial of the iron-enriched layer below the redox boundary. The abrupt fluctuations in sedimentation rate were a response to the maximum flooding event of the second Rupelian third-order relative sea-level cycle, which caused a brief pushback of the detrital sediment wedge to its source areas. As this response is logically explained by the general sequence stratigraphic model [Spec. Publ.-Soc. Econ. Paleontol. Mineral. 42 (1988) 109], early diagenetic siderite may be widespread at maximum flooding surfaces in rapidly prograding marine mudstones.

Analytical volcano deformation source models

USGS Publications Warehouse

Lisowski, Michael; Dzurisin, Daniel

2007-01-01

Primary volcanic landforms are created by the ascent and eruption of magma. The ascending magma displaces and interacts with surrounding rock and fluids as it creates new pathways, flows through cracks or conduits, vesiculates, and accumulates in underground reservoirs. The formation of new pathways and pressure changes within existing conduits and reservoirs stress and deform the surrounding rock. Eruption products load the crust. The pattern and rate of surface deformation around volcanoes reflect the tectonic and volcanic processes transmitted to the surface through the mechanical properties of the crust.

A Review of Experimental Observations and Remaining Questions Concerning Formation, Persistence and Disappearance of Sea Slicks

DTIC Science & Technology

1991-05-06

the dimensions of single molecules, i.e., less than 10 nm. Oil Slick - An oil slick is caused when petroleum products are spilled on the sea. These... products and has a connotation implying that the substance is man-made. A detergent is a specific type of surfactant. Surfactants can form...increases the rate of tra .sport of surface-active material to the sea surface and may contribute significantly to the production of slicks observed behind

Protein Adsorption and Layer Formation at the Stainless Steel-Solution Interface Mediates Shear-Induced Particle Formation for an IgG1 Monoclonal Antibody.

PubMed

Kalonia, Cavan K; Heinrich, Frank; Curtis, Joseph E; Raman, Sid; Miller, Maria A; Hudson, Steven D

2018-03-05

Passage of specific protein solutions through certain pumps, tubing, and/or filling nozzles can result in the production of unwanted subvisible protein particles (SVPs). In this work, surface-mediated SVP formation was investigated. Specifically, the effects of different solid interface materials, interfacial shear rates, and protein concentrations on SVP formation were measured for the National Institute of Standards and Technology monoclonal antibody (NISTmAb), a reference IgG1 monoclonal antibody (mAb). A stainless steel rotary piston pump was used to identify formulation and process parameters that affect aggregation, and a flow cell (alumina or stainless steel interface) was used to further investigate the effect of different interface materials and/or interfacial shear rates. SVP particles produced were monitored using flow microscopy or flow cytometry. Neutron reflectometry and a quartz crystal microbalance with dissipation monitoring were used to characterize adsorption and properties of NISTmAb at the stainless steel interface. Pump/shear cell experiments showed that the NISTmAb concentration and interface material had a significant effect on SVP formation, while the effects of interfacial shear rate and passage number were less important. At the higher NISTmAb concentrations, the adsorbed protein became structurally altered at the stainless steel interface. The primary adsorbed layer remained largely undisturbed during flow, suggesting that SVP formation at high NISTmAb concentration was caused by the disruption of patches and/or secondary interactions.

High-surface-area mesoporous TiO2 microspheres via one-step nanoparticle self-assembly for enhanced lithium-ion storage

NASA Astrophysics Data System (ADS)

Wang, Hsin-Yi; Chen, Jiazang; Hy, Sunny; Yu, Linghui; Xu, Zhichuan; Liu, Bin

2014-11-01

Mesoporous TiO2 microspheres assembled from TiO2 nanoparticles with specific surface areas as high as 150 m2 g-1 were synthesized via a facile one-step solvothermal reaction of titanium isopropoxide and anhydrous acetone. Aldol condensation of acetone gradually releases structural H2O, which hydrolyzes and condenses titanium isopropoxide, forming TiO2 nanocrystals. Simultaneous growth and aggregation of TiO2 nanocrystals leads to the formation of high-surface-area TiO2 microspheres under solvothermal conditions. After a low-temperature post-synthesis calcination, carbonate could be incorporated into TiO2 as a dopant with the carbon source coming from the organic byproducts during the synthesis. Carbonate doping modifies the electronic structure of TiO2 (e.g., Fermi level, Ef), and thus influences its electrochemical properties. Solid electrolyte interface (SEI) formation, which is not common for titania, could be initiated in carbonate-doped TiO2 due to elevated Ef. After removing carbonate dopants by high-temperature calcination, the mesoporous TiO2 microspheres showed much improved performance in lithium insertion and stability at various current rates, attributed to a synergistic effect of high surface area, large pore size and good anatase crystallinity.Mesoporous TiO2 microspheres assembled from TiO2 nanoparticles with specific surface areas as high as 150 m2 g-1 were synthesized via a facile one-step solvothermal reaction of titanium isopropoxide and anhydrous acetone. Aldol condensation of acetone gradually releases structural H2O, which hydrolyzes and condenses titanium isopropoxide, forming TiO2 nanocrystals. Simultaneous growth and aggregation of TiO2 nanocrystals leads to the formation of high-surface-area TiO2 microspheres under solvothermal conditions. After a low-temperature post-synthesis calcination, carbonate could be incorporated into TiO2 as a dopant with the carbon source coming from the organic byproducts during the synthesis. Carbonate doping modifies the electronic structure of TiO2 (e.g., Fermi level, Ef), and thus influences its electrochemical properties. Solid electrolyte interface (SEI) formation, which is not common for titania, could be initiated in carbonate-doped TiO2 due to elevated Ef. After removing carbonate dopants by high-temperature calcination, the mesoporous TiO2 microspheres showed much improved performance in lithium insertion and stability at various current rates, attributed to a synergistic effect of high surface area, large pore size and good anatase crystallinity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04729j

Forming a structure of the CoNiFe alloys by X-ray irradiation

NASA Astrophysics Data System (ADS)

Valko, Natalia; Kasperovich, Andrey; Koltunowicz, Tomasz N.

The experimental data of electrodeposition kinetics researches and structure formation of ternary CoNiFe alloys deposited onto low-carbon steel 08kp in the presence of X-rays are presented. Relations of deposit rate, current efficiencies, element and phase compositions of CoNiFe coatings formed from sulfate baths with respect to cathode current densities (0.5-3A/dm2), electrolyte composition and irradiation were obtained. It is shown that, the CoNiFe coatings deposited by the electrochemical method involving exposure of the X-rays are characterized by more perfect morphology surfaces with less developed surface geometry than reference coatings. The effect of the X-ray irradiation on the electrodeposition of CoNiFe coatings promotes formatting of alloys with increased electropositive component and modified phase composition.

Orientation of ripples induced by ultrafast laser pulses on copper in different liquids

NASA Astrophysics Data System (ADS)

Maragkaki, Stella; Elkalash, Abdallah; Gurevich, Evgeny L.

2017-12-01

Formation of laser-induced periodic surface structures (LIPSS or ripples) was studied on a metallic surface of polished copper using irradiation with multiple femtosecond laser pulses in different environmental conditions (air, water, ethanol and methanol). Uniform LIPSS have been achieved by controlling the peak fluence and the overlapping rate. Ripples in both orientations, perpendicular and parallel to laser polarization, were observed in all liquids simultaneously. The orientation of these ripples in the center of the ablated line was changing with the incident light intensity. For low intensities the orientation of the ripples is perpendicular to the laser polarization, whereas for high intensities it turns parallel to it without considerable changes in the period. Multi-directional LIPSS formation was also observed for moderate peak fluence in liquid environments.

Partially Oxidized SnS2 Atomic Layers Achieving Efficient Visible-Light-Driven CO2 Reduction.

PubMed

Jiao, Xingchen; Li, Xiaodong; Jin, Xiuyu; Sun, Yongfu; Xu, Jiaqi; Liang, Liang; Ju, Huanxin; Zhu, Junfa; Pan, Yang; Yan, Wensheng; Lin, Yue; Xie, Yi

2017-12-13

Unraveling the role of surface oxide on affecting its native metal disulfide's CO 2 photoreduction remains a grand challenge. Herein, we initially construct metal disulfide atomic layers and hence deliberately create oxidized domains on their surfaces. As an example, SnS 2 atomic layers with different oxidation degrees are successfully synthesized. In situ Fourier transform infrared spectroscopy spectra disclose the COOH* radical is the main intermediate, whereas density-functional-theory calculations reveal the COOH* formation is the rate-limiting step. The locally oxidized domains could serve as the highly catalytically active sites, which not only benefit for charge-carrier separation kinetics, verified by surface photovoltage spectra, but also result in electron localization on Sn atoms near the O atoms, thus lowering the activation energy barrier through stabilizing the COOH* intermediates. As a result, the mildly oxidized SnS 2 atomic layers exhibit the carbon monoxide formation rate of 12.28 μmol g -1 h -1 , roughly 2.3 and 2.6 times higher than those of the poorly oxidized SnS 2 atomic layers and the SnS 2 atomic layers under visible-light illumination. This work uncovers atomic-level insights into the correlation between oxidized sulfides and CO 2 reduction property, paving a new way for obtaining high-efficiency CO 2 photoreduction performances.

The Link Between Rare-Earth Peak Formation and the Astrophysical Site of the R Process

DOE PAGES

Mumpower, Matthew R.; McLaughlin, Gail C.; Surman, Rebecca; ...

2016-12-20

The primary astrophysical source of the rare-earth elements is the rapid neutron capture process (r process). The rare-earth peak that is seen in the solar r-process residuals has been proposed to originate as a pile-up of nuclei during the end of the r process. Here, we introduce a new method utilizing Monte Carlo studies of nuclear masses in the rare-earth region, that includes self-consistently adjusting β-decay rates and neutron capture rates, to find the mass surfaces necessary for the formation of the rare-earth peak. We demonstrate our method with two types of astrophysical scenario, one corresponding to conditions typical ofmore » hot winds from core-collapse supernovae and stellar-mass accretion disks, and one corresponding to conditions typical of the ejection of the material from the tidal tails of neutron star mergers. In each type of astrophysical condition, this method successfully locates a region of enhanced stability in the mass surface that is responsible for the rare-earth peak. Finally, for each scenario, we find that the change in the mass surface has qualitatively different features, thus future measurements can shed light on the type of environment in which the r process occurred.« less

The Link Between Rare-Earth Peak Formation and the Astrophysical Site of the R Process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mumpower, Matthew R.; McLaughlin, Gail C.; Surman, Rebecca

The primary astrophysical source of the rare-earth elements is the rapid neutron capture process (r process). The rare-earth peak that is seen in the solar r-process residuals has been proposed to originate as a pile-up of nuclei during the end of the r process. Here, we introduce a new method utilizing Monte Carlo studies of nuclear masses in the rare-earth region, that includes self-consistently adjusting β-decay rates and neutron capture rates, to find the mass surfaces necessary for the formation of the rare-earth peak. We demonstrate our method with two types of astrophysical scenario, one corresponding to conditions typical ofmore » hot winds from core-collapse supernovae and stellar-mass accretion disks, and one corresponding to conditions typical of the ejection of the material from the tidal tails of neutron star mergers. In each type of astrophysical condition, this method successfully locates a region of enhanced stability in the mass surface that is responsible for the rare-earth peak. Finally, for each scenario, we find that the change in the mass surface has qualitatively different features, thus future measurements can shed light on the type of environment in which the r process occurred.« less

THE LINK BETWEEN RARE-EARTH PEAK FORMATION AND THE ASTROPHYSICAL SITE OF THE R PROCESS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mumpower, Matthew R.; McLaughlin, Gail C.; Surman, Rebecca

The primary astrophysical source of the rare-earth elements is the rapid neutron capture process ( r process). The rare-earth peak that is seen in the solar r -process residuals has been proposed to originate as a pile-up of nuclei during the end of the r process. We introduce a new method utilizing Monte Carlo studies of nuclear masses in the rare-earth region, that includes self-consistently adjusting β -decay rates and neutron capture rates, to find the mass surfaces necessary for the formation of the rare-earth peak. We demonstrate our method with two types of astrophysical scenario, one corresponding to conditionsmore » typical of hot winds from core-collapse supernovae and stellar-mass accretion disks, and one corresponding to conditions typical of the ejection of the material from the tidal tails of neutron star mergers. In each type of astrophysical condition, this method successfully locates a region of enhanced stability in the mass surface that is responsible for the rare-earth peak. For each scenario, we find that the change in the mass surface has qualitatively different features, thus future measurements can shed light on the type of environment in which the r process occurred.« less

A Volume Flux Approach to Cryolava Dome Emplacement on Europa

NASA Technical Reports Server (NTRS)

Quick, Lynnae C.; Fagents, Sarah A.; Hurford, Terry A.; Prockter, Louise M.

2017-01-01

We previously modeled a subset of domes on Europa with morphologies consistent with emplacement by viscous extrusions of cryolava. These models assumed instantaneous emplacement of a fixed volume of fluid onto the surface, followed by relaxation to form domes. However, this approach only allowed for the investigation of late-stage eruptive processes far from the vent and provided little insight into how cryolavas arrived at the surface. Consideration of dome emplacement as cryolavas erupt at the surface is therefore pertinent. A volume flux approach, in which lava erupts from the vent at a constant rate, was successfully applied to the formation of steep-sided volcanic domes on Venus. These domes are believed to have formed in the same manner as candi-date cryolava domes on Europa. In order to gain a more complete understanding of the potential for the emplacement of Europa domes via extrusive volcanism, we have applied this new volume flux approach to the formation of putative cryovolcanic domes on Europa. Assuming as in that europan cryolavas are briny, aqueous solutions which may or may not contain some ice crystal fraction, we present the results of this modeling and explore theories for the formation of low-albedo moats that surround some domes.

Active Pacific meridional overturning circulation (PMOC) during the warm Pliocene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burls, Natalie J.; Fedorov, Alexey V.; Sigman, Daniel M.

An essential element of modern ocean circulation and climate is the Atlantic meridional overturning circulation (AMOC), which includes deep-water formation in the subarctic North Atlantic. However, a comparable overturning circulation is absent in the Pacific, theworld’s largest ocean,where relatively fresh surface waters inhibitNorth Pacific deep convection. We present complementary measurement and modeling evidence that the warm, ~400–ppmv (parts per million by volume) CO 2 world of the Pliocene supported subarctic North Pacific deep-water formation and a Pacific meridional overturning circulation (PMOC) cell. In Pliocene subarctic North Pacific sediments, we report orbitally paced maxima in calcium carbonate accumulation rate, with accompanyingmore » pigment and total organic carbon measurements supporting deep-ocean ventilation-driven preservation as their cause. Together with high accumulation rates of biogenic opal, these findings require vigorous bidirectional communication between surface waters and interior waters down to ~3 km in the western subarctic North Pacific, implying deep convection. Redoxsensitive trace metal data provide further evidence of higher Pliocene deep-ocean ventilation before the 2.73-Ma (million years) transition. This observational analysis is supported by climate modeling results, demonstrating that atmospheric moisture transport changes, in response to the reduced meridional sea surface temperature gradients of the Pliocene, were capable of eroding the halocline, leading to deep-water formation in the western subarctic Pacific and a strong PMOC. This second Northern Hemisphere overturning cell has important implications for heat transport, the ocean/atmosphere cycle of carbon, and potentially the equilibrium response of the Pacific to global warming.« less

Active Pacific meridional overturning circulation (PMOC) during the warm Pliocene

PubMed Central

Burls, Natalie J.; Fedorov, Alexey V.; Sigman, Daniel M.; Jaccard, Samuel L.; Tiedemann, Ralf; Haug, Gerald H.

2017-01-01

An essential element of modern ocean circulation and climate is the Atlantic meridional overturning circulation (AMOC), which includes deep-water formation in the subarctic North Atlantic. However, a comparable overturning circulation is absent in the Pacific, the world’s largest ocean, where relatively fresh surface waters inhibit North Pacific deep convection. We present complementary measurement and modeling evidence that the warm, ~400–ppmv (parts per million by volume) CO2 world of the Pliocene supported subarctic North Pacific deep-water formation and a Pacific meridional overturning circulation (PMOC) cell. In Pliocene subarctic North Pacific sediments, we report orbitally paced maxima in calcium carbonate accumulation rate, with accompanying pigment and total organic carbon measurements supporting deep-ocean ventilation-driven preservation as their cause. Together with high accumulation rates of biogenic opal, these findings require vigorous bidirectional communication between surface waters and interior waters down to ~3 km in the western subarctic North Pacific, implying deep convection. Redox-sensitive trace metal data provide further evidence of higher Pliocene deep-ocean ventilation before the 2.73-Ma (million years) transition. This observational analysis is supported by climate modeling results, demonstrating that atmospheric moisture transport changes, in response to the reduced meridional sea surface temperature gradients of the Pliocene, were capable of eroding the halocline, leading to deep-water formation in the western subarctic Pacific and a strong PMOC. This second Northern Hemisphere overturning cell has important implications for heat transport, the ocean/atmosphere cycle of carbon, and potentially the equilibrium response of the Pacific to global warming. PMID:28924606

Active Pacific meridional overturning circulation (PMOC) during the warm Pliocene

DOE PAGES

Burls, Natalie J.; Fedorov, Alexey V.; Sigman, Daniel M.; ...

2017-09-13

An essential element of modern ocean circulation and climate is the Atlantic meridional overturning circulation (AMOC), which includes deep-water formation in the subarctic North Atlantic. However, a comparable overturning circulation is absent in the Pacific, theworld’s largest ocean,where relatively fresh surface waters inhibitNorth Pacific deep convection. We present complementary measurement and modeling evidence that the warm, ~400–ppmv (parts per million by volume) CO 2 world of the Pliocene supported subarctic North Pacific deep-water formation and a Pacific meridional overturning circulation (PMOC) cell. In Pliocene subarctic North Pacific sediments, we report orbitally paced maxima in calcium carbonate accumulation rate, with accompanyingmore » pigment and total organic carbon measurements supporting deep-ocean ventilation-driven preservation as their cause. Together with high accumulation rates of biogenic opal, these findings require vigorous bidirectional communication between surface waters and interior waters down to ~3 km in the western subarctic North Pacific, implying deep convection. Redoxsensitive trace metal data provide further evidence of higher Pliocene deep-ocean ventilation before the 2.73-Ma (million years) transition. This observational analysis is supported by climate modeling results, demonstrating that atmospheric moisture transport changes, in response to the reduced meridional sea surface temperature gradients of the Pliocene, were capable of eroding the halocline, leading to deep-water formation in the western subarctic Pacific and a strong PMOC. This second Northern Hemisphere overturning cell has important implications for heat transport, the ocean/atmosphere cycle of carbon, and potentially the equilibrium response of the Pacific to global warming.« less

Dendritic azo compounds as a new type amorphous molecular material with quick photoinduced surface-relief-grating formation ability

NASA Astrophysics Data System (ADS)

He, Yaning; Gu, Xinyu; Guo, Miaocai; Wang, Xiaogong

2008-09-01

A series of dendritic azobenzene-containing compounds have been synthesized as a new type amorphous molecular material, which can show quick surface-relief-grating (SRG) formation ability upon light irradiation. For the synthesis, the dendritic precursor tris(2-(ethyl(phenyl)amino)ethyl)benzene-1,3,5-tricarboxylate and tris(3,5-bis(2-(ethyl(phenyl)amino)ethoxy)benzyl)benzene-1,3,5-tricarboxylate were prepared by esterification reactions between 1,3,5-benzenetricarbonyl chloride and N-ethyl- N-hydroxyethyl-aniline and 3,5-bis[2-( N-ethylanilino)ethoxy] benzylalcohol. The precursors were, respectively reacted with the diazonium salts of 4-nitroaniline, 4-aminobenzoic acid, and 4-aminobenzonitrile to introduce different types of donor-acceptor azo chromophores at the peripheral positions. The structure and properties of the dendritic azo compounds were characterized by the spectroscopic methods and thermal analysis. The surface-relief-grating (SRG) formation behavior of the dendritic azo compounds was studied by exposing the spin-coated thin films to an interference pattern of laser beams (532 nm) at modest intensity (100 mW/cm 2). The results show that the azo compounds can form stable amorphous glasses in a broad temperature range. The glass transition temperatures ( Tgs) depend on the backbone structures and the type of the peripheral azo chromophors. The type of the electron withdrawing groups in the p-positions of the terminal azobenzene units shows a significant influence on the SRG inscription rate. For the compounds containing the same type azo chromophores, the SRG inscription rate is also affected by the backbone structure.

Ammonolysis of ketene as a potential source of acetamide in the troposphere: a quantum chemical investigation.

PubMed

Sarkar, Saptarshi; Mallick, Subhasish; Kumar, Pradeep; Bandyopadhyay, Biman

2018-05-16

Quantum chemical calculations at the CCSD(T)/CBS//MP2/aug-cc-pVTZ levels of theory have been carried out to investigate a potential new source of acetamide in Earth's atmosphere through the ammonolysis of the simplest ketene. It was found that the reaction can occur via the addition of ammonia at either the C[double bond, length as m-dash]C or C[double bond, length as m-dash]O bond of ketene. The potential energy surface as well as calculated rate coefficients indicate that under tropospheric conditions, ammonolysis would occur almost exclusively via ammonia addition at the C[double bond, length as m-dash]O bond with negligible contribution from addition at the C[double bond, length as m-dash]C bond. The reaction of ketene with water has also been investigated in order to compare between hydrolysis and ammonolysis, as the former is known to be responsible for the formation of acetic acid. The rate coefficient for the formation of acetamide was found to be ∼106 to 109 times higher than that for the formation of acetic acid from the same ketene source in the troposphere. By means of the relative rate of ammonolysis with respect to hydrolysis, it was shown that acetamide formation would dominate over acetic acid formation at various altitudes in the troposphere.

Past and future star formation in disk galaxies

NASA Astrophysics Data System (ADS)

Kennicutt, Robert C., Jr.; Tamblyn, Peter; Congdon, Charles E.

1994-11-01

We have combined H-alpha and UBV measurements of 210 nearby Sa-Irr galaxies with new photometric synthesis models to reanalyze the past and future star formation timescales in disks. The integrated photoionization rates and colors of disks are best fitted by a stellar initial mass function (IMF) which is enriched in massive stars by a factor of 2-3 relative to the Scalo solar neighborhood IMF. We have used published surface photometry of spiral galaxies to analyze the star formation histories of disks independent of their bulge properties. The ratio of the current star formation rate (SFR) to the average past rate increases from of order 0.01 in Sa galaxies to 1 in Sc-Irr disks. This confirms that the pronounced change in the photometric properties of spiral galaxies along the Hubble sequence is predominantly due to changes in the star formation histories of disks, and only secondarily to changes in the bulge/disk ratio. A comparison of current SFRs and gas masses of the sample yields median timescales for gas consumption of approximately 3 Gyr, in the absence of stellar recycling. However, a proper time-dependent treatment of the gas return from stars shows that recycling extends the gas lifetimes of disks by factors of 1.5-4 for typical disk parameters. Consequently the current SFRs in many (but not all) disks can be sustained for periods comparable to the Hubble time.

Mineralogy and cooling history of magnesian lunar granulite 67415

NASA Technical Reports Server (NTRS)

Takeda, Hiroshi; Miyamoto, Masamichi

1993-01-01

Apollo granulite 67415 was investigated by mineralogical techniques to gain better understanding of cooling histories of lunar granulities. Cooling rates were estimated from chemical zoning of olivines in magnesian granulitic clasts by computer simulation of diffusion processes. The cooling rate of 10 deg C/yr obtained is compatible with a model of the granulite formation, in which the impact deposit was cooled from high temperature or annealed, at the depth of about 25 m beneath the surface.

Why do gelatinized starch granules not dissolve completely? Roles for amylose, protein, and lipid in granule "ghost" integrity.

PubMed

Debet, Martine R; Gidley, Michael J

2007-06-13

After gelatinization in water, starch granules persist in swollen hydrated forms known as ghosts. Three potential mechanisms for ghost formation are tested. Proteins and lipids on the granule surface are found to be a determinant of ghost robustness, but not ghost formation. Proteins inside pre-made maize or wheat starch ghosts are degraded extensively by proteases without any apparent change in ghost properties, making an internal protein cross-linking mechanism unlikely. Waxy maize mutants with a range of amylose contents have ghost integrities that correlate with (low) apparent amylose levels. It is hypothesized that ghost formation is due to cross-linking of polysaccharide chains within swollen granules, most likely involving double helices formed from polymer chains that become free to move following heat-induced granule swelling. The size and robustness of granule ghosts is proposed to be determined by the relative rates of swelling and cross-linking, modulated by surface non-polysaccharide components.

In situ nanoscale observations of gypsum dissolution by digital holographic microscopy.

PubMed

Feng, Pan; Brand, Alexander S; Chen, Lei; Bullard, Jeffrey W

2017-06-01

Recent topography measurements of gypsum dissolution have not reported the absolute dissolution rates, but instead focus on the rates of formation and growth of etch pits. In this study, the in situ absolute retreat rates of gypsum (010) cleavage surfaces at etch pits, at cleavage steps, and at apparently defect-free portions of the surface are measured in flowing water by reflection digital holographic microscopy. Observations made on randomly sampled fields of view on seven different cleavage surfaces reveal a range of local dissolution rates, the local rate being determined by the topographical features at which material is removed. Four characteristic types of topographical activity are observed: 1) smooth regions, free of etch pits or other noticeable defects, where dissolution rates are relatively low; 2) shallow, wide etch pits bounded by faceted walls which grow gradually at rates somewhat greater than in smooth regions; 3) narrow, deep etch pits which form and grow throughout the observation period at rates that exceed those at the shallow etch pits; and 4) relatively few, submicrometer cleavage steps which move in a wave-like manner and yield local dissolution fluxes that are about five times greater than at etch pits. Molar dissolution rates at all topographical features except submicrometer steps can be aggregated into a continuous, mildly bimodal distribution with a mean of 3.0 µmolm -2 s -1 and a standard deviation of 0.7 µmolm -2 s -1 .

Hydroxyapatite formation on titania-based materials in a solution mimicking body fluid: Effects of manganese and iron addition in anatase.

PubMed

Shin, Euisup; Kim, Ill Yong; Cho, Sung Baek; Ohtsuki, Chikara

2015-03-01

Hydroxyapatite formation on the surfaces of implanted materials plays an important role in osteoconduction of bone substitutes in bone tissues. Titania hydrogels are known to instigate hydroxyapatite formation in a solution mimicking human blood plasma. To date, the relationship between the surface characteristics of titania and hydroxyapatite formation on its surface remains unclear. In this study, titania powders with varying surface characteristics were prepared by addition of manganese or iron to examine hydroxyapatite formation in a type of simulated body fluid (Kokubo solution). Hydroxyapatite formation was monitored by observation of deposited particles with scale-like morphology on the prepared titania powders. The effect of the titania surface characteristics, i.e., crystal structure, zeta potential, hydroxy group content, and specific surface area, on hydroxyapatite formation was examined. Hydroxyapatite formation was observed on the surface of titania powders that were primarily anatase, and featured a negative zeta potential and low specific surface areas irrespective of the hydroxy group content. High specific surface areas inhibited the formation of hydroxyapatite because calcium and phosphate ions were mostly consumed by adsorption on the titania surface. Thus, these surface characteristics of titania determine its osteoconductivity following exposure to body fluid. Copyright © 2014 Elsevier B.V. All rights reserved.

Multiscale Investigation on Biofilm Distribution and Its Impact on Macroscopic Biogeochemical Reaction Rates: BIOFILM DISTRIBUTION AND RATE SCALING

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Zhifeng; Liu, Chongxuan; Liu, Yuanyuan

Biofilms are critical locations for biogeochemical reactions in the subsurface environment. The occurrence and distribution of biofilms at microscale as well as their impacts on macroscopic biogeochemical reaction rates are still poorly understood. This paper investigated the formation and distributions of biofilms in heterogeneous sediments using multiscale models, and evaluated the effects of biofilm heterogeneity on local and macroscopic biogeochemical reaction rates. Sediment pore structures derived from X-ray computed tomography were used to simulate the microscale flow dynamics and biofilm distribution in the sediment column. The response of biofilm formation and distribution to the variations in hydraulic and chemical propertiesmore » was first examined. One representative biofilm distribution was then utilized to evaluate its effects on macroscopic reaction rates using nitrate reduction as an example. The results revealed that microorganisms primarily grew on the surfaces of grains and aggregates near preferential flow paths where both electron donor and acceptor were readily accessible, leading to the heterogeneous distribution of biofilms in the sediments. The heterogeneous biofilm distribution decreased the macroscopic rate of biogeochemical reactions as compared with those in homogeneous cases. Operationally considering the heterogeneous biofilm distribution in macroscopic reactive transport models such as using dual porosity domain concept can significantly improve the prediction of biogeochemical reaction rates. Overall, this study provided important insights into the biofilm formation and distribution in soils and sediments as well as their impacts on the macroscopic manifestation of reaction rates.« less

Solidification observations and sliding wear behavior of vacuum arc melting processed Ni-Al-TiC composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karantzalis, A.E., E-mail: akarantz@cc.uoi.gr; Lekatou, A.; Tsirka, K.

2012-07-15

Monolithic Ni{sub 3}Al and Ni-25 at.%Al intermetallic matrix TiC-reinforced composites were successfully produced by vacuum arc melting. TiC crystals were formed through a dissolution-reprecipitation mechanism and their final morphology is explained by means of a) Jackson's classical nucleation and growth phenomena and b) solidification rate considerations. The TiC presence altered the matrix microconstituents most likely due to specific melt-particle interactions and crystal plane epitaxial matching. TiC particles caused a significant decrease on the specific wear rate of the monolithic Ni{sub 3}Al alloy and the possible wear mechanisms are approached by means of a) surface oxidation, b) crack/flaws formation, c) materialmore » detachment and d) debris-counter surfaces interactions. - Highlights: Black-Right-Pointing-Pointer Vacuum arc melting (VAM) of Ni-Al based intermetallic matrix composite materials. Black-Right-Pointing-Pointer Solidification phenomena examination. Black-Right-Pointing-Pointer TiC crystal formation and growth mechanisms. Black-Right-Pointing-Pointer Sliding wear examination.« less

Formation of the prebiotic molecule NH2CHO on astronomical amorphous solid water surfaces: accurate tunneling rate calculations.

PubMed

Song, Lei; Kästner, Johannes

2016-10-26

Investigating how formamide forms in the interstellar medium is a hot topic in astrochemistry, which can contribute to our understanding of the origin of life on Earth. We have constructed a QM/MM model to simulate the hydrogenation of isocyanic acid on amorphous solid water surfaces to form formamide. The binding energy of HNCO on the ASW surface varies significantly between different binding sites, we found values between ∼0 and 100 kJ mol -1 . The barrier for the hydrogenation reaction is almost independent of the binding energy, though. We calculated tunneling rate constants of H + HNCO → NH 2 CO at temperatures down to 103 K combining QM/MM with instanton theory. Tunneling dominates the reaction at such low temperatures. The tunneling reaction is hardly accelerated by the amorphous solid water surface compared to the gas phase for this system, even though the activation energy of the surface reaction is lower than the one of the gas-phase reaction. Both the height and width of the barrier affect the tunneling rate in practice. Strong kinetic isotope effects were observed by comparing to rate constants of D + HNCO → NHDCO. At 103 K we found a KIE of 231 on the surface and 146 in the gas phase. Furthermore, we investigated the gas-phase reaction NH 2 + H 2 CO → NH 2 CHO + H and found it unlikely to occur at cryogenic temperatures. The data of our tunneling rate constants are expected to significantly influence astrochemical models.

Outstanding resistance and passivation behaviour of new Fe-Co metal-metal glassy alloys in alkaline media

PubMed Central

Al-Harbi, Albandaree K.

2018-01-01

The electrochemical behavior of the oxide layers on two metal-metal glassy alloys, Fe78Co9Cr10Mo2Al1 (VX9)and Fe49Co49V2 (VX50) (at.%), were studied using electrochemical techniques including electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) measurements. The morphology and composition of the alloy surfaces were investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion rate and surface roughness of both alloys increased as the concentration of NaOH in aqueous solution was raised. The presence of some protective elements in the composition of the alloys led to the formation of a spontaneous passive layer on the alloy surface. The higher resistance values of both alloys were associated with the magnitude of the dielectric properties of the passive films formed on their surfaces. Both alloys are classified as having outstanding resistance to corrosion, which results from the formation of a passive film that acts as an efficient barrier to corrosion in alkaline solution. PMID:29337992

Outstanding resistance and passivation behaviour of new Fe-Co metal-metal glassy alloys in alkaline media.

PubMed

Emran, Khadijah M; Al-Harbi, Albandaree K

2018-01-01

The electrochemical behavior of the oxide layers on two metal-metal glassy alloys, Fe78Co9Cr10Mo2Al1 (VX9)and Fe49Co49V2 (VX50) (at.%), were studied using electrochemical techniques including electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) measurements. The morphology and composition of the alloy surfaces were investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion rate and surface roughness of both alloys increased as the concentration of NaOH in aqueous solution was raised. The presence of some protective elements in the composition of the alloys led to the formation of a spontaneous passive layer on the alloy surface. The higher resistance values of both alloys were associated with the magnitude of the dielectric properties of the passive films formed on their surfaces. Both alloys are classified as having outstanding resistance to corrosion, which results from the formation of a passive film that acts as an efficient barrier to corrosion in alkaline solution.

Plasma Surface Modification for Immobilization of Bone Morphogenic Protein-2 on Polycaprolactone Scaffolds

NASA Astrophysics Data System (ADS)

Kim, Byung Hoon; Myung, Sung Woon; Jung, Sang Chul; Ko, Yeong Mu

2013-11-01

The immobilization of recombinant human bone formation protein-2 (rhBMP-2) on polycaprolactone (PCL) scaffolds was performed by plasma polymerization. RhBMP-2, which induces osteoblast differentiation in various cell types, is a growth factor that plays an important role in bone formation and repair. The surface of the PCL scaffold was functionalized with the carboxyl groups of plasma-polymerized acrylic acid (PPAA) thin films. Plasma polymerization was carried out at a discharge power of 60 W at an acrylic acid flow rate of 7 sccm for 5 min. The PPAA thin film exhibited moderate hydrophilic properties and possessed a high density of carboxyl groups. Carboxyl groups and rhBMP-2 on the PCL scaffolds surface were identified by attenuated total reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, respectively. The alkaline phosphatase activity assay showed that the rhBMP-2 immobilized PCL scaffold increased the level of MG-63 cell differentiation. Plasma surface modification for the preparation of biomaterials, such as biofunctionalized polymer scaffolds, can be used for the binding of bioactive molecules in tissue engineering.

The stratigraphic filter and bias in measurement of geologic rates

USGS Publications Warehouse

Schumer, Rina; Jerolmack, Douglas; McElroy, Brandon

2011-01-01

Erosion and deposition rates estimated from the stratigraphic record frequently exhibit a power-law dependence on measurement interval. This dependence can result from a power-law distribution of stratigraphic hiatuses. By representing the stratigraphic filter as a stochastic process called a reverse ascending ladder, we describe a likely origin of power-law hiatuses, and thus, rate scaling. While power-law hiatuses in certain environments can be a direct result of power-law periods of stasis (no deposition or erosion), they are more generally the result of randomness in surface fluctuations irrespective of mean subsidence or uplift. Autocorrelation in fluctuations can make hiatuses more or less heavy-tailed, but still exhibit power-law characteristics. In addition we show that by passing stratigraphic data backward through the filter, certain statistics of surface kinematics from their formative environments can be inferred.

Investigations of the Formation of Molecular Hydrogen on Dust Grain Analogues

NASA Technical Reports Server (NTRS)

Vidali, Gianfranco; Roser, Joseph E.; Manico, Giulio; Pirronello, Valerio

2002-01-01

In the last four years we have been working to investigate the formation of molecular hydrogen on surfaces of materials of astrophysical interest, such as silicates, carbonaceous particles and ices, and in conditions approximating the ones present in a variety of astrophysical environments. Our experimental studies - the first of their kind and complemented with computer simulations and theoretical analyses - have given not only hydrogen recombination rates under different ISM conditions, but they have also offered new insights into this fundamental astrophysical problem. Here we summarize our experimental methods and most significant results.

The effect of butterfly-scale inspired patterning on leading-edge vortex growth

NASA Astrophysics Data System (ADS)

Wilroy, Jacob Aaron

Leading edge vortices (LEVs) are important for generating thrust and lift in flapping flight, and the surface patterning (scales) on butterfly wings is hypothesized to play a role in the vortex formation of the LEV. To simplify this complex flow problem, an experiment was designed to focus on the alteration of 2-D vortex development with a variation in surface patterning. Specifically, the secondary vorticity generated by the LEV interacting at the patterned surface was studied, as well as the subsequent effect on the LEV's growth rate and peak circulation. For this experiment, rapid-prototyped grooves based on the scale geometry of the Monarch butterfly (Danaus plexippus) were created using additive manufacturing and were attached to a flat plate with a chordwise orientation, thus increasing plate surface area. The vortex generated by the grooved plate was then compared to a smooth plate case in an experiment where the plate translated vertically through a 2 x 3 x 5 cubic foot tow tank. The plate was impulsively started in quiescent water and flow fields at Rec = 1416, 2833, and 5667 are examined using Digital Particle Image Velocimetry (DPIV). The maximum vortex formation number is 2.8 and is based on the flat plate travel length and chord length. Flow fields from each case show the generation of a secondary vortex whose interaction with the shear layer and LEV caused different behaviors depending upon the surface type. The vortex development process varied for each Reynolds number and it was found that for the lowest Reynolds number case a significant difference does not exist between surface types, however, for the other two cases the grooves affected the secondary vortex's behavior and the LEV's ability to grow at a rate similar to the smooth plate case.

The linking of the upper-middle and lower reaches of the Yellow River as a result of fluvial entrenchment

NASA Astrophysics Data System (ADS)

Hu, ZhenBo; Pan, BaoTian; Bridgland, David; Vandenberghe, Jef; Guo, LianYong; Fan, YunLong; Westaway, Rob

2017-06-01

The upper-middle Yellow River flows through the Fenwei graben, a structure resulting from extensional tectonism that was formed and repeatedly extended during the Cenozoic. The drainage system within this graben was formerly isolated from the lower reaches of the Yellow River system by the Xiaoshan mountains, an actively growing ∼ NW-SE trending range. The modern course of the Yellow River takes it through this range along the Sanmen gorge, the formation of which was of great significance in that it initiated through-going drainage between the upper-middle and lower reaches of the system. The timing of this event, which was clearly a critical point in the evolution of the Yellow River, can be established by dating the terraces in the gorge. Intermittent deepening of this gorge by the Yellow River from a high-level planation surface capping the mountain range has resulted in the formation of five terraces. Magnetostratigraphic records from aeolian deposits accumulated on these surfaces provide a geochronological sequence for this geomorphic archive, in which the ages of the planation surface and of terraces T5, T4, T3, T2, and T1 have been determined as ∼3.63 Ma, ∼1.24 Ma, ∼0.86 Ma, ∼0.62 Ma, ∼129 ka, and ∼12 ka, respectively. Under the constraint of this chronological framework, a model for landscape evolution is proposed here. Uplift of the inner Fenwei graben and of the surrounding mountain ranges led to dissection of the 3.63 Ma old planation surface in conjunction with the formation of the Sanmen gorge. Drainage of the lake previously occupying the basin would have promoted incision into the fluvio-lacustrine graben sediments; indeed, gorge formation through the Xiaoshan may have been initiated or intensified by lake overflow. The ages obtained for the planation surface and uppermost terrace suggest that the formation of the Sanmen gorge and the initiation of the through-going eastward drainage of the Yellow River occurred between 3.63 and 1.24 Ma. Before the start of gorge entrenchment, the products of erosion in the modern upper catchment of the Yellow River were unable to reach the sea. The dramatic increase in deposition rates in the Bohai Gulf (at the mouth of the modern Yellow River in the East China Sea), ∼1.0 Ma ago, thus resulted from the initiation of an integral (enlarged) Yellow River catchment drainage through the Sanmen gorge; it does not imply an increase in erosion rates at that time.

SOA formation potential of emissions from soil and leaf litter.

PubMed

Faiola, Celia L; Vanderschelden, Graham S; Wen, Miao; Elloy, Farah C; Cobos, Douglas R; Watts, Richard J; Jobson, B Thomas; Vanreken, Timothy M

2014-01-21

Soil and leaf litter are significant global sources of small oxidized volatile organic compounds, VOCs (e.g., methanol and acetaldehyde). They may also be significant sources of larger VOCs that could act as precursors to secondary organic aerosol (SOA) formation. To investigate this, soil and leaf litter samples were collected from the University of Idaho Experimental Forest and transported to the laboratory. There, the VOC emissions were characterized and used to drive SOA formation via dark, ozone-initiated reactions. Monoterpenes dominated the emission profile with emission rates as high as 228 μg-C m(-2) h(-1). The composition of the SOA produced was similar to biogenic SOA formed from oxidation of ponderosa pine emissions and α-pinene. Measured soil and litter monoterpene emission rates were compared with modeled canopy emissions. Results suggest surface soil and litter monoterpene emissions could range from 12 to 136% of canopy emissions in spring and fall. Thus, emissions from leaf litter may potentially extend the biogenic emissions season, contributing to significant organic aerosol formation in the spring and fall when reduced solar radiation and temperatures reduce emissions from living vegetation.

Short-term effects of growth hormone and insulin-like growth factor I on cancellous bone in rhesus macaque monkeys.

PubMed

Sass, D A; Jerome, C P; Bowman, A R; Bennett-Cain, A; Ginn, T A; LeRoith, D; Epstein, S

1997-04-01

The purpose of our study was to determine the effects of GH and insulin-like growth factor I (IGF-I) administration singly and in combination on vertebral, tibial, and femoral bone in aged female monkeys as well as the various treatment effects on serum hormone levels and osteocalcin gene expression. Twenty-one ovulating female monkeys (rhesus macaque), aged 16-20 yr (5-6 kg), were divided into four groups to receive the following treatment for 7 weeks via Alzet pumps inserted sc: A, eluant (control group); B, recombinant human IGF-I (rhIGF-I; 120 micrograms/kg.day); C) rhGH (100 micrograms/kg.day); D, combination of rhIGF-I (120 micrograms/kg.day) and rhGH (100 micrograms/kg.day). Serum was assayed serially for glucose, IGF-I, GH, and IGF-binding protein-3 levels. All groups received double labeling with calcein. On the day of death, the primates' second lumbar vertebrae, tibiae, and femora were carefully dissected, fixed in 70% ethanol, and subjected to histomorphometric analysis. Ribonucleic acid was extracted from contralateral tibiae for the purpose of osteocalcin gene expression analysis. Serum glucose was unaffected by treatment. Serum GH was significantly elevated in groups C and D, whereas serum IGF-I and IGFBP-3 were only significantly increased in group D. Histomorphometric analysis showed no significant differences or trends for bone volume in any treatment group. Bone formation rate, surface and/or bone volume referent were significantly higher in both groups treated with GH (C and D) in tibia and femur, with a similar trend in vertebrae. The increase in bone formation rate was due mainly to a significant increase in mineral apposition rate, but there was also an increase in tibial mineralizing surface by GH by factorial analysis (P < 0.05). There were significant treatment effects on osteoid surface and osteoclastic surface in femur in the combination treatment group vs. the controls. Osteocalcin gene expression analysis supported an enhanced expression in both groups treated with GH. These findings are consistent with a short term effect of GH to increase bone remodeling and predominantly osteoblastic activity in the appendicular skeleton. In contrast, other than an isolated increase in osteoclastic surface in femoral bone, IGF-I, when administered alone, was unable to significantly influence bone formation or resorption activity in this short term study.

Film depth and concentration banding in free-surface Couette flow of a suspension.

PubMed

Timberlake, Brian D; Morris, Jeffrey F

2003-05-15

The film depth of a free-surface suspension flowing in a partially filled horizontal concentric-cylinder, or Couette, device has been studied in order to assess its role in the axial concentration banding observed in this flow. The flow is driven by rotation of the inner cylinder. The banding phenomenon is characterized by particle-rich bands which under flow appear as elevated regions at the free surface separated axially by regions dilute relative to the mean concentration. The concentric cylinders studied had outer radius R(o) = 2.22 cm and inner radii R(i) = 0.64, 0.95 and 1.27 cm; the suspension, of bulk particle volume fraction phi = 0.2 in all experiments described, was composed of particles of either 250-300 microm diameter or less than 106 microm diameter, with the suspending fluid an equal density liquid of viscosity 160 P. The ratio of the maximum to the minimum particle volume fraction along the axis in the segregated condition varies from O(1) to infinite. The latter case implies complete segregation, with bands of clear fluid separating the concentrated bands. The film depth has been varied through variation of the filled fraction, f, of the annular gap between the cylinders and through the rotation rate. Film depth was analysed by edge detection of video images of the free surface under flow, and the time required for band formation was determined for all conditions at which film depth was studied. The film depth increases roughly as the square root of rotation speed for f = 0.5. Band formation is more rapid for thicker films associated with more rapid rotation rates at f = 0.5, whereas slower formation rates are observed with thicker films caused by large f, f > 0.65. It is observed that the film depth over the inner cylinder grows prior to onset of banding, for as yet unknown reasons. A mechanism for segregation of particles and liquid in film flows based upon 'differential drainage' of the particle and liquid phase in the gravity-driven flow within the film over the inner cylinder is formulated to describe the onset of concentration fluctuations. This model predicts that suspension drainage flows lead to growth of fluctuations in phi under regions of negative surface curvature.

Global trends in peatland methane production

NASA Astrophysics Data System (ADS)

Hoyt, A.; Corbett, J. E.; Gandois, L.; Cobb, A.; Pangala, S. R.; Gauci, V.; Harvey, C. F.

2017-12-01

Peatland methane production rates and fluxes to the atmosphere vary globally. Here we present a systematic comparison of peatland CH4 production across latitudes. We developed and applied an isotope-based mass transport model to characterize rates of methanogenesis and recharge rates across ten ombrotrophic peatlands from around the world. We validated our model against peat incubations and surface fluxes where data was available. We found striking similarities in the DIC and CH4 concentrations and δ13C isotope profiles across northern bogs, despite highly variable precipitation, recharge rates, and peat characteristics. Profiles from northern sites were similar because increased recharge rates were always compensated by increased CH4 production rates. This could represent a feedback mechanism between recharge rates and methanogenesis in northern bogs or could represent a shared dependence of these two properties on the degree of peat decomposition. We also found strong differences between northern and tropical sites, both in the rate of CH4 production, the recharge rate, and in the transport pathways and fluxes to the atmosphere. Our findings have important implications for methane transport and release to the atmosphere. In northern bogs, low flow rates allow CH4 concentrations to build up, and CH4 escapes by surface diffusion, ebullition, and plant-mediated transport. Thus, the majority of CH4 produced escapes through the peat surface. In tropical peatlands, high flow rates suppress CH4 concentrations, which do not build up above the threshold for ebullition. Instead, CH4 leaves the peat by lateral transport and surface fluxes are small. This work provides evidence that peat properties and hydrology are fundamental controls on decomposition, CH4 production, and peat formation across latitudes.

Hydrological responses to channelization and the formation of valley plugs and shoals

USGS Publications Warehouse

Pierce, Aaron R.; King, Sammy L.

2017-01-01

Rehabilitation of floodplain systems focuses on restoring interactions between the fluvial system and floodplain, however, there is a paucity of information on the effects of valley plugs and shoals on floodplain hydrological processes. We investigated hydrologic regimes in floodplains at three valley plug sites, two shoal sites, and three unchannelized sites. Valley plug sites had altered surface and sub-surface hydrology relative to unchannelized sites, while only sub-surface hydrology was affected at shoal sites. Some of the changes were unexpected, such as reduced flood duration and flood depth in floodplains associated with valley plugs. Our results emphasize the variability associated with hydrologic processes around valley plugs and our rudimentary understanding of the effects associated with these geomorphic features. Water table levels were lower at valley plug sites compared to unchannelized sites, however, valley plug sites had a greater proportion of days when water table inundation was above mean root collar depth than both shoal and unchannelized sites as a result of lower root collar depths and higher deposition rates. This study has provided evidence that valley plugs can affect both surface and sub-surface hydrology in different ways than previously thought and illustrates the variability in hydrological responses to valley plug formation.

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

NASA Astrophysics Data System (ADS)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

Surface monofunctionalized polymethyl pentene hollow fiber membranes by plasma treatment and hemocompatibility modification for membrane oxygenators

NASA Astrophysics Data System (ADS)

Huang, Xin; Wang, Weiping; Zheng, Zhi; Fan, Wenling; Mao, Chun; Shi, Jialiang; Li, Lei

2016-01-01

The hemocompatibility of polymethyl pentene (PMP) hollow fiber membranes (HFMs) was improved through surface modification for membrane oxygenator applications. The modification was performed stepwise with the following: (1) oxygen plasma treatment, (2) functionalization of monosort hydroxyl groups through NaBH4 reduction, and (3) grafting 2-methacryloyloxyethyl phosphorylcholine (MPC) or heparin. SEM, ATR-FTIR, and XPS analyses were conducted to confirm successful grafting during the modification. The hemocompatibility of PMP HFMs was analyzed and compared through protein adsorption, platelet adhesion, and coagulation tests. Pure CO2 and O2 permeation rates, as well as in vitro gas exchange rates, were determined to evaluate the mass transfer properties of PMP HFMs. SEM results showed that different nanofibril topographies were introduced on the HFM surface. ATR-FTIR and XPS spectra indicated the presence of functionalization of monosort hydroxyl group and the grafting of MPC and heparin. Hemocompatibility evaluation results showed that the modified PMP HFMs presented optimal hemocompatibility compared with pristine HFMs. Gas permeation results revealed that gas permeation flux increased in the modified HFMs because of dense surface etching during the plasma treatment. The results of in vitro gas exchange rates showed that all modified PMP HFMs presented decreased gas exchange rates because of potential surface fluid wetting. The proposed strategy exhibits a potential for fabricating membrane oxygenators for biomedical applications to prevent coagulation formation and alter plasma-induced surface topology and composition.

SDSS IV MaNGA: Deep observations of extra-planar, diffuse ionized gas around late-type galaxies from stacked IFU spectra

NASA Astrophysics Data System (ADS)

Jones, A.; Kauffmann, G.; D'Souza, R.; Bizyaev, D.; Law, D.; Haffner, L.; Bahé, Y.; Andrews, B.; Bershady, M.; Brownstein, J.; Bundy, K.; Cherinka, B.; Diamond-Stanic, A.; Drory, N.; Riffel, R. A.; Sánchez, S. F.; Thomas, D.; Wake, D.; Yan, R.; Zhang, K.

2017-03-01

We have conducted a study of extra-planar diffuse ionized gas using the first year data from the MaNGA IFU survey. We have stacked spectra from 49 edge-on, late-type galaxies as a function of distance from the midplane of the galaxy. With this technique we can detect the bright emission lines Hα, Hβ, [O II]λλ3726, 3729, [O III]λ5007, [N II]λλ6549, 6584, and [S II]λλ6717, 6731 out to about 4 kpc above the midplane. With 16 galaxies we can extend this analysis out to about 9 kpc, I.e. a distance of 2Re, vertically from the midplane. In the halo, the surface brightnesses of the [O II] and Hα emission lines are comparable, unlike in the disk where Hα dominates. When we split the sample by specific star-formation rate, concentration index, and stellar mass, each subsample's emission line surface brightness profiles and ratios differ, indicating that extra-planar gas properties can vary. The emission line surface brightnesses of the gas around high specific star-formation rate galaxies are higher at all distances, and the line ratios are closer to ratios characteristic of H II regions compared with low specific star-formation rate galaxies. The less concentrated and lower stellar mass samples exhibit line ratios that are more like H II regions at larger distances than their more concentrated and higher stellar mass counterparts. The largest difference between different subsamples occurs when the galaxies are split by stellar mass. We additionally infer that gas far from the midplane in more massive galaxies has the highest temperatures and steepest radial temperature gradients based on their [N II]/Hα and [O II]/Hα ratios between the disk and the halo. SDSS IV.

The role of advanced reactive surface area characterization in improving predictions of mineral reaction rates

NASA Astrophysics Data System (ADS)

Beckingham, L. E.; Zhang, S.; Mitnick, E.; Cole, D. R.; Yang, L.; Anovitz, L. M.; Sheets, J.; Swift, A.; Kneafsey, T. J.; Landrot, G.; Mito, S.; Xue, Z.; Steefel, C. I.; DePaolo, D. J.; Ajo Franklin, J. B.

2014-12-01

Geologic sequestration of CO2 in deep sedimentary formations is a promising means of mitigating carbon emissions from coal-fired power plants but the long-term fate of injected CO2 is challenging to predict. Reactive transport models are used to gain insight over long times but rely on laboratory determined mineral reaction rates that have been difficult to extrapolate to field systems. This, in part, is due to a lack of understanding of mineral reactive surface area. Many models use an arbitrary approximation of reactive surface area, applying orders of magnitude scaling factors to measured BET or geometric surface areas. Recently, a few more sophisticated approaches have used 2D and 3D image analyses to determine mineral-specific reactive surface areas that account for the accessibility of minerals. However, the ability of these advanced surface area estimates to improve predictions of mineral reaction rates has yet to be determined. In this study, we fuse X-ray microCT, SEM QEMSCAN, XRD, SANS, and SEM-FIB analysis to determine mineral-specific accessible reactive surface areas for a core sample from the Nagaoka pilot CO2 injection site (Japan). This sample is primarily quartz, plagioclase, smectite, K-feldspar, and pyroxene. SEM imaging shows abundant smectite cement and grain coatings that decrease the fluid accessibility of other minerals. However, analysis of FIB-SEM images reveals that smectite nano-pores are well connected such that access to underlying minerals is not occluded by smectite coatings. Mineral-specific accessible surfaces are determined, accounting for the connectivity of the pore space with and without connected smectite nano-pores. The large-scale impact of variations in accessibility and dissolution rates are then determined through continuum scale modeling using grid-cell specific information on accessible surface areas. This approach will be compared with a traditional continuum scale model using mineral abundances and common surface area estimates. Ultimately, the effectiveness of advanced surface area characterization to improve mineral dissolution rates will be evaluated by comparison of model results with dissolution rates measured from a flow-through column experiment.

Surface roughening of undoped and in situ B-doped SiGe epitaxial layers deposited by using reduced pressure chemical vapor deposition

NASA Astrophysics Data System (ADS)

Kim, Youngmo; Park, Jiwoo; Sohn, Hyunchul

2018-01-01

Si1- x Ge x (:B) epitaxial layers were deposited by using reduced pressure chemical vapor deposition with SiH4, GeH4, and B2H6 source gases, and the dependences of the surface roughness of undoped Si1- x Ge x on the GeH4 flow rate and of Si1- x Ge x :B on the B2H6 flow rate were investigated. The root-mean-square (RMS) roughness value of the undoped Si1- x Ge x at constant thickness increased gradually with increasing Ge composition, resulting from an increase in the amplitude of the wavy surface before defect formation. At higher Ge compositions, the residual strain in Si1- x Ge x significantly decreased through the formation of defects along with an abrupt increase in the RMS roughness. The variation of the surface roughness of Si1- x Ge x :B depended on the boron (B) concentration. At low B concentrations, the RMS roughness of Si1- x Ge x remained constant regardless of Ge composition, which is similar to that of undoped Si1- x Ge x . However, at high B concentrations, the RMS roughness of Si1- x Ge x :B increased greatly due to B islanding. In addition, at very high B concentrations ( 9.9 at%), the RMS roughness of Si1- x Ge x :B decreased due to non-epitaxial growth.

Surface chemistry associated with the cooling and subaerial weathering of recent basalt flows

USGS Publications Warehouse

White, A.F.; Hochella, M.F.

1992-01-01

The surface chemistry of fresh and weathered historical basalt flows was characterized using surface-sensitive X-ray photoelectron spectroscopy (XPS). Surfaces of unweathered 1987-1990 flows from the Kilauea Volcano, Hawaii, exhibited variable enrichment in Al, Mg, Ca, and F due to the formation of refractory fluoride compounds and pronounced depletion in Si and Fe from the volatilization of SiF4 and FeF3 during cooling. These reactions, as predicted from shifts in thermodynamic equilibrium with temperature, are induced by diffusion of HF from the flow interiors to the cooling surface. The lack of Si loss and solid fluoride formation for recent basalts from the Krafla Volcano, Iceland, suggest HF degassing at higher temperatures. Subsequent short-term subaerial weathering reactions are strongly influenced by the initial surface composition of the flow and therefore its cooling history. Successive samples collected from the 1987 Kilauea flow demonstrated that the fluoridated flow surfaces leached to a predominantly SiO2 composition by natural weathering within one year. These chemically depleted surfaces were also observed on Hawaiian basalt flows dating back to 1801 AD. Solubility and kinetic models, based on thermodynamic and kinetic data for crystalline AlF3, MgF2, and CaF2, support observed elemental depletion rates due to chemical weathering. Additional loss of alkalis from the Hawaiian basalt occurs from incongruent dissolution of the basalt glass substrate during weathering. ?? 1992.

A model for the origin of bursty star formation in galaxies

NASA Astrophysics Data System (ADS)

Faucher-Giguère, Claude-André

2018-01-01

We propose a simple analytic model to understand when star formation is time steady versus bursty in galaxies. Recent models explain the observed Kennicutt-Schmidt relation between star formation rate and gas surface densities in galaxies as resulting from a balance between stellar feedback and gravity. We argue that bursty star formation occurs when such an equilibrium cannot be stably sustained, and identify two regimes in which galaxy-scale star formation should be bursty: (i) at high redshift (z ≳ 1) for galaxies of all masses, and (ii) at low masses (depending on gas fraction) for galaxies at any redshift. At high redshift, characteristic galactic dynamical time-scales become too short for supernova feedback to effectively respond to gravitational collapse in galactic discs (an effect recently identified for galactic nuclei), whereas in dwarf galaxies star formation occurs in too few bright star-forming regions to effectively average out. Burstiness is also enhanced at high redshift owing to elevated gas fractions in the early Universe. Our model can thus explain the bursty star formation rates predicted in these regimes by recent high-resolution galaxy formation simulations, as well as the bursty star formation histories observationally inferred in both local dwarf and high-redshift galaxies. In our model, bursty star formation is associated with particularly strong spatiotemporal clustering of supernovae. Such clustering can promote the formation of galactic winds and our model may thus also explain the much higher wind mass loading factors inferred in high-redshift massive galaxies relative to their z ∼ 0 counterparts.

Periodic structures on germanium induced by high repetition rate femtosecond laser

NASA Astrophysics Data System (ADS)

Lin, Xiaoming; Li, Xiaohong; Zhang, Yanbin; Xie, Changxin; Liu, Kaijun; Zhou, Qiang

2018-05-01

Laser-induced periodic surface structures (LIPSS) are studied on germanium surface in air by the femtosecond pulsed laser with repetition frequency of 76 MHz and wavelength λ of 800 nm. Three types of LIPSS were found and they are low-spatial-frequency LIPSS (LSFL), high-spatial-frequency LIPSS (HSFL), and LSFL superimposed with HSFL. The period ΛLSFL of LSFL shrinks quickly from approximately 650 nm to 400 nm (∼λ/2) when lowering the scanning speed. Comparatively, the period ΛHSFL of HSFL keeps almost constant between 90 and 100 nm (∼λ/8) when the scanning speed and the laser pulse energy vary. LSFL and HSFL coexist when the laser pulse energy is around 3.3 nJ/pulse and the scanning speed ranges between 3 and 8 mm/s. The surface plasmon polariton waves make a contribution to the formation of LIPSS and the fourth harmonic generation (FHG) might be involved in the formation of HSFL.

Improvements of electronic and optical characteristics of n-GaN-based structures by photoelectrochemical oxidation in glycol solution

NASA Astrophysics Data System (ADS)

Shiozaki, Nanako; Hashizume, Tamotsu

2009-03-01

Surface control of n-GaN was performed by applying a photoelectrochemical oxidation method in a glycol solution to improve the optical and electronic characteristics. The fundamental properties of the oxidation were investigated. The oxidation, chemical composition, and bonding states were analyzed by x-ray photoelectron spectroscopy and micro-Auger electron spectroscopy, in which confirmed the formation of gallium oxide on the surface. The oxide formation rate was about 8 nm/min under UV illumination of 4 mW/cm2. After establishing the basic properties for control of n-GaN oxidation, the surface control technique was applied to achieve low-damage etching, enhancement of the photoluminescence intensity, and selective passivation of the air-exposed sidewalls in an AlGaN/GaN high electron mobility transistor wire structure. The capacitance-voltage measurement revealed the minimum interface-state density between GaN and anodic oxide to be about 5×1011 cm-2 eV-1, which is rather low value for compound semiconductors.

Generation of alkali-free and high-proton concentration layer in a soda lime glass using non-contact corona discharge

NASA Astrophysics Data System (ADS)

Ikeda, Hiroshi; Sakai, Daisuke; Funatsu, Shiro; Yamamoto, Kiyoshi; Suzuki, Toshio; Harada, Kenji; Nishii, Junji

2013-08-01

Formation mechanisms of alkali-free and high-proton concentration surfaces were investigated for a soda lime glass using a corona discharge treatment under an atmospheric pressure. Protons produced by high DC voltage around an anode needle electrode were incorporated into a sodium ion site in the anode side glass. The sodium ion was swept away to the cathode side as a charge carrier. Then it was discharged. The precipitated sodium was transformed to a Na2CO3 powder when the surface contacted with air. The sodium ion in the glass surface layer of the anode side was replaced completely by protons. The concentration of OH groups in the layer was balanced with the amount of excluded sodium ions. The substitution reaction of sodium ions with protons tends to be saturated according to a square root function of time. The alkali depletion layer formation rate was affected by the large difference in mobility between sodium ions and protons in the glass.

The effect of simulated low earth orbit radiation on polyimides (UV degradation study)

NASA Technical Reports Server (NTRS)

Forsythe, John S.; George, Graeme A.; Hill, David J. T.; Odonnell, James H.; Pomery, Peter J.; Rasoul, Firas A.

1995-01-01

UV degradation of polyimide films in air and vacuum were studied using UV-visible, ESR, FTIR, and XPS spectroscopies. The UV-visible spectra of polyimide films showed a blue shift in the absorption compared to Kapton. This behavior was attributed to the presence of bulky groups and kinks along the polymer chains which disrupt the formation of a charge transfer complex. The UV-visible spectra showed also that UV irradiation of polyimides result extensively in surface degradation, leaving the bulk of the polymer intact. ESR spectra of polyimides irradiated in vacuum revealed the formation of stable carbon-centered radicals which give a singlet ESR spectrum, while polyimides irradiated in air produced an asymmetric signal shifted to a lower magnetic field, with a higher g value and line width. This signal was attributed to oxygen-cenetered radicals of peroxy and/or alkoxy type. The rate of radical formation in air was two fold higher than for vacuum irradiation, and reached a plateau after a short time. This suggests a continuous depletion of radicals on the surface via an ablative degradation process. FTIR, XPS, and weight loss studies supported this postulate. An XPS study of the surface indicated a substantial increase in the surface oxidation after irradiation in air. The sharp increase in the C-O binding energy peak relative to the C-C peak was believed to be associated with an aromatic ring opening reaction.

Micro-mechanisms of Surface Defects Induced on Aluminum Alloys during Plastic Deformation at Elevated Temperatures

NASA Astrophysics Data System (ADS)

Gali, Olufisayo A.

Near-surface deformed layers developed on aluminum alloys significantly influence the corrosion and tribological behavior as well as reduce the surface quality of the rolled aluminum. The evolution of the near-surface microstructures induced on magnesium containing aluminum alloys during thermomechanical processing has been investigated with the aim generating an understanding of the influence of individual forming parameters on its evolution and examine the microstructure of the roll coating induced on the mating steel roll through material transfer during rolling. The micro-mechanisms related to the various features of near-surface microstructure developed during tribological conditions of the simulated hot rolling process were identified. Thermomechanical processing experiments were performed with the aid of hot rolling (operating temperature: 550 to 460 °C, 4, 10 and 20 rolling pass schedules) and hot forming (operating temperature: 350 to 545 °C, strain rate: 4 x 10-2 s-1) tribo-simulators. The surface, near-surface features and material transfer induced during the elevated temperature plastic deformation were examined and characterized employing optical interferometry, SEM/EDS, FIB and TEM. Near-surface features characterized on the rolled aluminum alloys included; cracks, fractured intermetallic particles, aluminum nano-particles, oxide decorated grain boundaries, rolled-in oxides, shingles and blisters. These features were related to various individual rolling parameters which included, the work roll roughness, which induced the formation of shingles, rolling marks and were responsible for the redistribution of surface oxide and the enhancements of the depth of the near-surface damage. The enhanced stresses and strains experienced during rolling were related to the formation and propagation of cracks, the nanocrystalline structure of the near-surface layers and aluminum nano-particles. The mechanism of the evolution of the near-surface microstructure were determined to include grain boundary sliding which induced the cracks at the surface and subsurface of the alloy, magnesium diffusion to free surfaces, crack propagation from shear stresses and the shear strains inducing the nanocrystalline grain structure, the formation of shingles by the shear deformation of micro-wedges induced by the work roll grooves, and the deformation of this oxide covered micro-wedges inducing the rolled-in oxides. Magnesium diffusion to free surfaces was identified as inducing crack healing due to the formation of MgO within cracks and was responsible for the oxide decorated grain boundaries. An examination of the roll coating revealed a complex layered microstructure that was induced through tribo-chemical and mechanical entrapment mechanisms. The microstructure of the roll coating suggested that the work roll material and the rolled aluminum alloy were essential in determining its composition and structure. Subsequent hot forming processes revealed the rich oxide-layer of the near-surface microstructure was beneficial for reducing the coefficient of friction during tribological contact with the steel die. Damage to the microstructure include cracks induced from grain boundary sliding of near-surface grains and the formation of oxide fibres within cracks of the near-surface deformed layers.

Magma Supply Rate Controls Vigor (And Longevity) of Kīlauea's Ongoing East Rift Zone Eruption

NASA Astrophysics Data System (ADS)

Poland, M. P.; Anderson, K. R.

2015-12-01

Since 1983, Kīlauea Volcano, Hawai'i, has erupted almost continuously from vents on the East Rift Zone—at 32 years and counting, this is the longest-duration eruption in the past 500 years. Although forecasting the onset of eruptive activity using geophysical, geochemical, and geological monitoring has been demonstrated repeatedly at Kīlauea and elsewhere, little progress has been made in forecasting an eruption's waning or end, particularly in the case of long-lived eruptions. This is especially important at Kīlauea for at least two reasons: (1) caldera formation at the end of another decades-long eruption, in the 15th century, raises the possibility of a link between eruption duration and caldera formation; and (2) long-lived eruptions can have an enduring effect on local population and infrastructure, as demonstrated by the repeated destruction of property by Kīlauea's ongoing rift zone eruption. Data from the past 15 years indicate that the magma supply rate to Kīlauea is an important control on eruptive activity. Joint inversions of geophysical, geochemical, and geological observations demonstrate that in 2006 the supply rate was nearly double that of 2000-2001, resulting in an increase in lava discharge, summit inflation, and the formation of new eruptive vents. In contrast, the magma supply during 2012, and likely through 2014, was less than that of 2000-2001. This lower supply rate was associated with a lower lava discharge and may have played a role in the stalling of lava flows above population centers in the Puna District during 2014-2015. Heightened eruptive vigor may be expected if magma supply increases in the future; however, a further decrease in supply rate—which is likely already below the long-term average—may result in cessation of the eruption. Multidisciplinary monitoring, and particularly tracking of CO2 emissions and surface deformation, should be able to detect changes in supply rate before they are strongly manifested at the surface.

Spontaneous and Flow-Driven Interfacial Phase Change: Dynamics of Microemulsion Formation at the Pore Scale.

PubMed

Tagavifar, Mohsen; Xu, Ke; Jang, Sung Hyun; Balhoff, Matthew T; Pope, Gary A

2017-11-14

The dynamic behavior of microemulsion-forming water-oil-amphiphiles mixtures is investigated in a 2.5D micromodel. The equilibrium phase behavior of such mixtures is well-understood in terms of macroscopic phase transitions. However, what is less understood and where experimental data are lacking is the coupling between the phase change and the bulk flow. Herein, we study the flow of an aqueous surfactant solution-oil mixture in porous media and analyze the dependence of phase formation and spatial phase configurations on the bulk flow rate. We find that a microemulsion forms instantaneously as a boundary layer at the initial surface of contact between the surfactant solution and oil. The boundary layer is temporally continuous because of the imposed convection. In addition to the imposed flow, we observe spontaneous pulsed Marangoni flows that drag the microemulsion and surfactant solution into the oil stream, forming large (macro)emulsion droplets. The formation of the microemulsion phase at the interface distinguishes the situation from that of the more common Marangoni flow with only two phases present. Additionally, an emulsion forms via liquid-liquid nucleation or the Ouzo effect (i.e., spontaneous emulsification) at low flow rates and via mechanical mixing at high flow rates. With regard to multiphase flow, contrary to the common belief that the microemulsion is the wetting liquid, we observe that the minor oil phase wets the solid surface. We show that a layered flow pattern is formed because of the out-of-equilibrium phase behavior at high volumetric flow rates (order of 2 m/day) where advection is much faster than the diffusive interfacial mass transfer and transverse mixing, which promote equilibrium behavior. At lower flow rates (order of 30 cm/day), however, the dynamic and equilibrium phase behaviors are well-correlated. These results clearly show that the phase change influences the macroscale flow behavior.

A CANDELS-3D-HST synergy: Resolved Star Formation Patterns at 0.7 < z < 1.5

NASA Astrophysics Data System (ADS)

Wuyts, Stijn; Förster Schreiber, Natascha M.; Nelson, Erica J.; van Dokkum, Pieter G.; Brammer, Gabe; Chang, Yu-Yen; Faber, Sandra M.; Ferguson, Henry C.; Franx, Marijn; Fumagalli, Mattia; Genzel, Reinhard; Grogin, Norman A.; Kocevski, Dale D.; Koekemoer, Anton M.; Lundgren, Britt; Lutz, Dieter; McGrath, Elizabeth J.; Momcheva, Ivelina; Rosario, David; Skelton, Rosalind E.; Tacconi, Linda J.; van der Wel, Arjen; Whitaker, Katherine E.

2013-12-01

We analyze the resolved stellar populations of 473 massive star-forming galaxies at 0.7 < z < 1.5, with multi-wavelength broadband imaging from CANDELS and Hα surface brightness profiles at the same kiloparsec resolution from 3D-HST. Together, this unique data set sheds light on how the assembled stellar mass is distributed within galaxies, and where new stars are being formed. We find the Hα morphologies to resemble more closely those observed in the ACS I band than in the WFC3 H band, especially for the larger systems. We next derive a novel prescription for Hα dust corrections, which accounts for extra extinction toward H II regions. The prescription leads to consistent star formation rate (SFR) estimates and reproduces the observed relation between the Hα/UV luminosity ratio and visual extinction, on both a pixel-by-pixel and a galaxy-integrated level. We find the surface density of star formation to correlate with the surface density of assembled stellar mass for spatially resolved regions within galaxies, akin to the so-called "main sequence of star formation" established on a galaxy-integrated level. Deviations from this relation toward lower equivalent widths are found in the inner regions of galaxies. Clumps and spiral features, on the other hand, are associated with enhanced Hα equivalent widths, bluer colors, and higher specific SFRs compared to the underlying disk. Their Hα/UV luminosity ratio is lower than that of the underlying disk, suggesting that the ACS clump selection preferentially picks up those regions of elevated star formation activity that are the least obscured by dust. Our analysis emphasizes that monochromatic studies of galaxy structure can be severely limited by mass-to-light ratio variations due to dust and spatially inhomogeneous star formation histories.

A CANDELS-3d-HST Synergy: Resolved Star Formation Patterns at 0.7 less than z less than 1.5

NASA Technical Reports Server (NTRS)

Wuyts, Stijn; Foerster Schreiber, Natascha M.; Nelson, Erica J.; Van Dokkum, Pieter G.; Brammer, Gabe; Chang, Yu-Yen; Faber, Sandra M.; Ferguson, Henry C.; Franx, Marijn; Fumagalli, Mattia;

Multiscale Investigation on Biofilm Distribution and Its Impact on Macroscopic Biogeochemical Reaction Rates

NASA Astrophysics Data System (ADS)

Yan, Zhifeng; Liu, Chongxuan; Liu, Yuanyuan; Bailey, Vanessa L.

2017-11-01

Biofilms are critical locations for biogeochemical reactions in the subsurface environment. The occurrence and distribution of biofilms at microscale as well as their impacts on macroscopic biogeochemical reaction rates are still poorly understood. This paper investigated the formation and distributions of biofilms in heterogeneous sediments using multiscale models and evaluated the effects of biofilm heterogeneity on local and macroscopic biogeochemical reaction rates. Sediment pore structures derived from X-ray computed tomography were used to simulate the microscale flow dynamics and biofilm distribution in the sediment column. The response of biofilm formation and distribution to the variations in hydraulic and chemical properties was first examined. One representative biofilm distribution was then utilized to evaluate its effects on macroscopic reaction rates using nitrate reduction as an example. The results revealed that microorganisms primarily grew on the surfaces of grains and aggregates near preferential flow paths where both electron donor and acceptor were readily accessible, leading to the heterogeneous distribution of biofilms in the sediments. The heterogeneous biofilm distribution decreased the macroscopic rate of biogeochemical reactions as compared with those in homogeneous cases. Operationally considering the heterogeneous biofilm distribution in macroscopic reactive transport models such as using dual porosity domain concept can significantly improve the prediction of biogeochemical reaction rates. Overall, this study provided important insights into the biofilm formation and distribution in soils and sediments as well as their impacts on the macroscopic manifestation of reaction rates.

Effects of phosphorus supply on growth, phosphate concentration and cluster-root formation in three Lupinus species

PubMed Central

Abdolzadeh, Ahmad; Wang, Xing; Veneklaas, Erik J.; Lambers, Hans

2010-01-01

Background and Aims In some lupin species, phosphate deficiency induces cluster-root formation, which enhances P uptake by increasing root surface area and, more importantly, the release of root exudates which enhances P availability. Methods Three species of Lupinus, L. albus, L. atlanticus and L. micranthus, with inherently different relative growth rates were cultivated under hydroponics in a greenhouse at four phosphate concentrations (1, 10, 50 and 150 µm) to compare the role of internal P in regulating cluster-root formation. Key Results The highest growth rate was observed in L. atlanticus, followed by L. albus and L. micranthus. At 1 µm P, cluster-root formation was markedly induced in all three species. The highest P uptake and accumulation was observed in L. micranthus, followed by L. atlanticus and then L. albus. Inhibition of cluster-root formation was severe at 10 µm P in L. atlanticus, but occurred stepwise with increasing P concentration in the root medium in L. albus. Conclusions In L. atlanticus and L. albus cluster-root formation was suppressed by P treatments above 10 µm, indicating a P-inducible regulating system for cluster-root formation, as expected. By contrast, production of cluster roots in L. micranthus, in spite of a high internal P concentration, indicated a lower sensitivity to P status, which allowed P-toxicity symptoms to develop. PMID:20037142

Formation of diamond nanoparticle thin films by electrophoretic deposition

NASA Astrophysics Data System (ADS)

Goto, Yosuke; Ohishi, Fujio; Tanaka, Kuniaki; Usui, Hiroaki

2016-03-01

Thin films of diamond nanoparticles were prepared by electrophoretic deposition (EPD) using 0.5 wt % dispersions in water, ethanol, and 2-propanol. The film growth rate increased with increasing voltage applied to the electrodes. However, an excessive increase in voltage caused the degradation of film morphology. The optimum voltage was 4 V with an electrode separation of 5 mm. The film growth rate was higher in organic solvents than in water. The deposited film had a smooth surface with an average surface roughness comparable to the size of primary particles of the source material. It is notable that the EPD films had a considerably higher physical stability than spin-coated and cast films. The stability was further improved by thermally annealing the films. IR analysis revealed that the diamond nanoparticles have carboxy and amino groups on their surfaces. It is considered that the stability of the EPD films originate from a chemical reaction between these functional groups.

Kinetics of gas phase formic acid decomposition on platinum single crystal and polycrystalline surfaces

NASA Astrophysics Data System (ADS)

Detwiler, Michael D.; Milligan, Cory A.; Zemlyanov, Dmitry Y.; Delgass, W. Nicholas; Ribeiro, Fabio H.

2016-06-01

Formic acid dehydrogenation turnover rates (TORs) were measured on Pt(111), Pt(100), and polycrystalline Pt foil surfaces at a total pressure of 800 Torr between 413 and 513 K in a batch reactor connected to an ultra-high vacuum (UHV) system. The TORs, apparent activation energies, and reaction orders are not sensitive to the structure of the Pt surface, within the precision of the measurements. CO introduced into the batch reactor depressed the formic acid dehydrogenation TOR and increased the reaction's apparent activation energies on Pt(111) and Pt(100), consistent with behavior predicted by the Temkin equation. Two reaction mechanisms were explored which explain the formic acid decomposition mechanism on Pt, both of which include dissociative adsorption of formic acid, rate limiting formate decomposition, and quasi-equilibrated hydrogen recombination and CO adsorption. No evidence was found that catalytic supports used in previous studies altered the reaction kinetics or mechanism.

Effect of Processing Steps on the Mechanical Properties and Surface Appearance of 6063 Aluminium Extruded Products

PubMed Central

Asensio-Lozano, Juan; Suárez-Peña, Beatriz; Vander Voort, George F.

2014-01-01

6063 aluminum anodized extrusions may exhibit a common surface defect known as streaking, characterized by the formation of narrow bands with a surface gloss different from the surrounding material. The origin of this banding lies in the differential surface topography produced after etching during the anodizing stage, shown to be connected to certain microstructural characteristics. The present study has attempted to determine the origin of these defects and measure the mechanical properties in these zones, properties which were either barely acceptable or did not meet the specification’s requirements. Quantitative metallography and mechanical testing, both tensile and microhardness, were used for materials assessment at the different steps of the process of manufacturing 6063 anodized extrusions. The results of this research show that nonequilibrium solidification rates during billet casting could lead to the formation of coarse eutectic Mg2Si particles which have a deleterious effect on both mechanical properties and surface appearance in the anodized condition. However, differences in the size and density of the coarse Mg2Si particles have been found to exist in the streak profile compared to the surrounding zones. The study revealed the importance of these particles in explaining the origin of the marginal or sub-marginal properties and anodizing surface defects found. PMID:28788673

Effect of Processing Steps on the Mechanical Properties and Surface Appearance of 6063 Aluminium Extruded Products.

PubMed

Asensio-Lozano, Juan; Suárez-Peña, Beatriz; Vander Voort, George F

2014-05-30

6063 aluminum anodized extrusions may exhibit a common surface defect known as streaking, characterized by the formation of narrow bands with a surface gloss different from the surrounding material. The origin of this banding lies in the differential surface topography produced after etching during the anodizing stage, shown to be connected to certain microstructural characteristics. The present study has attempted to determine the origin of these defects and measure the mechanical properties in these zones, properties which were either barely acceptable or did not meet the specification's requirements. Quantitative metallography and mechanical testing, both tensile and microhardness, were used for materials assessment at the different steps of the process of manufacturing 6063 anodized extrusions. The results of this research show that nonequilibrium solidification rates during billet casting could lead to the formation of coarse eutectic Mg₂Si particles which have a deleterious effect on both mechanical properties and surface appearance in the anodized condition. However, differences in the size and density of the coarse Mg₂Si particles have been found to exist in the streak profile compared to the surrounding zones. The study revealed the importance of these particles in explaining the origin of the marginal or sub-marginal properties and anodizing surface defects found.

Room temperature deposition of gold onto the diffuse and sharp diffraction spot Si(111)-( 3 × 3) R30° Au surfaces

NASA Astrophysics Data System (ADS)

Plass, Richard; Marks, Laurence D.

1996-06-01

Room temperature gold depositions onto Si(111)-( 3 × 3) R30° Au surfaces with diffuse and sharp diffraction spots [Surf. Sci. 242 (1991) 73] (diffuse and sharp 3 × 3 Au hereafter) under UHV conditions has been monitored using transmission electron diffraction (TED). Both systems display an increase in surface structure diffraction spot intensities up to the completion of 1.0 monolayer (ML) after which the surface beams display an exponential decrease in intensity with coverage. The exponential decay rate decreases after roughly 1.33 ML. These results can be attributed to gold initially diffusing to and filling 3 × 3 Au gold trimer sites in vacancy type surface domain walls [Surf. Sci. 342 (1995) 233], then filling one of three possible sites on the 3 × 3 Au structure with essentially no surface diffusion, disrupting nearby gold trimers. Gold deposition onto the diffuse type structure caused the formation and expansion of satellite arcs around the strongest 3 × 3 beams similar to those seen by others [Surf. Sci. 242 (1991) 73; Jpn. J. Appl. Phys. 16 (1977) 891; J. Vac. Sci. Technol. A 10 (1992) 3486] at elevated temperatures while the sharp structure displayed only a modest shoulder formation near the strongest 3 × 3 beams.

Near Surface Vapor Bubble Layers in Buoyant Low Stretch Burning of Polymethylmethacrylate

NASA Technical Reports Server (NTRS)

Olson, Sandra L.; Tien, J. S.

1999-01-01

Large-scale buoyant low stretch stagnation point diffusion flames over solid fuel (polymethylmethacrylate) were studied for a range of aerodynamic stretch rates of 2-12/ sec which are of the same order as spacecraft ventilation-induced stretch in a microgravity environment. An extensive layer of polymer material above the glass transition temperature is observed. Unique phenomena associated with this extensive glass layer included substantial swelling of the burning surface, in-depth bubble formation, and migration and/or elongation of the bubbles normal to the hot surface. The bubble layer acted to insulate the polymer surface by reducing the effective conductivity of the solid. The reduced in-depth conduction stabilized the flame for longer than expected from theory neglecting the bubble layer. While buoyancy acts to move the bubbles deeper into the molten polymer, thermocapillary forces and surface regression both act to bring the bubbles to the burning surface. Bubble layers may thus be very important in low gravity (low stretch) burning of materials. As bubbles reached the burning surface, monomer fuel vapors jetted from the surface, enhancing burning by entraining ambient air flow. Popping of these bubbles at the surface can expel burning droplets of the molten material, which may increase the fire propagation hazards at low stretch rates.

Surface phenomena revealed by in situ imaging: studies from adhesion, wear and cutting

NASA Astrophysics Data System (ADS)

Viswanathan, Koushik; Mahato, Anirban; Yeung, Ho; Chandrasekar, Srinivasan

2017-03-01

Surface deformation and flow phenomena are ubiquitous in mechanical processes. In this work we present an in situ imaging framework for studying a range of surface mechanical phenomena at high spatial resolution and across a range of time scales. The in situ framework is capable of resolving deformation and flow fields quantitatively in terms of surface displacements, velocities, strains and strain rates. Three case studies are presented demonstrating the power of this framework for studying surface deformation. In the first, the origin of stick-slip motion in adhesive polymer interfaces is investigated, revealing a intimate link between stick-slip and surface wave propagation. Second, the role of flow in mediating formation of surface defects and wear particles in metals is analyzed using a prototypical sliding process. It is shown that conventional post-mortem observation and inference can lead to erroneous conclusions with regard to formation of surface cracks and wear particles. The in situ framework is shown to unambiguously capture delamination wear in sliding. Third, material flow and surface deformation in a typical cutting process is analyzed. It is shown that a long-standing problem in the cutting of annealed metals is resolved by the imaging, with other benefits such as estimation of energy dissipation and power from the flow fields. In closure, guidelines are provided for profitably exploiting in situ observations to study large-strain deformation, flow and friction phenomena at surfaces that display a variety of time-scales.

Modeling, Fabrication and Characterization of Scalable Electroless Gold Plated Nanostructures for Enhanced Surface Plasmon Resonance

NASA Astrophysics Data System (ADS)

Jang, Gyoung Gug

The scientific and industrial demand for controllable thin gold (Au) film and Au nanostructures is increasing in many fields including opto-electronics, photovoltaics, MEMS devices, diagnostics, bio-molecular sensors, spectro-/microscopic surfaces and probes. In this study, a novel continuous flow electroless (CF-EL) Au plating method is developed to fabricate uniform Au thin films in ambient condition. The enhanced local mass transfer rate and continuous deposition resulting from CF-EL plating improved physical uniformity of deposited Au films and thermally transformed nanoparticles (NPs). Au films and NPs exhibited improved optical photoluminescence (PL) and surface plasmon resonance (SPR), respectively, relative to batch immersion EL (BI-EL) plating. Suggested mass transfer models of Au mole deposition are consistent with optical feature of CF-EL and BI-EL films. The prototype CF-EL plating system is upgraded an automated scalable CF-EL plating system with real-time transmission UV-vis (T-UV) spectroscopy which provides the advantage of CF-EL plating, such as more uniform surface morphology, and overcomes the disadvantages of conventional EL plating, such as no continuous process and low deposition rate, using continuous process and controllable deposition rate. Throughout this work, dynamic morphological and chemical transitions during redox-driven self-assembly of Ag and Au film on silica surfaces under kinetic and equilibrium conditions are distinguished by correlating real-time T-UV spectroscopy with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) measurements. The characterization suggests that four previously unrecognized time-dependent physicochemical regimes occur during consecutive EL deposition of silver (Ag) and Au onto tin-sensitized silica surfaces: self-limiting Ag activation; transitory Ag NP formation; transitional Au-Ag alloy formation during galvanic replacement of Ag by Au; and uniform morphology formation under controlled hydraulic conditions. A method to achieve the time-resolved optical profile of EL Au plating was devised and provided a new transitional EL Au film growth model which validated mass transfer model prediction of the deposited thickness of ≤100 nm thin films. As a part of the project, validation of mass transfer model, a spectrophotometric method for quantitative analysis of metal ion is developed that improves the limit of detection comparable to conventional instrumental analysis. The present work suggests that modeling, fabrication and characterization of this novel CF-EL plating method is performed to achieve an ultimate purpose: developing a reliable, inexpensive wet chemical process for controlled metal thin film and nanostructure fabrication.

Multivalent-Counterion-Induced Surfactant Multilayer Formation at Hydrophobic and Hydrophilic Solid-Solution Interfaces.

PubMed

Penfold, Jeffrey; Thomas, Robert K; Li, Peixun; Xu, Hui; Tucker, Ian M; Petkov, Jordan T; Sivia, Devinderjit S

2015-06-23

Surface multilayer formation from the anionic-nonionic surfactant mixture of sodium dodecyl dioxyethylene sulfate, SLES, and monododecyl dodecaethylene glycol, C12E12, by the addition of multivalent Al(3+) counterions at the solid-solution interface is observed and characterized by neutron reflectivity, NR. The ability to form surface multilayer structures on hydrophobic and hydrophilic silica and cellulose surfaces is demonstrated. The surface multilayer formation is more pronounced and more well developed on the hydrophilic and hydrophobic silica surfaces than on the hydrophilic and hydrophobic cellulose surfaces. The less well developed multilayer formation on the cellulose surfaces is attributed to the greater surface inhomogeneities of the cellulose surface which partially inhibit lateral coherence and growth of the multilayer domains at the surface. The surface multilayer formation is associated with extreme wetting properties and offers the potential for the manipulation of the solid surfaces for enhanced adsorption and control of the wetting behavior.

Smoothing metallic glasses without introducing crystallization by gas cluster ion beam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shao, Lin; Chen, Di; Myers, Michael

2013-03-11

We show that 30 keV Ar cluster ion bombardment of Ni{sub 52.5}Nb{sub 10}Zr{sub 15}Ti{sub 15}Pt{sub 7.5} metallic glass (MG) can remove surface mountain-like features and reduce the root mean square surface roughness from 12 nm to 0.7 nm. X-ray diffraction analysis reveals no crystallization after cluster ion irradiation. Molecular dynamics simulations show that, although damage cascades lead to local melting, the subsequent quenching rate is a few orders of magnitude higher than the critical cooling rate for MG formation, thus the melted zone retains its amorphous nature down to room temperature. These findings can be applied to obtain ultra-smooth MGsmore » without introducing crystallization.« less

Oxidation of Hydrocarbons on the Surface of Tin Dioxide Chemical Sensors

PubMed Central

Teterycz, Helena; Halek, Patryk; Wiśniewski, Kamil; Halek, Grzegorz; Koźlecki, Tomasz; Polowczyk, Izabela

2011-01-01

The paper presents the results of our investigation on the effect of the molecular structure of organic vapors on the characteristics of resistive chemical gas sensors. The sensors were based on tin dioxide and prepared by means of thick film technology. The electrical and catalytic examinations showed that the abstraction of two hydrogen atoms from the organic molecule and formation of a water in result of reaction with a chemisorbed oxygen ion, determine the rate of oxidation reactions, and thus the sensor performance. The rate of the process depends on the order of carbon atoms and Lewis acidity of the molecule. Therefore, any modification of the surface centers of a sensor material, modifies not only the sensor sensitivity, but also its selectivity. PMID:22163855

Correlations Among Ice Measurements, Impingement Rates Icing Conditions, and Drag Coefficients for Unswept NACA 65A004 Airfoil

NASA Technical Reports Server (NTRS)

Gray, Vernon H.

1958-01-01

An empirical relation has been obtained by which the change in drag coefficient caused by ice formations on an unswept NACA 65AO04 airfoil section can be determined from the following icing and operating conditions: icing time, airspeed, air total temperature, liquid-water content, cloud droplet impingement efficiencies, airfoil chord length, and angles of attack. The correlation was obtained by use of measured ice heights and ice angles. These measurements were obtained from a variety of ice formations, which were carefully photographed, cross-sectioned, and weighed. Ice weights increased at a constant rate with icing time in a rime icing condition and at progressively increasing rates in glaze icing conditions. Initial rates of ice collection agreed reasonably well with values predicted from droplet impingement data. Experimental droplet impingement rates obtained on this airfoil section agreed with previous theoretical calculations for angles of attack of 40 or less. Disagreement at higher angles of attack was attributed to flow separation from the upper surface of the experimental airfoil model.

Effects of Ag and Cu ions on the microbial corrosion of 316L stainless steel in the presence of Desulfovibrio sp.

PubMed

Unsal, Tuba; Ilhan-Sungur, Esra; Arkan, Simge; Cansever, Nurhan

2016-08-01

The utilization of Ag and Cu ions to prevent both microbial corrosion and biofilm formation has recently increased. The emphasis of this study lies on the effects of Ag and Cu ions on the microbial corrosion of 316L stainless steel (SS) induced by Desulfovibrio sp. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization were used to analyze the corrosion behavior. The biofilm formation, corrosion products and Ag and Cu ions on the surfaces were investigated using scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS) and elemental mapping. Through circuit modeling, EIS results were used to interpret the physicoelectric interactions between the electrode, biofilm and culture interfaces. EIS results indicated that the metabolic activity of Desulfovibrio sp. accelerated the corrosion rate of SS in both conditions with and without ions. However, due to the retardation in the growth of Desulfovibrio sp. in the presence of Ag and Cu ions, significant decrease in corrosion rate was observed in the culture with the ions. In addition, SEM and EIS analyses revealed that the presence of the ions leads to the formation on the SS of a biofilm with different structure and morphology. Elemental analysis with EDS detected mainly sulfide- and phosphorous-based corrosion products on the surfaces. Copyright © 2016 Elsevier B.V. All rights reserved.

Role of Marangoni stress during breakup of surfactant-covered liquid threads: Reduced rates of thinning and microthread cascades

NASA Astrophysics Data System (ADS)

Kamat, Pritish M.; Wagoner, Brayden W.; Thete, Sumeet S.; Basaran, Osman A.

2018-04-01

Adsorption onto and lowering of surface tension σ of fluid interfaces by surfactants is exploited in drop formation (e.g., inkjet printing) where a thinning liquid thread (radius h ) connects an about-to-form drop to the liquid that remains hanging from the nozzle when the former falls from it. Surfactants can affect thread pinch-off in two ways: first, by lowering σ , they lower capillary pressure (σ /h ), and second, as surfactant concentration along the interface can be nonuniform, they cause the interface to be subjected to a surface tension gradient or Marangoni stress. Recent studies show that the location where the thread breaks is devoid of surfactant, and others assert that the influence of Marangoni stress on pinch-off is negligible. We demonstrate by simulations and experiments that surfactants play a major role in drop formation and that Marangoni stresses acting near but not at the pinch point give rise to reduced rates of thread thinning and formation of multiple microthreads that distinguish pinch-off of surfactant-covered threads from surfactant-free ones. Thinning at finite Reynolds and Peclet numbers, Re and Pe, is shown to exhibit intermediate scaling regimes that have heretofore only been observed during pinch-off of threads undergoing creeping flow (Re=0 ) while convection of surfactant is weak compared to its diffusion (Pe<1 ).

Growth rate effects on the formation of dislocation loops around deep helium bubbles in Tungsten

DOE PAGES

Sandoval, Luis; Perez, Danny; Uberuaga, Blas P.; ...

2016-11-15

Here, the growth process of spherical helium bubbles located 6 nm below a (100) surface is studied using molecular dynamics and parallel replica dynamics simulations, over growth rates from 10 6 to 10 12 helium atoms per second. Slower growth rates lead to a release of pressure and lower helium content as compared with fast growth cases. In addition, at slower growth rates, helium bubbles are not decorated by multiple dislocation loops, as these tend to merge or emit given sufficient time. At faster rates, dislocation loops nucleate faster than they can emit, leading to a more complicated dislocation structuremore » around the bubble.« less

Extended Schmidt law holds for faint dwarf irregular galaxies

NASA Astrophysics Data System (ADS)

Roychowdhury, Sambit; Chengalur, Jayaram N.; Shi, Yong

2017-12-01

Context. The extended Schmidt law (ESL) is a variant of the Schmidt which relates the surface densities of gas and star formation, with the surface density of stellar mass added as an extra parameter. Although ESL has been shown to be valid for a wide range of galaxy properties, its validity in low-metallicity galaxies has not been comprehensively tested. This is important because metallicity affects the crucial atomic-to-molecular transition step in the process of conversion of gas to stars. Aims: We empirically investigate for the first time whether low metallicity faint dwarf irregular galaxies (dIrrs) from the local universe follow the ESL. Here we consider the "global" law where surface densities are averaged over the galactic discs. dIrrs are unique not only because they are at the lowest end of mass and star formation scales for galaxies, but also because they are metal-poor compared to the general population of galaxies. Methods: Our sample is drawn from the Faint Irregular Galaxy GMRT Survey (FIGGS) which is the largest survey of atomic hydrogen in such galaxies. The gas surface densities are determined using their atomic hydrogen content. The star formation rates are calculated using GALEX far ultraviolet fluxes after correcting for dust extinction, whereas the stellar surface densities are calculated using Spitzer 3.6 μm fluxes. The surface densities are calculated over the stellar discs defined by the 3.6 μm images. Results: We find dIrrs indeed follow the ESL. The mean deviation of the FIGGS galaxies from the relation is 0.01 dex, with a scatter around the relation of less than half that seen in the original relation. In comparison, we also show that the FIGGS galaxies are much more deviant when compared to the "canonical" Kennicutt-Schmidt relation. Conclusions: Our results help strengthen the universality of the ESL, especially for galaxies with low metallicities. We suggest that models of star formation in which feedback from previous generations of stars set the pressure in the interstellar medium and affect ongoing star formation, are promising candidates for explaining the ESL. We also confirm that ESL is an independent relation and not a form of a relation between star formation efficiency and metallicity.

Formation of thermochemical laser-induced periodic surface structures on Ti films by a femtosecond IR Gaussian beam: regimes, limiting factors, and optical properties

NASA Astrophysics Data System (ADS)

Dostovalov, A. V.; Korolkov, V. P.; Babin, S. A.

2017-01-01

The formation of thermochemical laser-induced periodic surface structures (TLIPSS) on 400-nm Ti films deposited onto a glass substrate is investigated under irradiation by a femtosecond laser with a wavelength of 1026 nm, pulse duration of 232 fs, repetition rate of 200 kHz, and with different spot sizes of 4-21 μm. The optimal fluence for TLIPSS formation reduces monotonously with increasing the spot diameter in the range. It is found that the standard deviation of the TLIPSS period depends significantly on the beam size and reaches approximately 2% when the beam diameter is in the range of 10-21 μm. In addition to TLIPSS formation with the main period slightly smaller than the laser wavelength, an effect of TLIPSS spatial frequency doubling is detected. The optical properties of TLIPSS (reflection spectrum and diffraction efficiency at different incident angles and polarizations) are investigated and compared with theoretical ones to give a basis for the development of an optical inspecting method. The refractive index and absorption coefficient of oxidized ridges of the TLIPSS are theoretically estimated by simulation of the experimental reflection spectrum in the zeroth diffraction order.

The presence of biofilm forming microorganisms on hydrotherapy equipment and facilities.

PubMed

Jarząb, Natalia; Walczak, Maciej

2017-10-01

Hydrotherapy equipment provides a perfect environment for the formation and growth of microbial biofilms. Biofilms may reduce the microbiological cleanliness of hydrotherapy equipment and harbour opportunistic pathogens and pathogenic bacteria. The aims of this study were to investigate the ability of microorganisms that colonize hydrotherapy equipment to form biofilms, and to assess the influence of temperature and nutrients on the rate of biofilm formation. Surface swab samples were collected from the whirlpool baths, inhalation equipment and submerged surfaces of a brine pool at the spa center in Ciechocinek, Poland. We isolated and identified microorganisms from the swab samples and measured their ability to form biofilms. Biofilm formation was observed at a range of temperatures, in both nutrient-deficient and nutrient-rich environments. We isolated and identified microorganisms which are known to form biofilms on medical devices (e.g. Stenotrophomonas maltophilia). All isolates were classified as opportunistic pathogens, which can cause infections in humans with weakened immunity systems. All isolates showed the ability to form biofilms in the laboratory conditions. The potential for biofilm formation was higher in the presence of added nutrients. In addition, the hydrolytic activity of the biofilm was connected with the presence of nutrients.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Tao; Xiao, Hai; Goddard, William A.

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions is not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or to carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). We carry out QM calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO 2 reduction reaction conditions) to examine the initial reaction pathways to form CO and formatemore » (HCOO –) from CO 2 through free energy calculations at 298 K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ-), with a free energy barrier of ΔG ‡ = 0.43 eV, the rate-determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 and 0.30 eV, respectively. HCOO– formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO – formation occurs in the first electron-transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Therefore, to alter the product distribution, we need to control this first step of CO 2 binding, which might involve controlling pH, alloying, or changing the structure at the nanoscale.« less

Predictive modeling of low solubility semiconductor alloys

NASA Astrophysics Data System (ADS)

Rodriguez, Garrett V.; Millunchick, Joanna M.

2016-09-01

GaAsBi is of great interest for applications in high efficiency optoelectronic devices due to its highly tunable bandgap. However, the experimental growth of high Bi content films has proven difficult. Here, we model GaAsBi film growth using a kinetic Monte Carlo simulation that explicitly takes cation and anion reactions into account. The unique behavior of Bi droplets is explored, and a sharp decrease in Bi content upon Bi droplet formation is demonstrated. The high mobility of simulated Bi droplets on GaAsBi surfaces is shown to produce phase separated Ga-Bi droplets as well as depressions on the film surface. A phase diagram for a range of growth rates that predicts both Bi content and droplet formation is presented to guide the experimental growth of high Bi content GaAsBi films.

Machinability of Al 6061 Deposited with Cold Spray Additive Manufacturing

NASA Astrophysics Data System (ADS)

Aldwell, Barry; Kelly, Elaine; Wall, Ronan; Amaldi, Andrea; O'Donnell, Garret E.; Lupoi, Rocco

2017-10-01

Additive manufacturing techniques such as cold spray are translating from research laboratories into more mainstream high-end production systems. Similar to many additive processes, finishing still depends on removal processes. This research presents the results from investigations into aspects of the machinability of aluminum 6061 tubes manufactured with cold spray. Through the analysis of cutting forces and observations on chip formation and surface morphology, the effect of cutting speed, feed rate, and heat treatment was quantified, for both cold-sprayed and bulk aluminum 6061. High-speed video of chip formation shows changes in chip form for varying material and heat treatment, which is supported by the force data and quantitative imaging of the machined surface. The results shown in this paper demonstrate that parameters involved in cold spray directly impact on machinability and therefore have implications for machining parameters and strategy.

HOW GALACTIC ENVIRONMENT REGULATES STAR FORMATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meidt, Sharon E.

2016-02-10

In a new simple model I reconcile two contradictory views on the factors that determine the rate at which molecular clouds form stars—internal structure versus external, environmental influences—providing a unified picture for the regulation of star formation in galaxies. In the presence of external pressure, the pressure gradient set up within a self-gravitating turbulent (isothermal) cloud leads to a non-uniform density distribution. Thus the local environment of a cloud influences its internal structure. In the simple equilibrium model, the fraction of gas at high density in the cloud interior is determined simply by the cloud surface density, which is itselfmore » inherited from the pressure in the immediate surroundings. This idea is tested using measurements of the properties of local clouds, which are found to show remarkable agreement with the simple equilibrium model. The model also naturally predicts the star formation relation observed on cloud scales and at the same time provides a mapping between this relation and the closer-to-linear molecular star formation relation measured on larger scales in galaxies. The key is that pressure regulates not only the molecular content of the ISM but also the cloud surface density. I provide a straightforward prescription for the pressure regulation of star formation that can be directly implemented in numerical models. Predictions for the dense gas fraction and star formation efficiency measured on large-scales within galaxies are also presented, establishing the basis for a new picture of star formation regulated by galactic environment.« less

Dynamics of altered surface layer formation on dissolving silicates

NASA Astrophysics Data System (ADS)

Daval, Damien; Bernard, Sylvain; Rémusat, Laurent; Wild, Bastien; Guyot, François; Micha, Jean Sébastien; Rieutord, François; Magnin, Valérie; Fernandez-Martinez, Alejandro

2017-07-01

The extrapolation of mineral dissolution kinetics experiments to geological timescales has frequently been challenged by the observation that mineral dissolution rates decrease with time. In the present study, we report a detailed investigation of the early stages of wollastonite dissolution kinetics, linking time-resolved measurements of wollastonite dissolution rate as a function of crystallographic orientation to the evolution of physicochemical properties (i.e., diffusivity, density, and thickness) of amorphous silica-rich layers (ASSLs) that developed on each surface. Batch dissolution experiments conducted at room temperature and at far-from-equilibrium conditions revealed that the initial (i.e., ASSL-free) dissolution rate of wollastonite (R(hkl)) based on Ca release observe the following trend: R(010) ≈R(100) >R(101) >R(001) . A gradual decrease of the dissolution rate of some faces by up to one order of magnitude resulted in a modification of this trend after two days: R(010) ≫R(100) ⩾R(101) ≈R(001) . In parallel, the diffusivity of ASSLs developed on each face was estimated based on the measurement of the concentration profile of a conservative tracer (methylene blue) across the ASSL using nanoSIMS. The apparent diffusion coefficients of methylene blue as a function of the crystallographic orientation (Dapp(hkl)) observe the following trend: Dapp(010) ⩾Dapp(100) >Dapp(101) ≫Dapp(001) , and decreases as a function of time for the (1 0 0) and (1 0 1) faces. Finally, the density of ASSL was estimated based on the modeling of X-ray reflectivity patterns acquired as a function of time. The density of ASSLs developed on the (0 1 0) faces remains low and constant, whereas it increases for the ASSLs developed on the (0 0 1) faces. On the whole, our results suggest that the impact of the formation of ASSLs on the wollastonite dissolution rate is anisotropic: while some crystal faces are weakly affected by the formation of non-passivating ASSLs (e.g., the (0 1 0) face), the dissolution of other faces is hampered by passivating ASSLs within a few hours. The observed passivation is suggested to originate from the progressive densification of the ASSL, which limits the transport of reactive species from and to the dissolving wollastonite surface, as evidenced by the estimated diffusivity of the ASSLs. Because the apparent face-specific diffusivity of the ASSLs is correlated with the face-specific initial (i.e., ASSL-free) dissolution rate of wollastonite, we propose that the extent of ASSL densification (and the resulting impact on ion transport) is (at least partly) controlled by the absolute mineral dissolution rate. Overall, this study argues that the formation and microstructural evolution of ASSLs are likely candidates for mineral ageing, highlighting the need for determining the parameters controlling the spontaneous changes of ASSL diffusivity as a function of the reaction progress.

In situ and time resolved nucleation and growth of silica nanoparticles forming under simulated geothermal conditions

NASA Astrophysics Data System (ADS)

Tobler, Dominique J.; Benning, Liane G.

2013-08-01

Detailed knowledge of the reaction kinetics of silica nanoparticle formation in cooling supersaturated waters is fundamental to the understanding of many natural processes including biosilicifcation, sinter formation, and silica diagenesis. Here, we quantified the formation of silica nanoparticles from solution as it would occur in geothermal waters. We used an in situ and real-time approach with silica polymerisation being induced by fast cooling of a 230 °C hot and supersaturated silica solution. Experiments were carried out using a novel flow-through geothermal simulator system that was designed to work on-line with either a synchrotron-based small angle X-ray scattering (SAXS) or a conventional dynamic light scattering (DLS) detector system. Our results show that the rate of silica nanoparticle formation is proportional to the silica concentration (640 vs. 960 ppm SiO2), and the first detected particles form spheres of approximately 3 nm in diameter. These initial nanoparticles grow and reach a final particle diameter of approximately 7 nm. Interestingly, neither variations in ionic strength (0.02 vs. 0.06) nor temperature (reactions at 30 to 60 °C, mimicking Earth surface values) seem to affect the formation kinetics or the final size of the silica nanoparticles formed. Comparing these results with our previous data from experiments where silica polymerisation and nanoparticle formation was induced by a drop in pH from 12 to near neutral (pH-induced, Tobler et al., 2009) showed that (a) the mechanisms and kinetics of silica nanoparticle nucleation and growth were unaffected by the means to induce silica polymerisation (T drop or pH drop), both following first order reactions kinetics coupled with a surface controlled reaction mechanism. However, the rates of the formation of silica nanoparticles were substantially (around 50%) slower when polymerisation was induced by fast cooling as opposed to pH change. This was evidenced by the occurrence of an induction period, the formation of larger critical nuclei, and the absence of particle aggregation in the T-induced experiments.

The reduction of HNO3 by volatile organic compounds emitted by motor vehicles

NASA Astrophysics Data System (ADS)

Rutter, A. P.; Malloy, Q. G. J.; Leong, Y. J.; Gutierrez, C. V.; Calzada, M.; Scheuer, E.; Dibb, J. E.; Griffin, R. J.

2014-04-01

Nitric acid (HNO3) was reduced in a flow tube by volatile organic carbon compounds (VOCs) generated from engine oil vapor. The primary reaction product was believed to be HONO. The reaction was not enhanced when Teflon® Raschig rings were added to the flow tube to increase surface area, thereby showing the reaction to be homogeneous under the conditions studied. The HONO formation observed ranged between 0.1 and 0.6 ppb h-1, with a mean of 0.3 ± 0.1 ppb h-1, for typical HNO3 concentrations of 4-5 ppb and estimated concentrations of the reactive components in the engine oil vapor between 200 and 300 ppt. The observations in this study compare well to a recently published field study conducted in Houston that observed average formation rates of 0.6 ± 0.3 ppb h-1. Water vapor was found to decrease the HONO formation rate by ˜0.1 ppb h-1 for every 1% increase in the water mixing ratio.

Statistical modeling of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2.

PubMed

Ushakov, Vladimir G; Troe, Jürgen; Johnson, Ryan S; Guo, Hua; Ard, Shaun G; Melko, Joshua J; Shuman, Nicholas S; Viggiano, Albert A

2015-08-14

The rates of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2 are modeled by statistical rate theory accounting for energy- and angular momentum-specific rate constants for formation of the primary and secondary cationic adducts and their backward and forward reactions. The reactions are both suggested to proceed on sextet and quartet potential energy surfaces with efficient, but probably not complete, equilibration by spin-inversion of the populations of the sextet and quartet adducts. The influence of spin-inversion on the overall reaction rate is investigated. The differences of the two reaction rates mostly are due to different numbers of entrance states (atom + linear rotor or linear rotor + linear rotor, respectively). The reaction Fe(+) + N2O was studied either with (6)Fe(+) or with (4)Fe(+) reactants. Differences in the rate constants of (6)Fe(+) and (4)Fe(+) reacting with N2O are attributed to different contributions from electronically excited potential energy surfaces, such as they originate from the open-electronic shell reactants.

Retardation of surface corrosion of biodegradable magnesium-based materials by aluminum ion implantation

NASA Astrophysics Data System (ADS)

Wu, Guosong; Xu, Ruizhen; Feng, Kai; Wu, Shuilin; Wu, Zhengwei; Sun, Guangyong; Zheng, Gang; Li, Guangyao; Chu, Paul K.

2012-07-01

Aluminum ion implantation is employed to modify pure Mg as well as AZ31 and AZ91 magnesium alloys and their surface degradation behavior in simulated body fluids is studied. Polarization tests performed in conjunction with scanning electron microscopy (SEM) reveal that the surface corrosion resistance after Al ion implantation is improved appreciably. This enhancement can be attributed to the formation of a gradient surface structure with a gradual transition from an Al-rich oxide layer to Al-rich metal layer. Compared to the high Al-content magnesium alloy (AZ91), a larger reduction in the degradation rate is achieved from pure magnesium and AZ31. Our results reveal that the surface corrosion resistance of Mg alloys with no or low Al content can be improved by Al ion implantation.

Slow positrons in the study of surface and near-surface defects

NASA Astrophysics Data System (ADS)

Lynn, K. G.

A general theoretical model is presented which includes the probability of a positron diffusing back to the surface after implantation, and thermalization in samples containing various defects. This model incorporates surface state and thermal desorption from this state, as well as reflection back into the bulk. With this model vacancy formation enthalpies, activation energies of positrons from surface states, and specific trapping rates are deduced from the positronium fraction data. An amorphous Al/sub x/O/sub y/ overlayer on Al is discussed as an example of trapping in overlayers. In well-annealed single crystal samples, the positron is shown to be freely diffusing at low temperatures, whereas in a neutron-irradiatied Al single crystal sample the positron is localized at low positron binding energy defects presumably created during irradiation.

Effect of Processing Parameters on Plastic Flow and Defect Formation in Friction-Stir-Welded Aluminum Alloy

NASA Astrophysics Data System (ADS)

Zeng, X. H.; Xue, P.; Wang, D.; Ni, D. R.; Xiao, B. L.; Ma, Z. Y.

2018-07-01

The effect of processing parameters on material flow and defect formation during friction stir welding (FSW) was investigated on 6.0-mm-thick 2014Al-T6 rolled plates with an artificially thickened oxide layer on the butt surface as the marker material. It was found that the "S" line in the stir zone (SZ) rotated with the pin and stayed on the retreating side (RS) and advancing side (AS) at low and high heat inputs, respectively. When the tool rotation rate was extremely low, the oxide layer under the pin moved to the RS first and then to the AS perpendicular to the welding direction, rather than rotating with the pin. The material flow was driven by the shear stresses produced by the forces at the pin-workpiece interface. With increases of the rotation rate, the depth of the shoulder-affected zone (SAZ) first decreased and then increased due to the decreasing shoulder friction force and increasing heat input. Insufficient material flow appeared in the whole of the SZ at low rotation rates and in the bottom of the SZ at high rotation rates, resulting in the formation of the "S" line. The extremely inadequate material flow is the reason for the lack of penetration and the kissing bonds in the bottom of the SZ at extremely low and low rotation rates, respectively.

Effect of Processing Parameters on Plastic Flow and Defect Formation in Friction-Stir-Welded Aluminum Alloy

NASA Astrophysics Data System (ADS)

Zeng, X. H.; Xue, P.; Wang, D.; Ni, D. R.; Xiao, B. L.; Ma, Z. Y.

2018-04-01

The effect of processing parameters on material flow and defect formation during friction stir welding (FSW) was investigated on 6.0-mm-thick 2014Al-T6 rolled plates with an artificially thickened oxide layer on the butt surface as the marker material. It was found that the "S" line in the stir zone (SZ) rotated with the pin and stayed on the retreating side (RS) and advancing side (AS) at low and high heat inputs, respectively. When the tool rotation rate was extremely low, the oxide layer under the pin moved to the RS first and then to the AS perpendicular to the welding direction, rather than rotating with the pin. The material flow was driven by the shear stresses produced by the forces at the pin-workpiece interface. With increases of the rotation rate, the depth of the shoulder-affected zone (SAZ) first decreased and then increased due to the decreasing shoulder friction force and increasing heat input. Insufficient material flow appeared in the whole of the SZ at low rotation rates and in the bottom of the SZ at high rotation rates, resulting in the formation of the "S" line. The extremely inadequate material flow is the reason for the lack of penetration and the kissing bonds in the bottom of the SZ at extremely low and low rotation rates, respectively.

Application of Laser Treatment for Hardening Parts of Gas Turbine Engines from Titanium Alloys

NASA Astrophysics Data System (ADS)

Girzhon, V. V.; Ovchinnikov, A. V.

2017-03-01

X-ray diffraction analysis and light microscopy are used to study the structure of surface layers of helically extruded specimens of titanium alloy VT25U after laser fusion of the surface. It is shown that the rates of cooling of the melt promote formation of a martensitic α″-phase in the zone of laser fusion and of a submicrocrystalline microstructure. The microhardness in the zone of fusion of the initial specimens exceeds the microhardness of the specimens after the extrusion.

Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

NASA Technical Reports Server (NTRS)

Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

1994-01-01

Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

The stratigraphic filter and bias in measurement of geologic rates

USGS Publications Warehouse

Schumer, R.; Jerolmack, D.; McElroy, B.

2011-01-01

Erosion and deposition rates estimated from the stratigraphic record frequently exhibit a power-law dependence on measurement interval. This dependence can result from a power-law distribution of stratigraphic hiatuses. By representing the stratigraphic filter as a stochastic process called a reverse ascending ladder, we describe a likely origin of power-law hiatuses, and thus, rate scaling. While power-law hiatuses in certain environments can be a direct result of power-law periods of stasis (no deposition or erosion), they are more generally the result of randomness in surface fluctuations irrespective of mean subsidence or uplift. Autocorrelation in fluctuations can make hiatuses more or less heavy-tailed, but still exhibit power-law characteristics. In addition we show that by passing stratigraphic data backward through the filter, certain statistics of surface kinematics from their formative environments can be inferred. Copyright ?? 2011 by the American Geophysical Union.

Tribological properties of multifunctional coatings with Shape Memory Effect in abrasive wear

NASA Astrophysics Data System (ADS)

Blednova, Zh. M.; Dmitrenko, D. V.; Balaev, E. U. O.

2018-01-01

The article gives research results of the abrasive wear process on samples made of Steel 1045, U10 and with applied composite surface layer "Nickel-Multicomponent material with Shape Memory Effect (SME) based on TiNi". For the tests we have chosen TiNiZr, which is in the martensite state and TiNiHfCu, which is in the austenitic state at the test temperature. The formation of the surface layer was carried out by high-speed oxygen-fuel deposition in a protective atmosphere of argon. In the wear test, Al2O3 corundum powder was used as an abrasive. It is shown that the wear rate of samples with a composite surface layer of multicomponent materials with SME is significantly reduced in comparison with the base, which is explained by reversible phase transformations of the surface layer with SME. After carrying out the additional surface plastic deformation (SPD), the resistance of the laminated composition to abrasion wear has greatly enhanced, due to the reinforcing effect of the SPD. It is recommended for products working in conditions of abrasive wear and high temperatures to use the complex formation technology of the surface composition "steel-nickel-material with high-temperature SME", including preparation of the substrate surface and the deposited material, high-speed spraying in the protective atmosphere of argon, followed by SPD.

Reaction and Aggregation Dynamics of Cell Surface Receptors

NASA Astrophysics Data System (ADS)

Wang, Michelle Dong

This dissertation is composed of both theoretical and experimental studies of cell surface receptor reaction and aggregation. Project I studies the reaction rate enhancement due to surface diffusion of a bulk dissolved ligand with its membrane embedded target, using numerical calculations. The results show that the reaction rate enhancement is determined by ligand surface adsorption and desorption kinetic rates, surface and bulk diffusion coefficients, and geometry. In particular, we demonstrate that the ligand surface adsorption and desorption kinetic rates, rather than their ratio (the equilibrium constant), are important in rate enhancement. The second and third projects are studies of acetylcholine receptor clusters on cultured rat myotubes using fluorescence techniques after labeling the receptors with tetramethylrhodamine -alpha-bungarotoxin. The second project studies when and where the clusters form by making time-lapse movies. The movies are made from overlay of the pseudocolored total internal reflection fluorescence (TIRF) images of the cluster, and the schlieren images of the cell cultures. These movies are the first movies made using TIRF, and they clearly show the cluster formation from the myoblast fusion, the first appearance of clusters, and the eventual disappearance of clusters. The third project studies the fine structural features of individual clusters observed under TIRF. The features were characterized with six parameters by developing a novel fluorescence technique: spatial fluorescence autocorrelation. These parameters were then used to study the feature variations with age, and with treatments of drugs (oligomycin and carbachol). The results show little variation with age. However, drug treatment induced significant changes in some parameters. These changes were different for oligomycin and carbachol, which indicates that the two drugs may eliminate clusters through different mechanisms.

Transient atomic behavior and surface kinetics of GaN

NASA Astrophysics Data System (ADS)

Moseley, Michael; Billingsley, Daniel; Henderson, Walter; Trybus, Elaissa; Doolittle, W. Alan

2009-07-01

An in-depth model for the transient behavior of metal atoms adsorbed on the surface of GaN is developed. This model is developed by qualitatively analyzing transient reflection high energy electron diffraction (RHEED) signals, which were recorded for a variety of growth conditions of GaN grown by molecular-beam epitaxy (MBE) using metal-modulated epitaxy (MME). Details such as the initial desorption of a nitrogen adlayer and the formation of the Ga monolayer, bilayer, and droplets are monitored using RHEED and related to Ga flux and shutter cycles. The suggested model increases the understanding of the surface kinetics of GaN, provides an indirect method of monitoring the kinetic evolution of these surfaces, and introduces a novel method of in situ growth rate determination.

Engineering Surfaces for Enhanced Nucleation and Droplet Removal During Dropwise Condensation

NASA Astrophysics Data System (ADS)

Dutta, Sanmitra; Khan, Sameera; Anand, Sushant

2017-11-01

Condensation plays critical role in numerous industrial applications, such as condensers, HVAC,etc In the most applications, fast formation (i.e. high nucleation) and subsequent removal of water droplets is critical for enhancing the efficiencies of their associated systems. Significant focus has been placed on the aspect of droplet removal from surfaces. This has led to, development of superhydrophobic surfaces with special textures on which droplets are self-removed after coalescence. However,because of their inherent low surface energy, nucleation energy barriers are also high on such surfaces. In contrast to conventional superhydrophobic surfaces, here we show that surfaces can be engineered such that the simultaneous benefits of high nucleation rates and fast droplet removal can be obtained during the condensation process.These benefits are obtained by impregnating a superhydrophobic surface with an oil that despite its defect-free interface provides low nucleation energy barrier during condensation. At the same time, the oil facilitates high droplet shedding rates by providing a lubricating layer below the droplets due to which droplets have negligible contact angle hysteresis. We provide a guide to choose oils that lead to enhanced nucleation, and provide experimental evidence supporting the proposed guide. We discuss the importance of different oil properties in affecting the droplet growth and subsequent removal of water droplets.

SURFACE CHEMKIN-III: A Fortran package for analyzing heterogeneous chemical kinetics at a solid-surface - gas-phase interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coltrin, M.E.; Kee, R.J.; Rupley, F.M.

1996-05-01

This document is the user`s manual for the SURFACE CHEMKIN-III package. Together with CHEMKIN-III, this software facilitates the formation, solution, and interpretation of problems involving elementary heterogeneous and gas-phase chemical kinetics in the presence of a solid surface. The package consists of two major software components: an Interpreter and a Surface Subroutine Library. The Interpreter is a program that reads a symbolic description of a user-specified chemical reaction mechanism. One output from the Interpreter is a data file that forms a link to the Surface Subroutine Library, which is a collection of about seventy modular Fortran subroutines that may bemore » called from a user`s application code to return information on chemical production rates and thermodynamic properties. This version of SURFACE CHEMKIN-III includes many modifications to allow treatment of multi-fluid plasma systems, for example modeling the reactions of highly energetic ionic species with a surface. Optional rate expressions allow reaction rates to depend upon ion energy rather than a single thermodynamic temperature. In addition, subroutines treat temperature as an array, allowing an application code to define a different temperature for each species. This version of SURFACE CHEMKIN-III allows use of real (non-integer) stoichiometric coefficients; the reaction order with respect to species concentrations can also be specified independent of the reaction`s stoichiometric coefficients. Several different reaction mechanisms can be specified in the Interpreter input file through the new construct of multiple materials.« less

Surface-catalyzed air oxidation of hydrazines: Environmental chamber studies

NASA Technical Reports Server (NTRS)

Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

1988-01-01

The surface-catalyzed air oxidation reactions of fuel hydrazines were studied in a 6500-liter fluorocarbon-film chamber at 80 to 100 ppm concentrations. First-order rate constants for the reactions catalyzed by aluminum, water-damaged aluminum (Al/Al2O3), stainless steel 304L, galvanized steel and titanium plates with surface areas of 2 to 24 sq m were determined. With 23.8 sq m of Al/Al2O3 the surface-catalyzed air oxidation of hydrazine had a half-life of 2 hours, diimide (N2H2) was observed as an intermediate and traces of ammonia were present in the final product mixture. The Al/Al2O3 catalyzed oxidation of monomethylhydrazine yielded methyldiazine (HN = NCH3) as an intermediate and traces of methanol. Unsymmetrical dimethylhydrazine gave no detectable products. The relative reactivities of hydrazine, MMH and UDMH were 130 : 7.3 : 1.0, respectively. The rate constants for Al/Al2O3-catalyzed oxidation of hydrazine and MMH were proportional to the square of the surface area of the plates. Mechanisms for the surface-catalyzed oxidation of hydrazine and diimide and the formation of ammonia are proposed.

Biodegradation improvement of poly(3-hydroxy-butyrate) films by entomopathogenic fungi and UV-assisted surface functionalization.

PubMed

Kessler, Felipe; Marconatto, Leticia; Rodrigues, Roberta da Silva Bussamara; Lando, Gabriela Albara; Schrank, Augusto; Vainstein, Marilene Henning; Weibel, Daniel Eduardo

2014-01-05

Ultraviolet (UV)-assisted surface modification in the presence of oxygen was used as initial step to achieve controlled degradation of poly(3-hydroxy-butyrate), PHB, films by entomopathogenic fungi. Treated surfaces were investigated by surface analysis techniques (water contact angle, Fourier Transformed Infrared Spectroscopy in Attenuated Total Reflectance mode, X-ray Photoelectron Spectroscopy, Near-edge X-ray Absorption Fine Structure, Gel Permeation Chromatography, Optical Microscopy, Scanning Electron Microscopy, and weight loss). After the UV-assisted treatments, new carbonyl groups in new chemical environments were detected by XPS and NEXAFS spectroscopy. The oxidizing atmosphere did not allow the formation of CC bonds, indicating that Norrish Type II mechanism is suppressed during or by the treatments. The higher hydrophilicity and concentration of oxygenated functional groups at the surface of the treated films possibly improved the biodegradation of the films. It was observed a clear increase in the growth of this fungus when oxygenated groups were grafted on the polymers surfaces. This simple methodology can be used to improve and control the degradation rate of PHB films in applications that require a controllable degradation rate. Copyright © 2013 Elsevier B.V. All rights reserved.

Relating Silica Scaling in Reverse Osmosis to Membrane Surface Properties.

PubMed

Tong, Tiezheng; Zhao, Song; Boo, Chanhee; Hashmi, Sara M; Elimelech, Menachem

2017-04-18

We investigated the relationship between membrane surface properties and silica scaling in reverse osmosis (RO). The effects of membrane hydrophilicity, free energy for heterogeneous nucleation, and surface charge on silica scaling were examined by comparing thin-film composite polyamide membranes grafted with a variety of polymers. Results show that the rate of silica scaling was independent of both membrane hydrophilicity and free energy for heterogeneous nucleation. In contrast, membrane surface charge demonstrated a strong correlation with the extent of silica scaling (R 2 > 0.95, p < 0.001). Positively charged membranes significantly facilitated silica scaling, whereas a more negative membrane surface charge led to reduced scaling. This observation suggests that deposition of negatively charged silica species on the membrane surface plays a critical role in silica scale formation. Our findings provide fundamental insights into the mechanisms governing silica scaling in reverse osmosis and highlight the potential of membrane surface modification as a strategy to reduce silica scaling.

Faraday efficiency and mechanism of electrochemical surface reactions: CO2 reduction and H2 formation on Pt(111).

PubMed

Hussain, Javed; Jónsson, Hannes; Skúlason, Egill

2016-12-22

An atomic scale model of the electrical double layer is used to calculate the mechanism and rate of electrochemical reduction of CO 2 as well as H 2 formation at a Pt(111) electrode. The water layer contains solvated protons and the electrode has excess electrons at the surface. Density functional theory within the generalized gradient approximation is used to describe the electronic structure while the mechanism and activation energy of the various elementary reactions is obtained by calculating minimum energy paths using the nudged elastic band method. The applied electrical potential is deduced from the calculated work function. The optimal reaction mechanism for CO 2 reduction to either methane or methanol is found and the estimated rate compared with that of the competing reaction, H 2 formation. When the free energy of only the intermediates and reactants is taken into account, not the activation energy, Pt(111) would seem to be a good electrocatalyst for CO 2 reduction, significantly better than Cu(111). This, however, contradicts experimental findings. Detailed calculations reported here show that the activation energy for CO 2 reduction is high for both Heyrovsky and Tafel mechanisms on Pt(111) in the relevant range of applied potential. The rate-limiting step of the Heyrovsky mechanism, *COOH + H + + e - → *CO + H 2 O, is estimated to have an activation energy of 0.95 eV at -0.9 V vs. standard hydrogen electrode. Under the same conditions, the activation energy for H 2 formation is estimated to be only 0.5 eV. This explains why attempts to reduce CO 2 using platinum electrodes have produced only H 2 . A comparison is made with analogous results for Cu(111) [J. Hussain et al., Procedia Comput. Sci., 2015, 51, 1865] where a reaction mechanism with low activation energy for CO 2 electroreduction to methane was identified. The difference between the two electrocatalysts is discussed.

Transitions from near-surface to interior redox upon lithiation in conversion electrode materials.

PubMed

He, Kai; Xin, Huolin L; Zhao, Kejie; Yu, Xiqian; Nordlund, Dennis; Weng, Tsu-Chien; Li, Jing; Jiang, Yi; Cadigan, Christopher A; Richards, Ryan M; Doeff, Marca M; Yang, Xiao-Qing; Stach, Eric A; Li, Ju; Lin, Feng; Su, Dong

2015-02-11

Nanoparticle electrodes in lithium-ion batteries have both near-surface and interior contributions to their redox capacity, each with distinct rate capabilities. Using combined electron microscopy, synchrotron X-ray methods and ab initio calculations, we have investigated the lithiation pathways that occur in NiO electrodes. We find that the near-surface electroactive (Ni(2+) → Ni(0)) sites saturated very quickly, and then encounter unexpected difficulty in propagating the phase transition into the electrode (referred to as a "shrinking-core" mode). However, the interior capacity for Ni(2+) → Ni(0) can be accessed efficiently following the nucleation of lithiation "fingers" that propagate into the sample bulk, but only after a certain incubation time. Our microstructural observations of the transition from a slow shrinking-core mode to a faster lithiation finger mode corroborate with synchrotron characterization of large-format batteries and can be rationalized by stress effects on transport at high-rate discharge. The finite incubation time of the lithiation fingers sets the intrinsic limitation for the rate capability (and thus the power) of NiO for electrochemical energy storage devices. The present work unravels the link between the nanoscale reaction pathways and the C-rate-dependent capacity loss and provides guidance for the further design of battery materials that favors high C-rate charging.

Kidney stones.

PubMed

Khan, Saeed R; Pearle, Margaret S; Robertson, William G; Gambaro, Giovanni; Canales, Benjamin K; Doizi, Steeve; Traxer, Olivier; Tiselius, Hans-Göran

2016-02-25

Kidney stones are mineral deposits in the renal calyces and pelvis that are found free or attached to the renal papillae. They contain crystalline and organic components and are formed when the urine becomes supersaturated with respect to a mineral. Calcium oxalate is the main constituent of most stones, many of which form on a foundation of calcium phosphate called Randall's plaques, which are present on the renal papillary surface. Stone formation is highly prevalent, with rates of up to 14.8% and increasing, and a recurrence rate of up to 50% within the first 5 years of the initial stone episode. Obesity, diabetes, hypertension and metabolic syndrome are considered risk factors for stone formation, which, in turn, can lead to hypertension, chronic kidney disease and end-stage renal disease. Management of symptomatic kidney stones has evolved from open surgical lithotomy to minimally invasive endourological treatments leading to a reduction in patient morbidity, improved stone-free rates and better quality of life. Prevention of recurrence requires behavioural and nutritional interventions, as well as pharmacological treatments that are specific for the type of stone. There is a great need for recurrence prevention that requires a better understanding of the mechanisms involved in stone formation to facilitate the development of more-effective drugs.

Feedback dew-point sensor utilizing optimally cut plastic optical fibres

NASA Astrophysics Data System (ADS)

Hadjiloucas, S.; Irvine, J.; Keating, D. A.

2000-01-01

A plastic optical fibre reflectance sensor that makes full use of the critical angle of the fibres is implemented to monitor dew formation on a Peltier-cooled reflector surface. The optical configuration permits isolation of optoelectronic components from the sensing head and better light coupling between the reflector and the detecting fibre, giving a better signal of the onset of dew formation on the reflector. Continuous monitoring of the rate of change in reflectance as well as the absolute reflectance signals, the use of a novel polymethyl-methacrylate-coated hydrophobic film reflector on the Peltier element and the application of feedback around the point of dew formation, further reduces the possibility of contamination of the sensor head. Under closed-loop operation, the sensor is capable of cycling around the point of dew formation at a frequency of 2.5 Hz.

The rate and latency of star formation in dense, massive clumps in the Milky Way

NASA Astrophysics Data System (ADS)

Heyer, M.; Gutermuth, R.; Urquhart, J. S.; Csengeri, T.; Wienen, M.; Leurini, S.; Menten, K.; Wyrowski, F.

2016-04-01

Context. Newborn stars form within the localized, high density regions of molecular clouds. The sequence and rate at which stars form in dense clumps and the dependence on local and global environments are key factors in developing descriptions of stellar production in galaxies. Aims: We seek to observationally constrain the rate and latency of star formation in dense massive clumps that are distributed throughout the Galaxy and to compare these results to proposed prescriptions for stellar production. Methods: A sample of 24 μm-based Class I protostars are linked to dust clumps that are embedded within molecular clouds selected from the APEX Telescope Large Area Survey of the Galaxy. We determine the fraction of star-forming clumps, f∗, that imposes a constraint on the latency of star formation in units of a clump's lifetime. Protostellar masses are estimated from models of circumstellar environments of young stellar objects from which star formation rates are derived. Physical properties of the clumps are calculated from 870 μm dust continuum emission and NH3 line emission. Results: Linear correlations are identified between the star formation rate surface density, ΣSFR, and the quantities ΣH2/τff and ΣH2/τcross, suggesting that star formation is regulated at the local scales of molecular clouds. The measured fraction of star forming clumps is 23%. Accounting for star formation within clumps that are excluded from our sample due to 24 μm saturation, this fraction can be as high as 31%, which is similar to previous results. Dense, massive clumps form primarily low mass (<1-2 M⊙) stars with emergent 24 μm fluxes below our sensitivity limit or are incapable of forming any stars for the initial 70% of their lifetimes. The low fraction of star forming clumps in the Galactic center relative to those located in the disk of the Milky Way is verified. Full Tables 2-4 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/588/A29

The initial cooling of pahoehoe flow lobes

USGS Publications Warehouse

Keszthelyi, L.; Denlinger, R.

1996-01-01

In this paper we describe a new thermal model for the initial cooling of pahoehoe lava flows. The accurate modeling of this initial cooling is important for understanding the formation of the distinctive surface textures on pahoehoe lava flows as well as being the first step in modeling such key pahoehoe emplacement processes as lava flow inflation and lava tube formation. This model is constructed from the physical phenomena observed to control the initial cooling of pahoehoe flows and is not an empirical fit to field data. We find that the only significant processes are (a) heat loss by thermal radiation, (b) heat loss by atmospheric convection, (c) heat transport within the flow by conduction with temperature and porosity-dependent thermal properties, and (d) the release of latent heat during crystallization. The numerical model is better able to reproduce field measurements made in Hawai'i between 1989 and 1993 than other published thermal models. By adjusting one parameter at a time, the effect of each of the input parameters on the cooling rate was determined. We show that: (a) the surfaces of porous flows cool more quickly than the surfaces of dense flows, (b) the surface cooling is very sensitive to the efficiency of atmospheric convective cooling, and (c) changes in the glass forming tendency of the lava may have observable petrographic and thermal signatures. These model results provide a quantitative explanation for the recently observed relationship between the surface cooling rate of pahoehoe lobes and the porosity of those lobes (Jones 1992, 1993). The predicted sensitivity of cooling to atmospheric convection suggests a simple field experiment for verification, and the model provides a tool to begin studies of the dynamic crystallization of real lavas. Future versions of the model can also be made applicable to extraterrestrial, submarine, silicic, and pyroclastic flows.

Investigating the BSA protein adsorption and bacterial adhesion of Al-alloy surfaces after creating a hierarchical (micro/nano) superhydrophobic structure.

PubMed

Moazzam, Parisa; Razmjou, Amir; Golabi, Mohsen; Shokri, Dariush; Landarani-Isfahani, Amir

2016-09-01

Bacterial adhesion and subsequent biofilm formation on metals such as aluminum (Al) alloys lead to serious issues in biomedical and industrial fields from both an economical and health perspective. Here, we showed that a careful manipulation of Al surface characteristics via a facile two-steps superhydrophobic modification can provide not only biocompatibility and an ability to control protein adsorption and bacterial adhesion, but also address the issue of apparent long-term toxicity of Al-alloys. To find out the roles of surface characteristics, surface modification and protein adsorption on microbial adhesion and biofilm formation, the surfaces were systematically characterized by SEM, EDX, XPS, AFM, FTIR, water contact angle (WCA) goniometry, surface free energy (SFE) measurement, MTT, Bradford, Lowry and microtiter plate assays and also flow-cytometry and potentiostat analyses. Results showed that WCA and SFE changed from 70° to 163° and 36.3 to 0.13 mN m(-1) , respectively. The stable and durable modification led to a substantial reduction in static/dynamic BSA adsorption. The effect of such a treatment on the biofilm formation was analyzed by using three different bacteria of Pseudomonas aeruginosa, Staphylococcus epidermidis, and Staphylococcus aureus. The microtiter plate assay and flow cytometry analysis showed that the modification not only could substantially reduce the bacterial adhesion but this biofouling resistance is independent of bacterium type. An excellent cell viability after exposure of HeLa cells to waters incubated with the modified samples was observed. Finally, the corrosion rate reduced sharply from 856.6 to 0.119 MPY after superhydrophobic modifications, which is an excellent stable corrosion inhibition property. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2220-2233, 2016. © 2016 Wiley Periodicals, Inc.

Fundamental issues in the geology and geophysics of venus.

PubMed

Solomon, S C; Head, J W

1991-04-12

A number of important and currently unresolved issues in the global geology and geophysics of Venus will be addressable with the radar imaging, altimetry, and gravity measurements now forthcoming from the Magellan mission. Among these are the global volcanic flux and the rate of formation of new crust; the global heat flux and its regional variations; the relative importance of localized hot spots and linear centers of crustal spreading to crustal formation and tectonics; and the planform of mantle convection on Venus and the nature of the interactions among interior convective flow, near-surface deformation and magmatism.

Functionalized granular activated carbon and surface complexation with chromates and bi-chromates in wastewater.

PubMed

Singha, Somdutta; Sarkar, Ujjaini; Luharuka, Pallavi

2013-03-01

Cr(VI) is present in the aqueous medium as chromate (CrO4(2-)) and bi-chromate (HCrO4(-)). Functionalized granular activated carbons (FACs) are used as adsorbents in the treatment of wastewaters containing hexavalent chromium. The FACs are prepared by chemical modifications of granular activated carbons (GACs) using functionalizing agents like HNO3, HCl and HF. The Brunauer, Emmett and Teller surface areas of FAC-HCl (693.5m(2)/g), FAC-HNO3 (648.8m(2)/g) and FAC-HF (726.2m(2)/g) are comparable to the GAC (777.7m(2)/g). But, the adsorption capacity of each of the FAC-HNO3, FAC-HCl and FAC-HF is found to be higher than the GAC. The functional groups play an important role in the adsorption process and pH has practically no role in this specific case. The FACs have hydrophilic protonated external surfaces in particular, along with the functional surface sites capable to make complexes with the CrO4(2-) and HCrO4(-) present. Surface complex formation is maximized in the order FAC-HNO3>FAC-HF>FAC-HCl, in proportion to the total surface acidity. This is also confirmed by the well-known pseudo second-order kinetic model. Physi-sorption equilibrium isotherms are parameterized by using standard Freundlich and Langmuir models. Langmuir fits better. The formation of surface complexes with the functional groups and hexavalent chromium is also revealed in the images of field emission scanning electron micrograph; energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy analysis after adsorption. The intra-particle diffusion is not the only rate-controlling factor. The Boyd's film diffusion model fits very well with R(2) as high as 98.1% for FAC-HNO3. This result demonstrates that the functionalization of the GAC by acid treatments would increase the diffusion rate, predominantly with a boundary layer diffusion effect. Copyright © 2013 Elsevier B.V. All rights reserved.

Stereopsis and 3D surface perception by spiking neurons in laminar cortical circuits: a method for converting neural rate models into spiking models.

PubMed

Cao, Yongqiang; Grossberg, Stephen

2012-02-01

A laminar cortical model of stereopsis and 3D surface perception is developed and simulated. The model shows how spiking neurons that interact in hierarchically organized laminar circuits of the visual cortex can generate analog properties of 3D visual percepts. The model describes how monocular and binocular oriented filtering interact with later stages of 3D boundary formation and surface filling-in in the LGN and cortical areas V1, V2, and V4. It proposes how interactions between layers 4, 3B, and 2/3 in V1 and V2 contribute to stereopsis, and how binocular and monocular information combine to form 3D boundary and surface representations. The model suggests how surface-to-boundary feedback from V2 thin stripes to pale stripes helps to explain how computationally complementary boundary and surface formation properties lead to a single consistent percept, eliminate redundant 3D boundaries, and trigger figure-ground perception. The model also shows how false binocular boundary matches may be eliminated by Gestalt grouping properties. In particular, the disparity filter, which helps to solve the correspondence problem by eliminating false matches, is realized using inhibitory interneurons as part of the perceptual grouping process by horizontal connections in layer 2/3 of cortical area V2. The 3D sLAMINART model simulates 3D surface percepts that are consciously seen in 18 psychophysical experiments. These percepts include contrast variations of dichoptic masking and the correspondence problem, the effect of interocular contrast differences on stereoacuity, Panum's limiting case, the Venetian blind illusion, stereopsis with polarity-reversed stereograms, da Vinci stereopsis, and perceptual closure. The model hereby illustrates a general method of unlumping rate-based models that use the membrane equations of neurophysiology into models that use spiking neurons, and which may be embodied in VLSI chips that use spiking neurons to minimize heat production. Copyright © 2011 Elsevier Ltd. All rights reserved.

A kinetic model of the formation of organic monolayers on hydrogen-terminated silicon by hydrosilation of alkenes.

PubMed

Woods, M; Carlsson, S; Hong, Q; Patole, S N; Lie, L H; Houlton, A; Horrocks, B R

2005-12-22

We have analyzed a kinetic model for the formation of organic monolayers based on a previously suggested free radical chain mechanism for the reaction of unsaturated molecules with hydrogen-terminated silicon surfaces (Linford, M. R.; Fenter, P. M.; Chidsey, C. E. D. J. Am. Chem. Soc 1995, 117, 3145). A direct consequence of this mechanism is the nonexponential growth of the monolayer, and this has been observed spectroscopically. In the model, the initiation of silyl radicals on the surface is pseudo first order with rate constant, ki, and the rate of propagation is determined by the concentration of radicals and unreacted Si-H nearest neighbor sites with a rate constant, kp. This propagation step determines the rate at which the monolayer forms by addition of alkene molecules to form a track of molecules that constitute a self-avoiding random walk on the surface. The initiation step describes how frequently new random walks commence. A termination step by which the radicals are destroyed is also included. The solution of the kinetic equations yields the fraction of alkylated surface sites and the mean length of the random walks as a function of time. In mean-field approximation we show that (1) the average length of the random walk is proportional to (kp/ki)1/2, (2) the monolayer surface coverage grows exponentially only after an induction period, (3) the effective first-order rate constant describing the growth of the monolayer and the induction period (kt) is k = (2ki kp)1/2, (4) at long times the effective first-order rate constant drops to ki, and (5) the overall activation energy for the growth kinetics is the mean of the activation energies for the initiation and propagation steps. Monte Carlo simulations of the mechanism produce qualitatively similar kinetic plots, but the mean random walk length (and effective rate constant) is overestimated by the mean field approximation and when kp > ki, we find k approximately ki0.7kp0.3 and Ea = (0.7Ei+ 0.3Ep). However the most striking prediction of the Monte Carlo simulations is that at long times, t > 1/k, the effective first-order rate constant decreases to ki even in the absence of a chemical termination step. Experimental kinetic data for the reaction of undec-1-ene with hydrogen-terminated porous silicon under thermal reflux in toluene and ethylbenzene gave a value of k = 0.06 min(-1) and an activation energy of 107 kJ mol(-1). The activation energy is in reasonable agreement with density functional calculations of the transition state energies for the initiation and propagation steps.

Self-organized pattern formation at organic-inorganic interfaces during deposition: Experiment versus modeling

NASA Astrophysics Data System (ADS)

Szillat, F.; Mayr, S. G.

2011-09-01

Self-organized pattern formation during physical vapor deposition of organic materials onto rough inorganic substrates is characterized by a complex morphological evolution as a function of film thickness. We employ a combined experimental-theoretical study using atomic force microscopy and numerically solved continuum rate equations to address morphological evolution in the model system: poly(bisphenol A carbonate) on polycrystalline Cu. As the key ingredients for pattern formation, (i) curvature and interface potential driven surface diffusion, (ii) deposition noise, and (iii) interface boundary effects are identified. Good agreement of experiments and theory, fitting only the Hamaker constant and diffusivity within narrow physical parameter windows, corroborates the underlying physics and paves the way for computer-assisted interface engineering.

Ozone and alkyl nitrate formation from the Deepwater Horizon oil spill atmospheric emissions

NASA Astrophysics Data System (ADS)

Neuman, J. A.; Aikin, K. C.; Atlas, E. L.; Blake, D. R.; Holloway, J. S.; Meinardi, S.; Nowak, J. B.; Parrish, D. D.; Peischl, J.; Perring, A. E.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Trainer, M.

2012-05-01

Ozone (O3), alkyl nitrates (RONO2), and other photochemical products were formed in the atmosphere downwind from the Deepwater Horizon (DWH) oil spill by photochemical reactions of evaporating hydrocarbons with NOx (=NO + NO2) emissions from spill response activities. Reactive nitrogen species and volatile organic compounds (VOCs) were measured from an instrumented aircraft during daytime flights in the marine boundary layer downwind from the area of surfacing oil. A unique VOC mixture, where alkanes dominated the hydroxyl radical (OH) loss rate, was emitted into a clean marine environment, enabling a focused examination of O3 and RONO2 formation processes. In the atmospheric plume from DWH, the OH loss rate, an indicator of potential O3 formation, was large and dominated by alkanes with between 5 and 10 carbons per molecule (C5-C10). Observations showed that NOx was oxidized very rapidly with a 0.8 h lifetime, producing primarily C6-C10 RONO2 that accounted for 78% of the reactive nitrogen enhancements in the atmospheric plume 2.5 h downwind from DWH. Both observations and calculations of RONO2 and O3 production rates show that alkane oxidation dominated O3 formation chemistry in the plume. Rapid and nearly complete oxidation of NOx to RONO2 effectively terminated O3 production, with O3 formation yields of 6.0 ± 0.5 ppbv O3 per ppbv of NOx oxidized. VOC mixing ratios were in large excess of NOx, and additional NOx would have formed additional O3 in this plume. Analysis of measurements of VOCs, O3, and reactive nitrogen species and calculations of O3 and RONO2 production rates demonstrate that NOx-VOC chemistry in the DWH plume is explained by known mechanisms.

Effect of Na poisoning catalyst (V2O5-WO3/TiO2) on denitration process and SO3 formation

NASA Astrophysics Data System (ADS)

Xiao, Haiping; Chen, Yu; Qi, Cong; Ru, Yu

2018-03-01

This paper aims to study the effect of alkali metal sodium (Na) poisoning on the performance of the Selective Catalytic Reduction (SCR) catalyst. The result showed that Na2SO4 poisoning leads to a reduced denitration rate of the SCR catalyst and an increase in the SO3 generation rate. Na2O poisoning leads to a significant reduction in the denitration rate of the SCR catalyst and marginally improves the formation of SO3. The maximum of the SO3 generation rate for a Na2SO4-poisoned catalyst reached 1.35%, whereas it was only 0.85% for the SCR catalyst. When the SO2 was contained in flue gas, the denitration rate for the Na2O-poisoned catalyst clearly increased by more than 28%. However, the effect of SO2 on the Na2SO4-poisoned catalyst was very slight. The denitration rate of the SCR catalyst decreased with an increase in the Na content. The BET and XRD results showed that Na poisoning of the catalyst decreased the number of acid sites, the reducibility of the catalyst, the surface area, and pore volume. The H2-TPR and NH3-TPD results show that Na decreases the number of acid sites and the reducibility of the catalyst. The FT-IR and XPS results showed that Na2O poisoning led to the decrease of V5+dbnd O bonds and the consumptions of oxygen atoms. Na2SO4 poisoning can improve surface adsorbed oxygen, which was beneficial for the SO2-SO3 conversion reaction.

Laminar Soot Processes (LSP)

NASA Technical Reports Server (NTRS)

Dai, Z.; El-Leathy, A. M.; Kim, C. H.; Krishnan, S. S.; Lin, K.-C.; Xu, F.; Faeth, G. M.

2002-01-01

This is the final report of a research program considering the structure and the soot surface reaction properties of laminar nonpremixed (diffusion) flames. The study was limited to ground-based measurements of buoyant laminar jet diffusion flames at pressures of 0.1-1.0 atm. The motivation for the research is that soot formation in flames is a major unresolved problem of combustion science that influences the pollutant emissions, durability and performance of power and propulsion systems, as well as the potential for developing computational combustion. The investigation was divided into two phases considering the structure of laminar soot-containing diffusion flames and the soot surface reaction properties (soot surface growth and oxidation) of these flames, in turn. The first phase of the research addressed flame and soot structure properties of buoyant laminar jet diffusion flames at various pressures. The measurements showed that H, OH and O radical concentrations were generally in superequilibrium concentrations at atmospheric pressure but tended toward subequilibrium concentrations as pressures decreased. The measurements indicated that the original fuel decomposed into more robust compounds at elevated temperatures, such as acetylene (unless the original fuel was acetylene) and H, which are the major reactants for soot surface growth, and that the main effect of the parent fuel on soot surface growth involved its yield of acetylene and H for present test conditions. The second phase of the research addressed soot surface reaction properties, e.g., soot surface growth and surface oxidation. It was found that soot surface growth rates in both laminar premixed and diffusion flames were in good agreement, that these rates were relatively independent of fuel type, and that these rates could be correlated by the Hydrogen-Abstraction/Carbon-Addition (HACA) mechanisms of Colket and Hall (1994), Frenklach et al. (1990,1994), and Kazakov et al. (1995). It was also found that soot surface oxidation rates were relatively independent of fuel type, were not correlated with O2, CO2, H2O and O collision rates but were correlated with the collision rates of OH with a collision efficiency of 0.14, in agreement with the early measurements in premixed flames of Neoh et al. (1980), after allowing for oxidation by O2 via the classical rate expression of Nagle and Strickland-Constable (1962).

A directional nucleation-zipping mechanism for triple helix formation

PubMed Central

Alberti, Patrizia; Arimondo, Paola B.; Mergny, Jean-Louis; Garestier, Thérèse; Hélène, Claude; Sun, Jian-Sheng

2002-01-01

A detailed kinetic study of triple helix formation was performed by surface plasmon resonance. Three systems were investigated involving 15mer pyrimidine oligonucleotides as third strands. Rate constants and activation energies were validated by comparison with thermodynamic values calculated from UV-melting analysis. Replacement of a T·A base pair by a C·G pair at either the 5′ or the 3′ end of the target sequence allowed us to assess mismatch effects and to delineate the mechanism of triple helix formation. Our data show that the association rate constant is governed by the sequence of base triplets on the 5′ side of the triplex (referred to as the 5′ side of the target oligopurine strand) and provides evidence that the reaction pathway for triple helix formation in the pyrimidine motif proceeds from the 5′ end to the 3′ end of the triplex according to the nucleation-zipping model. It seems that this is a general feature for all triple helices formation, probably due to the right-handedness of the DNA double helix that provides a stronger base stacking at the 5′ than at the 3′ duplex–triplex junction. Understanding the mechanism of triple helix formation is not only of fundamental interest, but may also help in designing better triple helix-forming oligonucleotides for gene targeting and control of gene expression. PMID:12490709

Excimer laser irradiation of metal surfaces

NASA Astrophysics Data System (ADS)

Kinsman, Grant

In this work a new method of enhancing CO2 laser processing by modifying the radiative properties of a metal surface is studied. In this procedure, an excimer laser (XeCl) or KrF) exposes the metal surface to overlapping pulses of high intensity, 10(exp 8) - 10(exp 9) W cm(exp -2), and short pulse duration, 30 nsec FWHM (Full Width Half Maximum), to promote structural and chemical change. The major processing effect at these intensities is the production of a surface plasma which can lead to the formation of a laser supported detonation wave (LSD wave). This shock wave can interact with the thin molten layer on the metal surface influencing to a varying degree surface oxidation and roughness features. The possibility of the expulsion, oxidation and redeposition of molten droplets, leading to the formation of micron thick oxide layers, is related to bulk metal properties and the incident laser intensity. A correlation is found between the expulsion of molten droplets and a Reynolds number, showing the interaction is turbulent. The permanent effects of these interactions on metal surfaces are observed through scanning electron microscopy (SEM), transient calorimetric measurements and Fourier transform infrared (FTIR) spectroscopy. Observed surface textures are related to the scanning procedures used to irradiate the metal surface. Fundamental radiative properties of a metal surface, the total hemispherical emissivity, the near-normal spectral absorptivity, and others are examined in this study as they are affected by excimer laser radiation. It is determined that for heavily exposed Al surface, alpha' (10.6 microns) can be increased to values close to unity. Data relating to material removal rates and chemical surface modification for excimer laser radiation is also discussed. The resultant reduction in the near-normal reflectivity solves the fundamental problem of coupling laser radiation into highly reflective and conductive metals such as copper and aluminum. The increased absorption at 10.6 microns enables enhanced CO2 laser drilling and cutting rates in electrolytic Cu at incident intensities, I(0) of approximately 10(exp 6) W cm(exp -2). Data showing enhanced drilling rates in Al 1100-H14 is also presented. In these regimes the majority of material is removed in the liquid state. The amount of molten material formed can be directly attributed to the enhanced initial coupling of the excimer laser irradiated surface. Previously, to process Cu and Al it has been required to increase I(0) until material removal occurs through vaporization. This fundamental data and analysis provides a basic framework for further work in this new field of study.

The Impact of Fluoride on Ameloblasts and the Mechanisms of Enamel Fluorosis

PubMed Central

Bronckers, A.L.J.J.; Lyaruu, D.M.; DenBesten, P.K.

2009-01-01

Intake of excess amounts of fluoride during tooth development cause enamel fluorosis, a developmental disturbance that makes enamel more porous. In mild fluorosis, there are white opaque striations across the enamel surface, whereas in more severe cases, the porous regions increase in size, with enamel pitting, and secondary discoloration of the enamel surface. The effects of fluoride on enamel formation suggest that fluoride affects the enamel-forming cells, the ameloblasts. Studies investigating the effects of fluoride on ameloblasts and the mechanisms of fluorosis are based on in vitro cultures as well as animal models. The use of these model systems requires a biologically relevant fluoride dose, and must be carefully interpreted in relation to human tooth formation. Based on these studies, we propose that fluoride can directly affect the ameloblasts, particularly at high fluoride levels, while at lower fluoride levels, the ameloblasts may respond to local effects of fluoride on the mineralizing matrix. A new working model is presented, focused on the assumption that fluoride increases the rate of mineral formation, resulting in a greater release of protons into the forming enamel matrix. PMID:19783795

Crystal orientation dependence of femtosecond laser-induced periodic surface structure on (100) silicon.

PubMed

Jiang, Lan; Han, Weina; Li, Xiaowei; Wang, Qingsong; Meng, Fantong; Lu, Yongfeng

2014-06-01

It is widely believed that laser-induced periodic surface structures (LIPSS) are independent of material crystal structures. This Letter reports an abnormal phenomenon of strong dependence of the anisotropic formation of periodic ripples on crystal orientation, when Si (100) is processed by a linearly polarized femtosecond laser (800 nm, 50 fs, 1 kHz). LIPSS formation sensitivity with a π/2 modulation is found along different crystal orientations with a quasi-cosinusoid function when the angle between the crystal orientation and polarization direction is changed from 0° to 180°. Our experiments indicate that it is much easier (or more difficult) to form ripple structures when the polarization direction is aligned with the lattice axis [011]/[011¯] (or [001]). The modulated nonlinear ionization rate along different crystal orientations, which arises from the direction dependence of the effective mass of the electron is proposed to interpret the unexpected anisotropic LIPSS formation phenomenon. Also, we demonstrate that the abnormal phenomenon can be applied to control the continuity of scanned ripple lines along different crystal orientations.

Mars brine formation experiment

NASA Technical Reports Server (NTRS)

Moore, Jeffrey M.; Bullock, Mark A.; Stoker, Carol R.

1992-01-01

Evaporites, particularly carbonates, nitrates, and sulfates, may be major sinks of volatiles scavenged from the martian atmosphere. Mars is thought to have once had a denser, warmer atmosphere that permitted the presence of liquid surface water. The conversion of atmospheric CO2 into carbonate is hypothesized to have degraded the martian climate to its present state of a generally subfreezing, desiccated desert. The rate for such a conversion under martian conditions is poorly known, so the time scale of climate degradation by this process cannot be easily evaluated. If some models are correct, carbonate formation may have been fast at geological time scales. The experiments of Booth and Kieffer also imply fast (10(exp 6) - 10(exp 7) yr) removal of the missing CO2 inventory, estimated to be 1 - 5 bar, by means of carbonate formation. The timing of formation of many of the fluvial features observed on Mars is, in large part, dependent on when and how fast the atmosphere changed. A knowledge of the rate at which carbonates and nitrates formed is also essential for assessing the probability that life, or its chemical precursors, could have developed on Mars. No previous experiments have quantitatively evaluated the rate of solution for a suite of mobile anions and cations from unaltered minerals and atmospheric gases into liquid water under Mars-like conditions. Such experiments are the focus of this task.

Acoustically-Enhanced Direct Contact Vapor Bubble Condensation

NASA Astrophysics Data System (ADS)

Boziuk, Thomas; Smith, Marc; Glezer, Ari

2017-11-01

Rate-limited, direct contact vapor condensation of vapor bubbles that are formed by direct steam injection through a nozzle in a quiescent subcooled liquid bath is accelerated using ultrasonic (MHz-range) actuation. A submerged, low power actuator produces an acoustic beam whose radiation pressure deforms the liquid-vapor interface, leading to the formation of a liquid spear that penetrates the vapor bubble to form a vapor torus with a significantly larger surface area and condensation rate. Ultrasonic focusing along the spear leads to the ejection of small, subcooled droplets through the vapor volume that impact the vapor-liquid interface and further enhance the condensation. High-speed Schlieren imaging of the formation and collapse of the vapor bubbles in the absence and presence of actuation shows that the impulse associated with the collapse of the toroidal volume leads to the formation of a turbulent vortex ring in the liquid phase. Liquid motions near the condensing vapor volume are investigated in the absence and presence of acoustic actuation using high-magnification PIV and show the evolution of a liquid jet through the center of the condensing toroidal volume and the formation and advection of vortex ring structures whose impulse appear to increase with temperature difference between the liquid and vapor phases. High-speed image processing is used to assess the effect of the actuation on the temporal and spatial variations in the characteristic scales and condensation rates of the vapor bubbles.

Cosmogenic 3He in hematite and goethite from Brazilian "canga" duricrust demonstrates the extreme stability of these surfaces

NASA Astrophysics Data System (ADS)

Shuster, David L.; Farley, Kenneth A.; Vasconcelos, Paulo M.; Balco, Greg; Monteiro, Hevelyn S.; Waltenberg, Kathryn; Stone, John O.

2012-05-01

Helium isotopes were measured in hematite and goethite samples from several lateritiric duricrusts (canga) developed on banded iron formations. These samples uniformly have high 3He concentrations which must arise from long periods of cosmic ray exposure. From coexisting phases from the Quadrilátero Ferrífero in east central Brazil, we determined the ratio of cosmogenic 3He in hematite to that of 21Ne in quartz to be 3.96 ± 0.19. Combined with best current estimates of the 21Ne production rate in quartz, this ratio implies a sea-level high latitude (SLHL) 3He production rate in hematite of 68.1 ± 8.1 atoms/g/yr; from the chemical composition we estimate the 3He production rate in goethite to be ~ 5% higher. We use these production rate estimates to interpret 3He concentrations measured in goethite and hematite from a ~ 10 m depth profile collected from a surface canga in Carajás, in the Amazon basin of Brazil. We find that the Carajás canga has experienced a very low rate of surface erosion (~ 0.16-0.54 m/Myr) over at least the last few millions of years. This iron-rich canga surface is remarkably resistant to erosion despite its location in a wet tropical environment. Details of the depth profile suggest that despite its stability, the canga has also been internally dynamic (translocation of material; solution and reprecipitation) over million-year timescales.

Hot spring siliceous stromatolites from Yellowstone National Park: assessing growth rate and laminae formation.

PubMed

Berelson, W M; Corsetti, F A; Pepe-Ranney, C; Hammond, D E; Beaumont, W; Spear, J R

2011-09-01

Stromatolites are commonly interpreted as evidence of ancient microbial life, yet stromatolite morphogenesis is poorly understood. We apply radiometric tracer and dating techniques, molecular analyses and growth experiments to investigate siliceous stromatolite morphogenesis in Obsidian Pool Prime (OPP), a hot spring in Yellowstone National Park. We examine rates of stromatolite growth and the environmental and/or biologic conditions that affect lamination formation and preservation, both difficult features to constrain in ancient examples. The "main body" of the stromatolite is composed of finely laminated, porous, light-dark couplets of erect (surface normal) and reclining (surface parallel) silicified filamentous bacteria, interrupted by a less-distinct, well-cemented "drape" lamination. Results from dating studies indicate a growth rate of 1-5 cm year(-1) ; however, growth is punctuated. (14)C as a tracer demonstrates that stromatolite cyanobacterial communities fix CO(2) derived from two sources, vent water (radiocarbon dead) and the atmosphere (modern (14)C). The drape facies contained a greater proportion of atmospheric CO(2) and more robust silica cementation (vs. the main body facies), which we interpret as formation when spring level was lower. Systematic changes in lamination style are likely related to environmental forcing and larger scale features (tectonic, climatic). Although the OPP stromatolites are composed of silica and most ancient forms are carbonate, their fine lamination texture requires early lithification. Without early lithification, whether silica or carbonate, it is unlikely that a finely laminated structure representing an ancient microbial mat would be preserved. In OPP, lithification on the nearly diurnal time scale is likely related to temperature control on silica solubility. © 2011 Blackwell Publishing Ltd.

Thiol surface complexation on growing CdS clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swayambunathan, V.; Hayes, D.; Schmidt, K.H.

1990-05-09

The growth of small CdS colloidal particles has been initiated by pulse radiolytic release of sulfide from thiol (3-mercapto-1,2-propanediol, RSH) in the presence of Cd{sup 2+} ions. The kinetics and stoichiometry of the ensuring reactions were followed by conductivity, absorption spectroscopy, and light-scattering techniques. The final CdS product has been identified by electron diffraction. The formation of Cd-thiolate complexes at the surface of the particles is indicated by conductivity and by energy dispersive analysis of X-ray (EDAX) results. The rate of formation of CdS clusters is strongly pH dependent due to the pH effect on the stability of Dd{sup 2+}/HS{supmore » {minus}} complexes. At low pHs (4.0-5.3) the growth mechanism is proposed to be primarily a cluster-molecule process. At this pH range Cd{sup 2+} ions at the CdS particle surface complex with thiolate ions stronger than in the bulk of the solution. The size control of the particles by thiols is proposed to result from a competition of thiolate ions with HS{sup {minus}} ions for cadmium ions at the surface of the growing particles.« less

A Rating System for the Concrete in Navigation Lock Monoliths. Repair, Evaluation, Maintenance, and Rehabilitation Research Program

DTIC Science & Technology

1989-05-01

surface of concrete, shaped like an icicle. A.2.14. Stalagmite : As stalactite , but upward formation. ITU A.2.15. Dusting: The development of a pow...area: Area of concrete suir- 4 face which gives off a hollow sound when struck. A.2.13. Stalactite : A downward pointing for- mation, hanging from the

On the gas-phase formation of the HCO radical: accurate quantum study of the H+CO radiative association

NASA Astrophysics Data System (ADS)

Stoecklin, Thierry; Halvick, Philippe; Yu, Hua-Gen; Nyman, Gunnar; Ellinger, Yves

2018-04-01

We present the first quantum study of the radiative association of H and CO to form the HCO molecule within a time-independent approach. We use a recently published 3D potential energy surface of spectroscopic accuracy and two 3D dipole moment surfaces, which were calculated for this study. We discuss the variation of the radiative association cross-section as a function of both the rotational angular momentum of CO and the total angular momentum and use the uniform J-shifting approach to obtain the global radiative association rate coefficient. The effect of the saddle point separating the HCO molecule from the H+CO reactants and the main features of the radiative association cross-sections are analysed and discussed. The calculated rate coefficient is below 10-23 cm3 molecule-1 s-1 for temperatures lower than 30 K, and increases up to 5 × 10-20 cm3 molecule-1 s-1 at T = 300 K. These results demonstrate that the gas-phase H+CO radiative association cannot be the process at the origin of the sequence leading to the formation of methanol in a cold interstellar medium.

Understanding photocatalytic metallization of preadsorbed ionic gold on titania, ceria, and zirconia.

PubMed

Kydd, Richard; Scott, Jason; Teoh, Wey Yang; Chiang, Ken; Amal, Rose

2010-02-02

A nonaqueous photodeposition procedure for forming Au nanoparticles on semiconducting supports (TiO(2), CeO(2), and ZrO(2)) was investigated. Intrinsic excitation of the support was sufficient to induce Au(0) nucleation, without the need for an organic hole-scavenging species. Photoreduction rates were higher over TiO(2) and ZrO(2) than over CeO(2), likely due to a lower rate of photogenerated electron recombination. Illumination resulted in metallization of the adsorbed Au species and formation of crystalline Au nanoparticles dispersed across the oxide surfaces. On the basis of transmission electron microscopy (TEM) evidence of a strong Au particle-metal oxide interaction, it is proposed that Au deposit formation proceeds via the nucleation of highly dispersed clusters which can diffuse and amalgamate at room temperature to form larger surface-defect-immobilized clusters, with the final particle size being significantly smaller than that achieved by conventional aqueous photodeposition. From this work, it is possible to draw several new fundamental insights, with regards to both the nonaqueous photodeposition process and the general mechanism by which dispersed metallic Au nanoparticles are formed from ionic precursors adsorbed upon metal oxide supports.

The influence of shale depositional fabric on the kinetics of hydrocarbon generation through control of mineral surface contact area on clay catalysis

NASA Astrophysics Data System (ADS)

Rahman, Habibur M.; Kennedy, Martin; Löhr, Stefan; Dewhurst, David N.; Sherwood, Neil; Yang, Shengyu; Horsfield, Brian

2018-01-01

Accurately assessing the temperature and hence the depth and timing of hydrocarbon generation is a critical step in the characterization of a petroleum system. Clay catalysis is a potentially significant modifier of hydrocarbon generation temperature, but experimental studies of clay catalysis show inconsistent or contradictory results. This study tests the hypothesis that source rock fabric itself is an influence on clay mineral catalysis as it controls the extent to which organic matter and clay minerals are physically associated. Two endmember clay-organic fabrics distinguish the source rocks studied: (1) a particulate fabric where organic matter is present as discrete, >5 μm particles and (2) a nanocomposite fabric in which amorphous organic matter is associated with clay mineral surfaces at sub-micron scale. High-resolution electron imaging and bulk geochemical characterisation confirm that samples of the Miocene Monterey Formation (California) are representative of the nanocomposite source rock endmember, whereas samples from the Permian Stuart Range Formation (South Australia) represent the particulate source rock endmember. Kinetic experiments are performed on paired whole rock and kerogen isolate samples from these two formations using open system, non-isothermal pyrolysis at three different heating rates (0.7, 2 and 5 K/min) to determine the effects of the different shale fabrics on hydrocarbon generation kinetics. Extrapolation to a modelled geological heating rate shows a 20 °C reduction in the onset temperature of hydrocarbon generation in Monterey Formation whole rock samples relative to paired kerogen isolates. This result is consistent with the Monterey Formations's nanocomposite fabric where clay catalysis can proceed because reactive clay minerals are intimately associated with organic matter. By contrast, there is no significant difference in the modelled hydrocarbon generation temperature of paired whole rock and kerogen isolates from the Stuart Range Formation. This is consistent with its particulate fabric, where relatively large, discrete organic particles have limited contact with the mineral matrix and the clay minerals are mainly diagenetic and physically segregated within pores. While heating rate may have a control on mineral matrix effects, this result shows that the extent to which organic matter and clay minerals are physically associated could have a significant effect on the timing of hydrocarbon generation, and is a function of the depositional environment and detrital vs diagenetic origin of clay minerals in source rocks.

Pattern formation and self-organization in plasmas interacting with surfaces

NASA Astrophysics Data System (ADS)

Trelles, Juan Pablo

2016-10-01

Pattern formation and self-organization are fascinating phenomena commonly observed in diverse types of biological, chemical and physical systems, including plasmas. These phenomena are often responsible for the occurrence of coherent structures found in nature, such as recirculation cells and spot arrangements; and their understanding and control can have important implications in technology, e.g. from determining the uniformity of plasma surface treatments to electrode erosion rates. This review comprises theoretical, computational and experimental investigations of the formation of spatiotemporal patterns that result from self-organization events due to the interaction of low-temperature plasmas in contact with confining or intervening surfaces, particularly electrodes. The basic definitions associated to pattern formation and self-organization are provided, as well as some of the characteristics of these phenomena within natural and technological contexts, especially those specific to plasmas. Phenomenological aspects of pattern formation include the competition between production/forcing and dissipation/transport processes, as well as nonequilibrium, stability, bifurcation and nonlinear interactions. The mathematical modeling of pattern formation in plasmas has encompassed from theoretical approaches and canonical models, such as reaction-diffusion systems, to drift-diffusion and nonequilibrium fluid flow models. The computational simulation of pattern formation phenomena imposes distinct challenges to numerical methods, such as high sensitivity to numerical approximations and the occurrence of multiple solutions. Representative experimental and numerical investigations of pattern formation and self-organization in diverse types of low-temperature electrical discharges (low and high pressure glow, dielectric barrier and arc discharges, etc) in contact with solid and liquid electrodes are reviewed. Notably, plasmas in contact with liquids, found in diverse emerging applications ranging from nanomaterial synthesis to medicine, show marked sensitivity to pattern formation and a broadened range of controlling parameters. The results related to the characteristics of the patterns, such as their geometric configuration and static or dynamic nature; as well as their controlling factors, including gas composition, driving voltage and current, electrode cooling, and imposed gas flow, are summarized and discussed. The article finalizes with an outlook of the research area, including theoretical, computational, and experimental needs to advance the field.

Lack of bedrock grain size influence on the soil production rate

NASA Astrophysics Data System (ADS)

Gontier, Adrien; Rihs, Sophie; Chabaux, Francois; Lemarchand, Damien; Pelt, Eric; Turpault, Marie-Pierre

2015-10-01

Our study deals with the part played by bedrock grain size on soil formation rates. U- and Th-series disequilibria were measured in two soil profiles developed from two different facies of the same bedrock, i.e., fine and coarse grain size granites, in the geomorphically flat landscape of the experimental Breuil-Chenue forest site, Morvan, France. The U- and Th-series disequilibria of soil layers and the inferred soil formation rate (1-2 mm ky-1) are nearly identical along the two profiles despite differences in bedrock grain size, variable weathering states and a significant redistribution of U and Th from the uppermost soil layers. This indicates that the soil production rate is more affected by regional geomorphology than by the underlying bedrock texture. Such a production rate inferred from residual soil minerals integrated over the age of the soil is consistent with the flat and slowly eroding geomorphic landscape of the study site. It also compares well to the rate inferred from dissolved solutes integrated over the shorter time scale of solute transport from granitic and basaltic watersheds under similar climates. However, it is significantly lower than the denudation or soil formation rates previously reported from either cosmogenic isotope or U-series measurements from similar climates and lithologies. Our results highlight the particularly low soil production rates of flat terrains in temperate climates. Moreover, they provide evidence that the reactions of mineral weathering actually take place in horizons deeper than 1 m, while a chemical steady state of both concentrations and U-series disequilibria is established in the upper most soil layers, i.e., above ∼70 cm depth. In such cases, the use of soil surface horizons for determining weathering rates is precluded and illustrates the need to focus instead on the deepest soil horizons.

SOA formation potential of emissions from soil and leaf litter

DOE PAGES

Faiola, Celia L.; VanderSchelden, Graham S.; Wen, Miao; ...

2013-12-13

Soil and leaf litter are significant global sources of small oxidized volatile organic compounds, VOCs (e.g., methanol and acetaldehyde). They may also be significant sources of larger VOCs that could act as precursors to secondary organic aerosol (SOA) formation. To investigate this, soil and leaf litter samples were collected from the University of Idaho Experimental Forest and transported to the laboratory. There, the VOC emissions were characterized and used to drive SOA formation via dark, ozone-initiated reactions. Monoterpenes dominated the emission profile with emission rates as high as 228 μg-C m –2 h –1. The composition of the SOA producedmore » was similar to biogenic SOA formed from oxidation of ponderosa pine emissions and α-pinene. Measured soil and litter monoterpene emission rates were compared with modeled canopy emissions. Results suggest surface soil and litter monoterpene emissions could range from 12 to 136% of canopy emissions in spring and fall. Furthermore, emissions from leaf litter may potentially extend the biogenic emissions season, contributing to significant organic aerosol formation in the spring and fall when reduced solar radiation and temperatures reduce emissions from living vegetation.« less

Dust-Corrected Star Formation Rates in Galaxies with Outer Rings

NASA Astrophysics Data System (ADS)

Kostiuk, I.; Silchenko, O.

2018-03-01

The star formation rates SFR, as well as the SFR surface densities ΣSFR and absolute stellar magnitudes MAB, are determined and corrected for interinsic dust absorption for 34 disk galaxies of early morphological types with an outer ring structure and ultraviolet emission from the ring. These characteristic are determined for the outer ring structures and for the galaxies as a whole. Data from the space telescopes GALEX (in the NUV and FUV ultraviolet ranges) and WISE (in the W4 22 μm infrared band) are used. The average relative deviation in the corrected SFR and ΣSFR derived from the NUV and FUV bands is only 19.0%, so their averaged values are used for statistical consideration. The relations between the dust-corrected SFR characteristics, UV colours, the galaxy morphological type, absolute magnitude are illustrated.

Ion-Doped Silicate Bioceramic Coating of Ti-Based Implant

PubMed Central

Mohammadi, Hossein; Sepantafar, Mohammadmajid

2016-01-01

Titanium and its alloy are known as important load-bearing biomaterials. The major drawbacks of these metals are fibrous formation and low corrosion rate after implantation. The surface modification of biomedical implants through various methods such as plasma spray improves their osseointegration and clinical lifetime. Different materials have been already used as coatings on biomedical implant, including calcium phosphates and bioglass. However, these materials have been reported to have limited clinical success. The excellent bioactivity of calcium silicate (Ca-Si) has been also regarded as coating material. However, their high degradation rate and low mechanical strength limit their further coating application. Trace element modification of (Ca-Si) bioceramics is a promising method, which improves their mechanical strength and chemical stability. In this review, the potential of trace element-modified silicate coatings on better bone formation of titanium implant is investigated. PMID:26979401

Free Surface Wave Interaction with a Horizontal Cylinder

NASA Astrophysics Data System (ADS)

Oshkai, P.; Rockwell, D.

1999-10-01

Classes of vortex formation from a horizontal cylinder adjacent to an undulating free-surface wave are characterized using high-image-density particle image velocimetry. Instantaneous representations of the velocity field, streamline topology and vorticity patterns yield insight into the origin of unsteady loading of the cylinder. For sufficiently deep submergence of the cylinder, the orbital nature of the wave motion results in multiple sites of vortex development, i.e., onset of vorticity concentrations, along the surface of the cylinder, followed by distinctive types of shedding from the cylinder. All of these concentrations of vorticity then exhibit orbital motion about the cylinder. Their contributions to the instantaneous values of the force coefficients are assessed by calculating moments of vorticity. It is shown that large contributions to the moments and their rate of change with time can occur for those vorticity concentrations having relatively small amplitude orbital trajectories. In a limiting case, collision with the surface of the cylinder can occur. Such vortex-cylinder interactions exhibit abrupt changes in the streamline topology during the wave cycle, including abrupt switching of the location of saddle points in the wave. The effect of nominal depth of submergence of the cylinder is characterized in terms of the time history of patterns of vorticity generated from the cylinder and the free surface. Generally speaking, generic types of vorticity concentrations are formed from the cylinder during the cycle of the wave motion for all values of submergence. The proximity of the free surface, however, can exert a remarkable influence on the initial formation, the eventual strength, and the subsequent motion of concentrations of vorticity. For sufficiently shallow submergence, large-scale vortex formation from the upper surface of the cylinder is inhibited and, in contrast, that from the lower surface of the cylinder is intensified. Moreover, decreasing the depth of submergence retards the orbital migration of previously shed concentrations of vorticity about the cylinder.

The effect of butterfly scales on flight efficiency and leading edge vortex formation

NASA Astrophysics Data System (ADS)

Lang, Amy; Wilroy, Jacob; Wahidi, Redha; Slegers, Nathan; Heilman, Micahel; Cranford, Jacob

2016-11-01

It is hypothesized that the scales on a butterfly wing lead to increased flight efficiency. Recent testing of live butterflies tracked their motion over 246 flights for 11 different specimens. Results show a 37.8 percent mean decrease in flight efficiency and a flapping amplitude reduction of 6.7 percent once the scales were removed. This change could be largely a result of how the leading edge vortex (LEV) interacts with the wing. To simplify this complex flow problem, an experiment was designed to focus on the alteration of 2-D vortex development with a variation in surface patterning. Specifically, the secondary vorticity generated by the LEV interacting at the patterned surface was studied, as well as the subsequent effect on the LEV's growth rate and peak circulation. For this experiment butterfly inspired grooves were created using additive manufacturing and were attached to a flat plate with a chordwise orientation, thus increasing plate surface area. The vortex generated by the grooved plate was then compared to a smooth case as the plate translated vertically through a tow tank at Re = 1500, 3000, and 6000. Using DPIV, the vortex formation was documented and a maximum vortex formation time of 4.22 was found based on the flat plate travel distance and chord length. Results indicate that the patterned surface slows down the growth of the vortex which corroborates the flight test results. Funding from NSF CBET Fluid Dynamcis is gratefully acknowledged.

A composite lithology log while drilling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tannenbaum, E.; Sutcliffe, B.; Franks, A.

A new method for producing a computerized composite lithology log (CLL) while drilling by integrating MWD (measurement while drilling) and surface data is described. At present, lithology logs are produced at the well site by mud loggers. They provide basic description and relative amounts of lithologies. Major difficulties are encountered in relating the cuttings to their original formations due to mixing in the drilling mud while transporting to the surface, sloughing shales, flawed sampling, etc. This results in a poor control on the stratigraphic sequence and on the depth of formation boundaries. A composite log can be produced after drillingmore » this additional inputs such as wireline, petrography, and paleontology. This process is labor intensive and expensive. The CLL integrates three types of data (MWD mechanical, MWD geophysical, and surface cuttings) acquired during drilling, in three time stages: (1) Real Time. MWD drilling mechanical data including the rate of penetration and the downhole torque. This stage would provide bed boundaries and some inferred lithology. This would assist the driller with immediate drilling decisions and determine formation tops for coring, casing point, and correlation. (2) MWD Time. Recomputation of the above by adding MWD geophysical data (gamma-ray, resistivity, neutron-density). This stage would upgrade the lithology inference, and give higher resolution to bed boundaries, (3) Lag Time. Detailed analysis of surface cuttings to confirm the inferred lithologies. This last input results in a high-quality CLL with accurate lithologies and bed boundaries.« less

Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Enrique Iglesia; Akio Ishikawa; Manual Ojeda

2007-09-30

A detailed study of the catalyst composition, preparation and activation protocol of Fe-based catalysts for the Fischer-Tropsch Synthesis (FTS) have been carried out in this project. We have studied the effects of different promoters on the catalytic performance of Fe-based catalysts. Specifically, we have focused on how their sequence of addition dramatically influences the performance of these materials in the Fischer-Tropsch synthesis. The resulting procedures have been optimized to improve further upon the already unprecedented rates and C{sub 5+} selectivities of the Fe-based catalysts that we have developed as part of this project. Selectivity to C{sub 5+} hydrocarbon was closemore » to 90 % (CO{sub 2}-free basis) and CO conversion rate was about 6.7 mol h{sup -1} g-at Fe{sup -1} at 2.14 MPa, 508 K and with substoichiometric synthesis gas; these rates were larger than any reported previously for Fe-based FTS catalysts at these conditions. We also tested the stability of Fe-based catalysts during FTS reaction (10 days); as a result, the high hydrocarbon formation rates were maintained during 10 days, though the gradual deactivation was observed. Our investigation has also focused on the evaluation of Fe-based catalysts with hydrogen-poor synthesis gas streams (H{sub 2}/CO=1). We have observed that the Fe-based catalysts prepared in this project display also a high hydrocarbon synthesis rate with substoichiometric synthesis gas (H{sub 2}/CO=1) stream, which is a less desirable reactant mixture than stoichiometric synthesis gas (H{sub 2}/CO=2). We have improved the catalyst preparation protocols and achieved the highest FTS reaction rates and selectivities so far reported at the low temperatures required for selectivity and stability. Also, we have characterized the catalyst structural change and active phases formed, and their catalytic behavior during the activation process to evaluate their influences on FTS reaction. The efforts of this project led to (i) structural evolution of Fe-Zn oxide promoted with K and Cu, and (ii) evaluation of hydrocarbon and CH{sub 4} formation rates during activation procedures at various temperature and H{sub 2}/CO ratios. On the basis of the obtained results, we suggest that lower reactor temperature can be sufficient to activate catalysts and lead to the high FTS performance. In this project, we have also carried out a detailed kinetic and mechanistic study of the Fischer-Tropsch Synthesis with Fe-based catalysts. We have proposed a reaction mechanism with two CO activation pathways: unassisted and H-assisted. Both routes lead to the formation of the same surface monomers (CH{sub 2}). However, the oxygen removal mechanism is different. In the H-assisted route, oxygen is removed exclusively as water, while oxygen is rejected as carbon dioxide in the unassisted CO dissociation. The validity of the mechanism here proposed has been found to be in agreement with the experimental observation and with theoretical calculations over a Fe(110) surface. Also, we have studied the validity of the mechanism that we propose by analyzing the H{sub 2}/D{sub 2} kinetic isotope effect (r{sub H}/r{sub D}) over a conventional iron-based Fischer-Tropsch catalyst Fe-Zn-K-Cu. We have observed experimentally that the use of D{sub 2} instead of H{sub 2} leads to higher hydrocarbons formation rates (inverse kinetic isotopic effect). On the contrary, primary carbon dioxide formation is not influenced. These experimental observations can be explained by two CO activation pathways. We have also explored the catalytic performance of Co-based catalysts prepared by using inverse micelles techniques. We have studied several methods in order to terminate the silanol groups on SiO{sub 2} support including impregnation, urea homogeneous deposition-precipitation, or zirconium (IV) ethoxide titration. Although hydroxyl groups on the SiO{sub 2} surface are difficult to be stoichiometrically titrated by ZrO{sub 2}, a requirement to prevent the formation of strongly-interacting Co oxide species on SiO{sub 2}, modification of ZrO{sub 2} on SiO{sub 2} surface can improve the Co clusters dispersion leading to a marked increase in the number of accessible Co sites. Inverse micelle method allowed the synthesis of small Co clusters on SiO{sub 2}, but the required surfactant removal steps led to the re-oxidation of Co metal clusters and to the formation of difficult to reduce CoO{sub x} species.« less

Effect of garlic powder on acrylamide formation in a low-moisture model system and bread baking.

PubMed

Li, Jinwang; Zuo, Jie; Qiao, Xuguang; Zhang, Yongju; Xu, Zhixiang

2016-02-01

Acrylamide (AA) is of concern worldwide because of its neurotoxicity, genotoxicity and reproductive/developmental toxicity. Consequently, methods for minimizing AA formation during food processing are vital. In this study, the formation and elimination of AA in an asparagine/glucose low-moisture model system were investigated by response surface methodology. The effect of garlic powder on the kinetics of AA formation/elimination was also evaluated. The AA content reached a maximum level (674.0 nmol) with 1.2 mmol of glucose and 1.2 mmol of asparagine after heating at 200 °C for 6 min. The AA content was greatly reduced with the addition of garlic powder. Compared to without garlic powder, an AA reduction rate of 43% was obtained with addition of garlic powder at a mass fraction of 0.05 g. Garlic powder inhibited AA formation during the generation-predominant kinetic stage and had no effect on the degradation-predominant kinetic stage. The effect of garlic powder on AA formation in bread and bread quality was also investigated. Adding a garlic powder mass fraction of 15 g to 500 g of dough significantly (P < 0.05) reduced the formation of AA (reduction rate of 46%) and had no obvious effect on the sensory qualities of the bread. This study provides a possible method for reducing the AA content in bread and other heat-treated starch-rich foods. © 2015 Society of Chemical Industry.

Physical defect formation in few layer graphene-like carbon on metals: influence of temperature, acidity, and chemical functionalization.

PubMed

Schumacher, Christoph M; Grass, Robert N; Rossier, Michael; Athanassiou, Evagelos K; Stark, Wendelin J

2012-03-06

A systematical examination of the chemical stability of cobalt metal nanomagnets with a graphene-like carbon coating is used to study the otherwise rather elusive formation of nanometer-sized physical defects in few layer graphene as a result of acid treatments. We therefore first exposed the core-shell nanomaterial to well-controlled solutions of altering acidity and temperature. The release of cobalt into these solutions over time offered a simple tool to monitor the progress of particle degradation. The results suggested that the oxidative damage of the graphene-like coatings was the rate-limiting step during particle degradation since only fully intact or entirely emptied carbon shells were found after the experiments. If ionic noble metal species were additionally present in the acidic solutions, the noble metal was found to reduce on the surface of specific, defective particles. The altered electrochemical gradients across the carbon shells were however not found to lead to a faster release of cobalt from the particles. The suggested mechanistic insight was further confirmed by the covalent chemical functionalization of the particle surface with chemically inert aryl species, which leads to an additional thickening of the shells. This leads to reduced cobalt release rates as well as slower noble metal reduction rates depending on the augmentation of the shell thickness.

Kinetic modelling and optimisation of antimicrobial compound production by Candida pyralidae KU736785 for control of Candida guilliermondii.

PubMed

Mewa-Ngongang, Maxwell; du Plessis, Heinrich W; Hutchinson, Ucrecia F; Mekuto, Lukhanyo; Ntwampe, Seteno Ko

2017-06-01

Biological antimicrobial compounds from yeast can be used to address the critical need for safer preservatives in food, fruit and beverages. The inhibition of Candida guilliermondii, a common fermented beverage spoilage organism, was achieved using antimicrobial compounds produced by Candida pyralidae KU736785. The antimicrobial production system was modelled and optimised using response surface methodology, with 22.5 ℃ and pH of 5.0 being the optimum conditions. A new concept for quantifying spoilage organism inhibition was developed. The inhibition activity of the antimicrobial compounds was observed to be at a maximum after 17-23 h of fermentation, with C. pyralidae concentration being between 0.40 and 1.25 × 10 9 CFU ml -1 , while its maximum specific growth rate was 0.31-0.54 h -1 . The maximum inhibitory activity was between 0.19 and 1.08 l contaminated solidified media per millilitre of antimicrobial compound used. Furthermore, the antimicrobial compound formation rate was 0.037-0.086 l VZI ml -1 ACU h -1 , respectively. The response surface methodology analysis showed that the model developed sufficiently described the antimicrobial compound formation rate 1.08 l VZI ml -1 ACU, as 1.17 l VZI ml -1 ACU, predicted under the optimum production conditions.

Sensitivities of NOx transformation and the effects on surface ozone and nitrate

NASA Astrophysics Data System (ADS)

Lei, H.; Wang, J. X. L.

2013-08-01

As precursors for tropospheric ozone and nitrate aerosols, Nitrogen oxides (NOx) in present atmosphere and its transformation in responding to emission and climate perturbations are studied by CAM-Chem model and air quality measurements including National Emission Inventory (NEI), Clean Air Status and Trends Network (CASTNET) and Environmental Protection Agency Air Quality System (EPA AQS). It is found that not only the surface ozone formation but also the nitrate formation is associated with the relative emissions of NOx and volatile organic compounds (VOC). Due to the availability of VOC and associated NOx titration, ozone productions in industrial regions increase in warmer conditions and slightly decrease against NOx emission increase, which is converse to the response in farming region. The decrease or small increase in ozone concentrations over industrial regions result in the responded nitrate increasing rate staying above the increasing rate of NOx emissions. It is indicated that ozone concentration change is more directly affected by changes in climate and precursor emissions, while nitrate concentration change is also affected by local ozone production types and their seasonal transfer. The sensitivity to temperature perturbations shows that warmer climate accelerates the decomposition of odd nitrogen (NOy) during the night. As a result, the transformation rate of NOx to nitrate decreases. Examinations on the historical emission and air quality records on typical pollution areas further confirm the conclusion drawn from modeling experiments.

Photochemical oxidant processes in the presence of dust: An evaluation of the impact of dust on particulate nitrate and ozone formation

NASA Technical Reports Server (NTRS)

Zhang, Yang; Sunwoo, Young; Kotamarthi, Veerabhadra; Carmichael, Gregory R.

1994-01-01

The influence of dust on the tropospheric photochemical oxidant cycle is studied through the use of a detailed coupled aerosol and gas-phase chemistry model. Dust is a significant component of the troposphere throughout Asia and provides a surface for a variety of heterogeneous reactions. Dust is found to be an important surface for particulate nitrate formation. For dust loading and ambient concentrations representative of conditions in East Asia, particulate nitrate levels of 1.5-11.5 micrograms/cubic meter are predicted, consistent with measured levels in this region. Dust is also found to reduce NO(x) levels by up to 50%, HO2 concentrations by 20%-80%, and ozone production rates by up to 25%. The magnitude of the influence of dust is sensitive to mass concentration of the aerosol, relative humidity, and the value of the accommodation coefficient.

Effect of Reclamation on the Skin Layer of Ductile Iron Cast in Furan Molds

NASA Astrophysics Data System (ADS)

Dańko, R.; Holtzer, M.; Górny, M.; Żymankowska-Kumon, S.

2013-11-01

The paper presents the results of investigations of the influence of the quality of molding sand with furan resin hardened by paratoluenesulfonic acid, on the formation of microstructure and surface quality of ductile iron castings. Within the studies different molding sands were used: molding sand prepared with fresh sand and molding sands prepared with reclaimed sands of a different purification degree, determined by the ignition loss value. Various concentrations of sulfur and nitrogen in the sand molds as a function of the ignition loss were shown in the paper. A series of experimental melts of ductile iron in molds made of molding sand characterized by different levels of surface-active elements (e.g., sulfur) and different gas evolution rates were performed. It was shown that there exists a significant effect of the quality of the sand on the formation of the graphite degeneration layer.

Investigation of Al Coated Mg for Biomedical Applications

NASA Astrophysics Data System (ADS)

Elmrabet, Nabila; Roe, Martin; Neate, Nigel; Grant, David M.; Brown, Paul D.

The corrosion resistant properties of 1-2 μm thick Al coatings deposited by radio frequency magnetron sputtering on polished Mg surfaces, within Ar and Ar/H2 environments, have been appraised. The coatings were heat-treated at 300°C for 5 h to induce the formation of bioinert Al2O3, and samples were corroded within phosphate buffered saline solution at 37°C to mimic the biological environment. Both the as-deposited and heat-treated coatings were found to delay the onset of corrosion, but showed higher initial corrosion rates, once established, as compared with polished Mg surfaces. Slightly improved performance of the coatings was achieved through the addition of H2 to the system which acted to inhibit Al-Mg alloying and MgO formation. However, localized accelerated corrosion associated with substrate polishing damage emphasized the need for improved process control and coating uniformity.

Laser annealing of ion implanted CZ silicon for solar cell junction formation

NASA Technical Reports Server (NTRS)

Katzeff, J. S.

1981-01-01

The merits of large spot size pulsed laser annealing of phosphorus implanted, Czochralski grown silicon for function formation of solar cells are evaluated. The feasibility and requirements are also determined to scale-up a laser system to anneal 7.62 cm diameter wafers at a rate of one wafer/second. Results show that laser annealing yields active, defect-free, shallow junction devices. Functional cells with AM 1 conversion efficiencies up to 15.4% for 2 x 2 cm and 2 x 4 cm sizes were attained. For larger cells, 7.62 cm dia., conversion efficiencies ranged up to 14.5%. Experiments showed that texture etched surfaces are not compatible with pulsed laser annealing due to the surface melting caused by the laser energy. When compared with furnace annealed cells, the laser annealed cells generally exhibited conversion efficiencies which were equal to or better than those furnace annealed. In addition, laser annealing has greater throughput potential.

Incorporation of new particle formation and early growth treatments into WRF/Chem: Model improvement, evaluation, and impacts of anthropogenic aerosols over East Asia

NASA Astrophysics Data System (ADS)

Cai, Changjie; Zhang, Xin; Wang, Kai; Zhang, Yang; Wang, Litao; Zhang, Qiang; Duan, Fengkui; He, Kebin; Yu, Shao-Cai

2016-01-01

New particle formation (NPF) provides an important source of aerosol particles and cloud condensation nuclei, which may result in enhanced cloud droplet number concentration (CDNC) and cloud shortwave albedo. In this work, several nucleation parameterizations and one particle early growth parameterization are implemented into the online-coupled Weather Research and Forecasting model coupled with chemistry (WRF/Chem) to improve the model's capability in simulating NPF and early growth of ultrafine particles over East Asia. The default 8-bin over the size range of 39 nm-10 μm used in the Model for Simulating Aerosol Interactions and Chemistry aerosol module is expanded to the 12-bin over 1 nm-10 μm to explicitly track the formation and evolution of new particles. Although model biases remain in simulating H2SO4, condensation sink, growth rate, and formation rate, the evaluation of July 2008 simulation identifies a combination of three nucleation parameterizations (i.e., COMB) that can best represent the atmospheric nucleation processes in terms of both surface nucleation events and the resulting vertical distribution of ultrafine particle concentrations. COMB consists of a power law of Wang et al. (2011) based on activation theory for urban areas in planetary boundary layer (PBL), a power law of Boy et al. (2008) based on activation theory for non-urban areas in PBL, and the ion-mediated nucleation parameterization of YU10 for above PBL. The application and evaluation of the improved model with 12-bin and the COMB nucleation parameterization in East Asia during January, April, July, and October in 2001 show that the model has an overall reasonably good skill in reproducing most observed meteorological variables and surface and column chemical concentrations. Relatively large biases in simulated precipitation and wind speeds are due to inaccurate surface roughness and limitations in model treatments of cloud formation and aerosol-cloud-precipitation interactions. Large biases in the simulated surface concentrations of PM10, NOx, CO, SO2, and VOCs at some sites are due in part to possible underestimations of emissions and in part to inaccurate meteorological predictions. The simulations of 2001 show that anthropogenic aerosols can increase aerosol optical depth by 64.0-228.3%, CDNC by 40.2-76.4%, and cloud optical thickness by 14.3-25.3%; they can reduce surface net shortwave radiation by up to 42.5-52.8 W m-2, 2-m temperature by up to 0.34-0.83 °C, and PBL height by up to 76.8-125.9 m. Such effects are more significant than those previously reported for the U.S. and Europe.

Summertime photochemistry during CAREBeijing-2007: ROx budgets and O3 formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zhen; Wang, Y.; Gu, Dasa

2012-08-28

We analyze summertime photochemistry near the surface in Beijing, China, using a 1-D photochemical model (Regional chEmical and trAnsport Model, REAM-1D) constrained by in situ observations, focusing on the budgets of ROx (OH + HO2 + RO2) radicals and O3 formation. While the modeling analysis focuses on near-surface photochemical budgets, the implications for the budget of O3 in the planetary boundary layer are also discussed. In terms of daytime average, the total ROx primary production rate near the surface in Beijing is 6.6 ppbv per hour (ppbv h{sup 1}, among the highest found in urban atmospheres. The largest primary ROxmore » source in Beijing is photolysis of oxygenated volatile organic compounds (OVOCs), which produces HO2 and RO2 at 2.5 ppbv h{sup 1}1 and 1.7 ppbv h{sup 1}, respectively. Photolysis of excess HONO from an unknown heterogeneous source is the predominant primary OH source at 2.2 ppbv h{sup 1}, much larger than that of O1D+H2O (0.4 ppbv h{sup 1}). The largest ROx sink is via OH + NO2 reaction (1.6 ppbv h{sup 1}), followed by formation of RO2NO2 (1.0 ppbv h{sup 1}) and RONO2 (0.7 ppbv h{sup 1}). Due to the large aerosol surface area, aerosol uptake of HO2 appears to be another important radical sink, although the estimate of its magnitude is highly variable depending on the uptake coefficient value used. The daytime average O3 production and loss rates near the surface are 32 ppbv h{sup 1} and 6.2 ppbv h{sup 1}, respectively. Assuming NO2 to be the source of excess HONO, the NO2 to HONO transformation leads to considerable O3 loss and reduction of its lifetime. Our observation-constrained modeling analysis suggests that oxidation of VOCs (especially aromatics) and heterogeneous reactions (e.g. HONO formation and aerosol uptake HO2) play potentially critical roles in the primary radical budget and O3 formation in Beijing. One important ramification is that O3 production is neither NOx nor VOC limited, but in a transition regime where reduction of either NOx or VOCs could result in reduction of O3 production. The transition regime implies more flexibility in the O3 control strategies than a binary system of either NOx or VOC limited regime. The co-benefit of concurrent reduction of both NOx and VOCs in reducing column O3 production integrated in the planetary boundary layer is significant. Further research on the spatial extent of the transition regime over the polluted eastern China is critically important for controlling regional O3 pollution.« less

Localized Surface Plasmon-Enhanced Electroluminescence in OLEDs by Self-Assembly Ag Nanoparticle Film

NASA Astrophysics Data System (ADS)

He, Xiaoxiao; Wang, Wenjun; Li, Shuhong; Wang, Qingru; Zheng, Wanquan; Shi, Qiang; Liu, Yunlong

2015-12-01

We fabricated Ag nanoparticle (NP) film in organic light emission diodes (OLEDs), and a 23 times increase in electroluminescence (EL) at 518 nm was probed by time-resolved EL measurement. The luminance and relative external quantum efficiency (REQE) were increased by 5.4 and 3.7 times, respectively. There comes a new energy transport way that localized surface plasmons (LSPs) would absorb energy that corresponds to the electron-hole pair before recombination, promoting the formation of electron-hole pair and exciting local surface plasmon resonance (LSPR). The extended lifetime of Alq3 indicates the existence of strong interaction between LSPR and exciton, which decreases the nonradiative decay rate of OLEDs.

Picosecond time scale dynamics of short pulse laser-driven shocks in tin

NASA Astrophysics Data System (ADS)

Grigsby, W.; Bowes, B. T.; Dalton, D. A.; Bernstein, A. C.; Bless, S.; Downer, M. C.; Taleff, E.; Colvin, J.; Ditmire, T.

2009-05-01

The dynamics of high strain rate shock waves driven by a subnanosecond laser pulse in thin tin slabs have been investigated. These shocks, with pressure up to 1 Mbar, have been diagnosed with an 800 nm wavelength ultrafast laser pulse in a pump-probe configuration, which measured reflectivity and two-dimensional interferometry of the expanding rear surface. Time-resolved rear surface expansion data suggest that we reached pressures necessary to shock melt tin upon compression. Reflectivity measurements, however, show an anomalously high drop in the tin reflectivity for free standing foils, which can be attributed to microparticle formation at the back surface when the laser-driven shock releases.

First-order dissolution rate law and the role of surface layers in glass performance assessment

NASA Astrophysics Data System (ADS)

Grambow, B.; Müller, R.

2001-09-01

The first-order dissolution rate law is used for nuclear waste glass performance predictions since 1984. A first discussion of the role of saturation effects was initiated at the MRS conference that year. In paper (1) it was stated that "For glass dissolution A* (the reaction affinity) cannot become zero since saturation only involves the reacting surface while soluble elements still might be extracted from the glass" [B. Grambow, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 15]. Saturation of silica at the surface and condensation of surface silanol groups was considered as being responsible for the slow down of reaction rates by as much as a factor of 1000. Precipitation of Si containing secondary phases such as quartz was invoked as a mechanism for keeping final dissolution affinities higher than zero. Another (2) paper [A.B. Barkatt, P.B. Macedo, B.C. Gibson, C.J. Montrose, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 3] stated that "… under repository conditions the extent of glass dissolution will be moderate due to saturation with respect to certain major elements (in particular, Si, Al and Ca). Consequently, the concentration levels of the more soluble glass constituents in the aqueous medium are expected to fall appreciable below their solubility limit." The formation of dense surface layers was considered responsible for explaining the saturation effect. The mathematical model assumed stop of reaction in closed systems, once solubility limits were achieved. For more than 15 years the question of the correctness of one or the other concept has seldom been posed and has not yet been resolved. The need of repository performance assessment for validated rate laws demands a solution, particularly since the consequences of the two concepts and research requirements for the long-term glass behavior are quite different. In concept (1) the stability of the `equilibrium surface region' is not relevant because, by definition, this region is stable chemically and after a potential mechanical destruction it will be reformed instantaneously. The same is true for radiation damage. The dissolution of silica from the surface in this concept is considered as rate limiting for the release of soluble elements from the glass. After surface stabilization by local solid/solution equilibrium the release of soluble radionuclides continues with lower rates, but this is considered as resulting from parallel leaching mechanism. In fact, the deconvolutions of the overall leach mechanism into individual parallel and sequential rate limiting steps (not necessarily elementary reactions) is fundamental to this concept. In concept (2) surface stability as well as surface morphology are fundamental. A fracture in the protective surface would increase glass corrosion. The protective effect is based on the low diffusivities of radionuclides and other glass constituents in this layer. However, a true relation between layer thickness and rates is seldom observed. Diffusion coefficients are considered to vary with time as well as with the surface area to solution volume S/ V ratio. Sometimes, extremely low diffusivities in extremely thin layers are invoked to explain experimental data. The two concepts are not so different from each other and one is tempted to think of a problem of semantics. In fact, there are two alternative ways by which the protective layer concept can be coupled to the saturation concept: (a) the layer may be formed by solubility effects as proposed in [loc.cit] and/or (b) the layer plays the role of a silica diffusion barrier limiting glass dissolution rates according to the first-order rate law at the interface between the pristine glass and the surface layer. However, the mathematical models based on these conceptual models yield quite different long-term predictions, even though the models may equally well fit a given set of experimental data. The models are also different with respect to the number of interrelated parameters. In the case of a model based on a surface layer slowing down glass network dissolution, the numerical value of the diffusion coefficient of silica, the layer thickness and the saturation concentration of dissolved silica are interrelated. Often, none of the parameters are measured directly. As a consequence this leads to not-sufficiently constrained models with poor predictive capacity. Recent research has indicated that there might be problems with the applicability of the first-order rate law [C. Jegou, thesis, University of Montpellier II, 1998]. Fresh glass or pre-altered glass samples were put in solutions over-saturated with silica. A decrease in reaction rates by as much as a factor of 10 was observed, but the rates remained much higher than predicted from a first-order rate law. It was argued that none of the kinetic models based on the notions of `chemical affinity' and `deviation from an equilibrium' is adapted to describe the kinetics of glass corrosion. In contrast, the formation of a surface gel and condensation of silanol groups are considered responsible for the decrease in reaction rates. The present communication argues against this view. Based on recent results of Monte Carlo calculations [M. Aertsens, Mater. Res. Soc. Symp. Proc. 556 (1999) 409] it is shown that some time of surface restructuration is necessary before saturation effects become fully effective in controlling long-term release of soluble glass constituents. The formation of a gel layer is not opposed to an affinity based kinetic concept, but it is in contrast a manifestation of this concept. It is the belief of the authors that much of the confusion related to the first-order rate law results from the fact that glass network dissolution is not considered as only one of a series of reaction mechanism and that glass network hydration and alkali ion exchange were ignored as parallel leaching mechanism. Our experimental results show that glass network hydration and ion exchange are important in short-term laboratory tests and in certain cases (closed system) also in the long term.

Self-assembly of marine exudate particles and their impact on the CCN properties of nascent marine aerosol

NASA Astrophysics Data System (ADS)

Schill, S.; Zimmermann, K.; Ryder, O. S.; Campbell, N.; Collins, D. B.; Gianneschi, N.; Bertram, T. H.

2013-12-01

Spontaneous self-assembly of marine exudate particles has previously been observed in filtered seawater samples. The chemicophysical properties of these particles may alter the chemical composition and CCN properties of nascent marine aerosol, yet to date simultaneous measurement of seawater exudate particle formation rates and number distributions, with aerosol particle formation rates and CCN activity are lacking. Here, we use a novel Marine Aerosol Reference Tank (MART) system to experimentally mimic a phytoplankton bloom via sequential addition of biological surrogates, including sterol, galactose, lipopolysaccharide, BSA protein, and dipalmitoylphosphatidylcholine. Nascent sea-spray aerosol are generated in the MART system via a continuous plunging waterfall. Exudate particle assembly in the water is monitored via dynamic light scattering (DLS) and transmission electron microscopy (TEM) to obtain both the assembly kinetics of the particles as well as particle number distributions Simultaneous characterization of both particle production rates and super-saturated particle hygroscopicity are also discussed. This study permits analysis of the controlling role of the molecular composition of dissolved organic carbon in setting the production rates of colloidal material in the surface oceans.

Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Glynn, P.D.; Blum, A.E.

1992-01-01

Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated non-stoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25??C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer ~ 60 A?? on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25 A?? (as much as 26 mol% SrCO3 on aragonite and 44 mol% CaCO3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO3)2)) than in solutions spiked with the more soluble component (Ca(HCO3)2), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a non-stoichiometric surface reactive zone significantly decreases dissolution rates. ?? 1992.

Formation Timescales of Amosphous Rims on Lunar Grains Derived from ARTEMIS Observations

NASA Technical Reports Server (NTRS)

Poppe, A. R.; Farrell, W. M.; Halekas, Jasper S.

2018-01-01

The weathering of airless bodies exposed to space is a fundamental process in the formation and evolution of planetary surfaces. At the Moon, space weathering induces a variety of physical, chemical, and optical changes including the formation of nanometer-sized amorphous rims on individual lunar grains. These rims are formed by vapor redeposition from micrometeoroid impacts and ion irradiation-induced amorphization of the crystalline matrix. For ion irradiation-induced rims, however, laboratory experiments of the depth and formation timescales of these rims stand in stark disagreement with observations of lunar soil grains. We use observations by the Acceleration, Reconnection, Turbulence, and Electrodynamics of the Moon's Interaction with the Sun (ARTEMIS) spacecraft in orbit around the Moon to compute the mean ion flux to the lunar surface between 10 eV and 5 MeV and convolve this flux with ion irradiation-induced vacancy production rates as a function of depth calculated using the Stopping Range of Ions in Matter model. By combining these results with laboratory measurements of the critical fluence for charged-particle amorphization in olivine, we can predict the formation timescale of amorphous rims as a function of depth in olivinic grains. This analysis resolves two outstanding issues: (1) the provenance of >100 nm amorphous rims on lunar grains and (2) the nature of the depth-age relationship for amorphous rims on lunar grains.

Formation Timescales of Amorphous Rims on Lunar Grains Derived From ARTEMIS Observations

NASA Astrophysics Data System (ADS)

Poppe, A. R.; Farrell, W. M.; Halekas, J. S.

2018-01-01

The weathering of airless bodies exposed to space is a fundamental process in the formation and evolution of planetary surfaces. At the Moon, space weathering induces a variety of physical, chemical, and optical changes including the formation of nanometer-sized amorphous rims on individual lunar grains. These rims are formed by vapor redeposition from micrometeoroid impacts and ion irradiation-induced amorphization of the crystalline matrix. For ion irradiation-induced rims, however, laboratory experiments of the depth and formation timescales of these rims stand in stark disagreement with observations of lunar soil grains. We use observations by the Acceleration, Reconnection, Turbulence, and Electrodynamics of the Moon's Interaction with the Sun (ARTEMIS) spacecraft in orbit around the Moon to compute the mean ion flux to the lunar surface between 10 eV and 5 MeV and convolve this flux with ion irradiation-induced vacancy production rates as a function of depth calculated using the Stopping Range of Ions in Matter model. By combining these results with laboratory measurements of the critical fluence for charged-particle amorphization in olivine, we can predict the formation timescale of amorphous rims as a function of depth in olivinic grains. This analysis resolves two outstanding issues: (1) the provenance of >100 nm amorphous rims on lunar grains and (2) the nature of the depth-age relationship for amorphous rims on lunar grains.

COSMIC-RAY-MEDIATED FORMATION OF BENZENE ON THE SURFACE OF SATURN'S MOON TITAN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou Li; Zheng Weijun; Kaiser, Ralf I.

2010-08-01

The aromatic benzene molecule (C{sub 6}H{sub 6})-a central building block of polycyclic aromatic hydrocarbon molecules-is of crucial importance for the understanding of the organic chemistry of Saturn's largest moon, Titan. Here, we show via laboratory experiments and electronic structure calculations that the benzene molecule can be formed on Titan's surface in situ via non-equilibrium chemistry by cosmic-ray processing of low-temperature acetylene (C{sub 2}H{sub 2}) ices. The actual yield of benzene depends strongly on the surface coverage. We suggest that the cosmic-ray-mediated chemistry on Titan's surface could be the dominant source of benzene, i.e., a factor of at least two ordersmore » of magnitude higher compared to previously modeled precipitation rates, in those regions of the surface which have a high surface coverage of acetylene.« less

Effect of Functional Groups on Biodegradation and Pre-osteoblastic Cell Response on the Plasma-Polymerized Magnesium Surface

NASA Astrophysics Data System (ADS)

Ko, Yeong-Mu; Lee, Kang; Kim, Byung-Hoon

2013-01-01

Magnesium (Mg) is light, has biocompatibility, and has mechanical properties close to those of natural bone. However, pure Mg severely corrodes in a physiological environment, which may result in fracture prior to substantial tissue healing. In this study, the Mg surface was modified by depositing a thin polymeric film containing COOH, NH2, and OH groups through plasma polymerization of acrylic acid, allyl amine, and allyl alcohol in order to improve its anticorrosion and bioactive properties. The -COOH group had a significant effect on bonelike apatite formation compared with -NH2 and -OH. It was also concluded that a bonelike-apatite formed COOH/Mg surface was more effective for reducing biodegradation rate than the other surfaces. The results of in vitro cell test revealed significantly enhanced cell proliferation and differentiation on the COOH/Mg and NH2/Mg surfaces compared with other surfaces.

Structural analysis of star-forming blue early-type galaxies. Merger-driven star formation in elliptical galaxies

NASA Astrophysics Data System (ADS)

George, Koshy

2017-02-01

Context. Star-forming blue early-type galaxies at low redshift can give insight to the stellar mass growth of L⋆ elliptical galaxies in the local Universe. Aims: We wish to understand the reason for star formation in these otherwise passively evolving red and dead stellar systems. The fuel for star formation can be acquired through recent accretion events such as mergers or flyby. The signatures of such events should be evident from a structural analysis of the galaxy image. Methods: We carried out structural analysis on SDSS r-band imaging data of 55 star-forming blue elliptical galaxies, derived the structural parameters, analysed the residuals from best-fit to surface brightness distribution, and constructed the galaxy scaling relations. Results: We found that star-forming blue early-type galaxies are bulge-dominated systems with axial ratio >0.5 and surface brightness profiles fitted by Sérsic profiles with index (n) mostly >2. Twenty-three galaxies are found to have n< 2; these could be hosting a disc component. The residual images of the 32 galaxy surface brightness profile fits show structural features indicative of recent interactions. The star-forming blue elliptical galaxies follow the Kormendy relation and show the characteristics of normal elliptical galaxies as far as structural analysis is concerned. There is a general trend for high-luminosity galaxies to display interaction signatures and high star formation rates. Conclusions: The star-forming population of blue early-type galaxies at low redshifts could be normal ellipticals that might have undergone a recent gas-rich minor merger event. The star formation in these galaxies will shut down once the recently acquired fuel is consumed, following which the galaxy will evolve to a normal early-type galaxy.